JP2936753B2 - Method for producing hydrotreating catalyst - Google Patents

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a method for producing a hydrotreating catalyst for a hydrocarbon oil.

[0002]

BACKGROUND ART hydrocarbon oils hydrogenation, desulfurization, denitrogenation, alumina as a catalyst to be used, such as the hydrogenation process for decomposition, titania, silica, periodic table Group 6 to the porous catalyst support such as activated carbon A catalyst supporting a metal and a Group VIII metal as active metals is used. Generally as the Group 6 metals Mo and W are used, although Ni or Co is used as the Group VIII metals, these active metals activity is low are supported by the oxide state on the catalyst support. For this reason, an appropriate pre-sulfurization treatment is performed to use the catalyst as a sulfide.

[0003] In the hydrotreating catalyst, active sites of the catalyst are formed on the surface of the active metal sulfide. Therefore,
It is known that the number of active sites increases as the surface area of the metal sulfide increases, resulting in a highly active catalyst. In order to increase the surface area of the sulfide, attempts have been made to make the metal sulfide finer and highly disperse, and various methods have been disclosed. For example, JP-A-59-102442
JP-A-59-69147 and JP-A-59-69147 disclose a method of impregnating a catalyst carrier such as alumina with a mixed solution of a carboxylic acid such as citric acid or malic acid and an active metal, followed by drying and firing. These production methods form a complex ion between the active metal and the carboxylic acid, and are intended to prevent the aggregation of the active metal by supporting the complex ion.Both methods involve impregnation at the final stage. Is not necessarily obtained because of roasting.

[0004] EP 0 810 35 A2 uses a nitrogen-containing organic compound such as nitrilotriacetic acid, ethylenediaminetetraacetic acid or diethylenetriamine as a complexing agent, and uses a mixed solution of these complexing agent and active metal as an alumina. It discloses a method in which a carrier or a silica carrier is impregnated, dried at 200 ° C. or lower, and is not roasted. Although the activity of the catalyst produced by this method shows a higher value than the conventional product, it enables the sulfur content in light oil to be reduced to 0.05% or less due to the tightening of exhaust gas regulations recently reported. It is not. In addition, since this method uses a nitrogen-containing organic compound as a complexing agent, it has been pointed out that there is a