JPH0549343B2 - - 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℃), 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 hydrogenation treatment, 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,
Since this operation is temporary, it is often not automated and requires a different and more complicated operation than usual, which places an extremely heavy burden on the operator. 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.

In this method, a catalyst having the general formula R-S(n)-R' (n is an integer of 3 to 20, R,
R' contains a polysulfide represented by a hydrogen atom or an organic group having 1 to 150 carbon atoms per molecule), and in the absence of hydrogen gas, at 65 to 275℃, 0.5 to 70℃.
In this method, the catalyst is heat-treated under the pressure of bar (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.

The catalyst used for pre-sulfurization 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 of drying and then heat treatment to convert the active metal into an oxide state, or a method of mixing alumina hydrate and an aqueous solution of a water-soluble compound of the active metal and forming it.
It is produced by drying and firing to support 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 is simpler than the above conventional method,
To provide a catalyst for hydrotreating hydrocarbons, which can be produced at low cost, can be used for hydrotreating without requiring preliminary sulfurization treatment, and can be directly subjected to hydrotreating without heat treatment, and a method for producing the same. That is the issue.

[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 water-soluble compound of a Group 6 metal or a Group 8 metal of the periodic table, and the general formula HS-(CH ₂ ) _o -COOR (In the formula,
n is an integer of 1 to 3, and R is an alkyl group consisting of 1 to 10 carbon atoms. is present at the bonding surface of each particle of one or both of boehmite-type alumina powder, γ-alumina powder, and a mixed unfired molded product thereof.

2. One or both of the boehmite-type alumina powder and the γ-alumina powder contains at least one water-soluble compound of a Group 6 metal or a Group 8 metal of the periodic table, and the general formula HS-(CH ₂ ) _o -COOR. (In the formula,
mercaptocarboxylic acid ester (n is an integer of 1 to 3, R is an alkyl group consisting of 1 to 10 carbon atoms) is kneaded, molded, and then dried. A method for producing a catalyst for hydrotreating.

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. The general formula HS−(CH ₂ ) _o −COOR is applied to the dried molded product.
After impregnating with a solution of mercaptocarboxylic acid ester represented by (where n is an integer of 1 to 3 and R is an alkyl group consisting of 1 to 10 carbon atoms),
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 has the general formula HS−(CH ₂ ) _o −
COOR (where n is an integer of 1 to 3, R is 1 to 10
A solution of a mercaptocarboxylic acid ester represented by an alkyl group consisting of carbon atoms) 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 hydrogenation of hydrocarbons, which comprises impregnating with an aqueous solution of at least one of the above 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 compound having the general formula HS-(CH ₂ ) _o −
COOR (where n is an integer of 1 to 3, R is 1 to 10
a mercaptocarboxylic acid ester represented by an alkyl group consisting of carbon atoms), and at least one or all of the water-soluble compound, phosphoric acid, and the mercaptocarboxylic acid ester are boehmite-type alumina powder, γ-alumina powder, A catalyst for hydrogenation treatment of hydrocarbons, which comprises a mixed unfired molded product of these particles interposed at the joint surface of each particle of one or both of the powders.

6 One or both of boehmite-type alumina powder and γ-alumina powder, a Group 6 metal of the periodic table,
At least one water-soluble compound of Group 8 metal, phosphoric acid, and the general formula HS−(CH ₂ ) _o −
COOR (where n is an integer of 1 to 3, R is 1 to 10
A method for producing a catalyst for hydrogenation of hydrocarbons, which comprises kneading a solution with a mercaptocarboxylic acid ester represented by an alkyl group consisting of 5 carbon atoms, shaping the mixture, and then drying the mixture.

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 and molded, and once dried, the dried molded product is given the general formula HS-
(CH ₂ ) _o -COOR (where n is an integer of 1 to 3, R
1. A method for producing a catalyst for hydrogenation of hydrocarbons, which comprises impregnating with a solution of a mercaptocarboxylic acid ester (alkyl group having 1 to 10 carbon atoms) and drying 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 compound having the general formula HS-
(CH ₂ ) _o -COOR (where n is an integer of 1 to 3, R
1. A method for producing a catalyst for hydrogenation of hydrocarbons, which comprises impregnating with a solution of a mercaptocarboxylic acid ester (alkyl group having 1 to 10 carbon atoms) and drying again.

9 One or both of boehmite type alumina powder and γ-alumina powder, a Group 6 metal of the periodic table,
At least one water-soluble compound of Group 8 metal and a compound having the general formula HS-( _CH2 ) _o -COOR (in the formula,
A solution with a mercaptocarboxylic acid ester (n is an integer of 1 to 3, R is an alkyl group consisting of 1 to 10 carbon atoms) is kneaded, molded and once dried, and the dried molded product is coated with phosphoric acid. 1. A method for producing a catalyst for hydrogenation of hydrocarbons, which comprises impregnating with an aqueous solution of and then drying again.

10 One or both of boehmite-type alumina powder and γ-alumina powder is combined with phosphoric acid according to the general formula
A solution with a mercaptocarboxylic acid ester represented by HS-(CH ₂ ) _o -COOR (where n is an integer of 1 to 3 and R is an alkyl group consisting of 1 to 10 carbon atoms) is kneaded and shaped. A hydrocarbon, characterized in that 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, and then dried again. A method for producing a catalyst for hydrogen treatment.

11 One or both of boehmite-type alumina powder and γ-alumina powder is combined with the general formula HS−(CH ₂ ) _o
-COOR (where n is an integer of 1 to 3, R is 1 to
A solution of a mercaptocarboxylic acid ester represented by an alkyl group consisting of 10 carbon atoms is kneaded, molded and once dried, and the dried molded product is mixed with water-soluble metals of Group 6 and Group 8 of the Periodic Table. A method for producing a catalyst for hydrogenation of hydrocarbons, which comprises impregnating with a solution of at least one of the compounds and phosphoric acid and then drying again.

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. At least one of the water-soluble compounds and the general formula HS−
(CH ₂ ) _o -COOR (where n is an integer of 1 to 3, R
1. A method for producing a catalyst for hydrogenation of hydrocarbons, which comprises impregnating with a solution of a mercaptocarboxylic acid ester (alkyl group having 1 to 10 carbon atoms) and drying again.

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 , FeO ₂ O ₃ , MgO, and CaO. When boehmite is heated, it dehydrates and becomes γ-alumina → δ-alumina → θ-
It changes in the order of alumina and turns into α-alumina (corundum) at temperatures above 1000℃. 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.

General formula HS-(CH ₂ ) _o -COOR (where n is 1
The amount of mercaptocarboxylic acid ester represented by an integer of ~3, R is an alkyl group consisting of 1 to 10 carbon atoms is determined by the amount of mercaptocarboxylic acid ester represented by an integer of 3 to 3, R being an alkyl group consisting of 1 to 10 carbon atoms. The amount of sulfur is preferably 1 to 3 times the amount required to form a sulfide form (for example, MOS ₂ , WS ₂ , CoS, NiS). 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 mercaptocarboxylic acid ester, the moiety that acts as a sulfurizing agent for active metals is the -SH group in the molecule of the mercaptocarboxylic acid ester, so when the number of carbon atoms in the hydrocarbon group increases, it acts as a sulfurizing agent for the active metal. Since the number of active parts 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, methyl mercaptoacetate (HSCH ₂ COOCH ₃ ), ethyl 2-mercaptoacetate (HSCH ₂ COOC ₂ H ₅ ), 2-ethylhexyl mercaptoacetate (HSCH ₂ COOC ₈ H ₁₇ ), methyl 3-mercaptopropionate (HSCH ₂ CH ₂ COOCH ₃ ),
It is preferable to use a mercaptocarboxylic acid ester having a small number of carbon atoms such as 15 carbon atoms at most.

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 directly packed into a reaction tower in a dry state and subjected to the hydrogenation treatment of hydrocarbon oil without pre-sulfurization treatment. 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 -
A mercaptocarboxylic acid ester having an SH group is
Since the active metal is supported on the carrier material along with the water-soluble compound, the active metal is converted to sulfide during the temperature rise to the hydrodesulfurization reaction temperature of hydrocarbon oil, and the active metal is converted to sulfide without any special pre-sulfurization treatment. , it can be directly subjected to the hydrodeflow reaction of hydrocarbon oil. Furthermore, the catalyst of the present invention exhibits excellent activity.
The reason for this is not clear, but 2-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. This is thought to be due to the

〔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°C) 0.844 Sulfur (weight%) 1.13 Nitrogen (weight ppm) 162 Distillation properties (initial boiling point, °C) 203.3 〃 (50% by volume, °C) 299.0 〃 (end point, °C) 391.8 Reaction The reaction was carried out using a flow reactor under the following reaction conditions.

Catalyst amount 3 ml Raw oil liquid space velocity 2.0 hr ^-1 Reaction pressure (hydrogen pressure) 30 Kg/cm ² Reaction temperature 330°C Hydrogen/oil ratio 300 Nl/l Oil passage time 8 hr The treated oil was sampled every 2 hours and the sulfur content was measured to determine the desulfurization rate. 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, 102.7 g of methyl mercaptoacetate was added to prepare a solution of metal mercaptide.

272 g of spray-dried boehmite-type alumina powder (Al ₂ O ₃ 73.5% by weight) with this metal mercaptide solution
was 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 was 15% by weight of molybdenum in terms of _MoO3 , 4% by weight of cobalt in terms of CoO, and the amount of methyl mercaptoacetate used was 1.5 times the theoretical amount. .

The desulfurization rate of this catalyst 1 was 82.7%.

Example 2 37.0g of tungsten trioxide, cobalt carbonate (Co
71.7 g of methyl mercaptoacetate was added to 300 ml of a solution prepared from 15.8 g (content 49.1% by weight), ammonia gas, and water to obtain 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 methyl mercaptoacetate 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 82.1%.

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. 272g of this solution and the boehmite-type alumina powder used in Example 1
were put into 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, the dried product was impregnated with 120 ml of an ethanol solution containing 116.3 g of methyl 3-mercaptopropionate, and then heated at 100°C.
After drying for 16 hours, catalyst 3 was obtained.

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

The metal content of catalyst 3 is 15% by weight of molybdenum in terms of MoO ₃ and 4% by weight of cobalt in terms of CoO _. The amount was 1.5 times the theoretical amount of sulfur required to form CoS.

The desulfurization rate of this catalyst 3 was 81.0%.

Example 4 272 g of the boehmite-type alumina powder used in Example 1 and 300 ml of an aqueous solution containing 116.3 g of ethyl 2-mercaptoacetate were placed in a kneader, kneaded to obtain a mixture, and 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.
Catalyst 4 was obtained by impregnating the entire amount with 150 ml of a solution prepared from 15.8 g of cobalt carbonate (Co content 49.1% by weight), ammonia gas and water, and drying at 100° C. for 16 hours twice.

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 ethyl ₂ -mercaptoacetate used is as follows: It was 1.5 times the theoretical amount of sulfur required to achieve this.

The desulfurization rate of this catalyst 4 was 81.5%.

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
106.8 g of methyl mercaptoacetate 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 solution of metal methylcaptide and dehydrated boehmite-type alumina gel (29.7% by weight Al ₂ O ₃ )
A mixture of alumina and metal mercaptide was obtained by putting 673 g into a heating kneader and performing heating kneading at 95° C. to evaporate excess water, and then molding.

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 methyl mercaptoacetate used was 1.5 times the theoretical amount of sulfur required to convert Mo and Co to MoS ₂ and CoS, respectively.

The desulfurization rate of this catalyst 5 was 82.2%.

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
106.8 g of methyl mercaptoacetate 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 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 methyl mercaptoacetate used was 1.5 times the theoretical amount of sulfur required to convert Mo and Co to MoS ₂ and CoS, respectively.

The desulfurization rate of this catalyst was 83.0%.

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
120.9 g of methyl 3-mercaptopropionate was added to 300 ml of a solution prepared from the above and water 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 methyl 3-mercaptopropionate used is
The amount was 1.5 times the theoretical amount of sulfur required to turn Mo and Co into MoS ₂ and CoS, respectively.

The desulfurization rate of this catalyst 7 was 82.0%.

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
120.9 g of methyl 3-mercaptopropionate was added to 300 ml of a solution prepared from the above and water 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 methyl 3-mercaptopropionate used is
The amount was 1.5 times the theoretical amount of sulfur required to turn Mo and Co into MoS ₂ and CoS, respectively.

The desulfurization rate of this catalyst 8 was 81.1%.

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
120.9 g of methyl 3-mercaptopropionate 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 the catalyst is 15% by weight of molybdenum converted to _MoO3 , 4% by weight of cobalt converted to CoO, and 3% by weight of phosphorus converted to _{P2O5 .}
-The amount of methyl mercaptopropionate used is:
The amount was 1.5 times the theoretical amount of sulfur required to turn Mo and Co into MoS ₂ and CoS, respectively.

The desulfurization rate of this catalyst 9 was 81.5%.

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
151.6 g of methyl mercaptoacetate was added to 300 ml of a solution prepared from 300 ml of water and 151.6 g of methyl mercaptoacetate 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 20% by weight of molybdenum converted to MoO ₃ and 4% by weight of nickel converted to NiO.
% by weight, phosphorus is 6.5% by weight converted to P ₂ O ₅ ,
The amount of methyl mercaptoacetate 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 79.0%.

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, the dried product was impregnated with 115 ml of an ethanol solution containing 106.8 g of methyl mercaptoacetate, and then
After drying at ℃ for 16 hours, catalyst 11 was obtained.

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

The metal content of catalyst 11 is 15% by weight of molybdenum converted to MoO ₃ and 4% of cobalt converted to CoO.
% by weight, phosphorus is 3% by weight converted to P ₂ O ₅ ,
The amount of methyl mercaptoacetate used was 1.5 times the theoretical amount of sulfur required to convert Mo and Co to MoS ₂ and CoS, respectively.

The desulfurization rate of this catalyst 11 was 81.8%.

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, it was 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 with 120 ml of ethanol solution containing 120.9 g of methyl 3-mercaptopropionate, it was heated at 100℃ for 16 hours.
After drying for hours, catalyst 12 was obtained.

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

The metal content of catalyst 12 is 15% by weight of molybdenum converted to MoO ₃ and 4% of cobalt converted to CoO.
% by weight, phosphorus is 3% by weight converted to P ₂ O ₅ ,
The amount of methyl 3-mercaptopropionate used is
The amount was 1.5 times the theoretical amount of sulfur required to turn Mo and Co into MoS ₂ and CoS, respectively.

The desulfurization rate of this catalyst 12 was 81.2%.

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, 120.9 g of methyl 2-mercaptoacetate 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 a total amount of 50 ml, it was dried at 100°C for 16 hours to obtain catalyst 13.

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

The metal content of catalyst 13 is molybdenum MoO ₃
Cobalt is 4% by weight in terms of _CoO , phosphorus is 3% by weight in terms of _P2O5 , and the amount of methyl 2-mercaptoacetate used is Mo,
The amount was 1.5 times the theoretical amount of sulfur required for Co to become MoS ₂ and CoS, respectively.

The desulfurization rate of this catalyst 13 was 81.8%.

Example 14 272 g of the boehmite-type alumina powder used in Example 1, 205.5 g of 2-ethylhexyl mercaptoacetate, 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.

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 the catalyst 14 is molybdenum.
The amount of mercaptoacetate _{-2-ethylhexyl used was 15% by weight in terms of MoO 3} , cobalt 4% by weight in terms of CoO, phosphorus 3% by weight in terms of P ₂ O ₅ , and the amount of mercaptoacetate-2-ethylhexyl used was Mo, The amount was 1.5 times the theoretical amount of sulfur required for Co to become MoS ₂ and CoS, respectively.

The desulfurization rate of this catalyst 14 was 81.2%.

Example 15 272 g of the boehmite-type alumina powder used in Example 1 and 300 ml of an aqueous solution containing 106.8 g of methyl mercaptoacetate 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 of phosphoric acid, 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 molybdenum MoO ₃
Cobalt is 4% by weight in terms of CoO, phosphorus is 3% by weight in terms of P ₂ O ₅ , and the amount of methyl mercaptoacetate used is Mo and Co are MoS ₂ and Co, respectively. The amount was 1.5 times the theoretical amount of sulfur required to form CoS.

The desulfurization rate of this catalyst 15 was 81.9%.

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 put into 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 solution of metal mercaptide obtained by adding 120.9 g of methyl 3-mercaptopropionate to a solution prepared from 16.4 g of ammonia gas and water, the catalyst 16 was dried at 100°C for 16 hours.
I got it.

The breaking strength of catalyst 16 was 1.5 kg/mm or more.

The metal content of catalyst 16 is molybdenum MoO ₃
Cobalt is 4% by weight in terms of CoO, phosphorus is 3% by weight in terms of _P2O5 , and the amounts of methyl 3-mercaptopropionate used are 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 16 was 80.9%.

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 presulfurization treatment.

Sulfurized oil 3% by weight n-butyl mercaptan / Kuwait atmospheric gas oil Catalyst amount 3ml Raw oil liquid space velocity 2.0hr ^-1 Reaction pressure (hydrogen pressure) 30Kg/cm ² Reaction temperature 316℃ Hydrogen/oil ratio 300N / Oil passage time 8hr The activity of this presulfurized catalyst was evaluated in the same manner as in the example, and the deflow 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.
A catalyst containing 15% by weight of MoO ₃ , 4% by weight of CoO, and 3% by weight of P ₂ O ₅ 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 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.
However, the catalyst of the present invention and the catalyst produced by the method for producing the same do not require presulfidation and can be used as is for hydrotreating without calcination, making them more economical than conventional methods. Can provide a 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 water-soluble compound of the surface metal and the general formula HS-( _CH2 ) _o -COOR (wherein, n is an integer of 1 to 3, and R is an alkyl group consisting of 1 to 10 carbon atoms). and a mercaptocarboxylic acid ester represented by A catalyst for hydrotreating hydrocarbons comprising a mixed unfired molded product of these. 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.
at least one water-soluble compound of group metal and the general formula HS-( _CH2 ) _o -COOR (wherein, n is an integer of 1 to 3, and R is an alkyl group consisting of 1 to 10 carbon atoms). A method for producing a catalyst for hydrogenation of hydrocarbons, which comprises kneading a solution with a mercaptocarboxylic acid ester represented by the formula, shaping the mixture, and then drying the mixture. 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, molded and once dried, and the dried molded product has the general formula HS-(CH ₂ ) _o -COOR (in the formula, n
is an integer of 1 to 3, and R is an alkyl group consisting of 1 to 10 carbon atoms. Catalyst manufacturing method. 4 One or both of boehmite-type alumina powder and γ-alumina powder has the general formula HS−(CH ₂ ) _o −
A solution of a mercaptocarboxylic acid ester represented by COOR (in the formula, n is an integer of 1 to 3, R is an alkyl group consisting of 1 to 10 carbon atoms) is kneaded and molded, and once dried, 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.
at least one water-soluble compound of group metal, phosphoric acid, and the general formula HS−(CH ₂ ) _o −COOR
(In the formula, n is an integer of 1 to 3, R is an alkyl group consisting of 1 to 10 carbon atoms). 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 acid esters are present on 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.
at least one water-soluble compound of group metal, phosphoric acid, and the general formula HS−(CH ₂ ) _o −COOR
(In the formula, n is an integer of 1 to 3, R is an alkyl group consisting of 1 to 10 carbon atoms) A solution with a mercaptocarboxylic acid ester is kneaded, molded, 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 has the general formula HS-(CH ₂ ) _o-
After impregnating with a solution of mercaptocarboxylic acid ester represented by COOR (where n is an integer of 1 to 3 and R is an alkyl group consisting of 1 to 10 carbon atoms),
A method for producing a catalyst for hydrotreating hydrocarbons, which comprises 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 type of water-soluble compound of group metals is kneaded, shaped and once dried, and the dried shaped product is mixed with phosphoric acid and the general formula HS-( _CH2 ) _o -COOR.
(In the formula, n is an integer of 1 to 3, R is an alkyl group consisting of 1 to 10 carbon atoms) Carbonization characterized by impregnation with a solution of mercaptocarboxylic acid ester and then drying again A method for producing a catalyst for hydrogen hydrotreating. 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.
at least one water-soluble compound of group metal and the general formula HS-( _CH2 ) _o -COOR (wherein, n is an integer of 1 to 3, and R is an alkyl group consisting of 1 to 10 carbon atoms). For hydrogenation treatment of hydrocarbons, which is characterized by kneading a solution with a mercaptocarboxylic acid ester represented by the formula, forming it, drying it once, impregnating the dried formed product with an aqueous solution of phosphoric acid, and drying it again. Catalyst manufacturing method. 10 One or both of boehmite type alumina powder and γ-alumina powder, phosphoric acid and general formula HS
-(CH ₂ ) _o -COOR (where n is an integer of 1 to 3, R
(alkyl group consisting of 1 to 10 carbon atoms) 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. A method for producing a catalyst for hydrotreating hydrocarbons, which comprises impregnating the catalyst with an aqueous solution of at least one of water-soluble metal compounds and then drying the catalyst again. 11 One or both of boehmite type alumina powder and γ-alumina powder has the general formula HS-(CH ₂ ) _o -
A solution of mercaptocarboxylic acid ester represented by COOR (in the formula, n is an integer of 1 to 3 and R is an alkyl group consisting of 1 to 10 carbon atoms) is kneaded, shaped and once dried, and the dried Hydrocarbon hydrogenation, characterized by impregnating a molded article 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 drying it again. Method for producing treatment catalyst. 12 One or both of the boehmite-type alumina powder and γ-alumina powder is 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. at least one of the compounds having the general formula HS−(CH ₂ ) _o −
It is characterized by being impregnated with a solution of a mercaptocarboxylic acid ester represented by COOR (where n is an integer of 1 to 3 and R is an alkyl group consisting of 1 to 10 carbon atoms) and then dried again. A method for producing a catalyst for hydrotreating hydrocarbons.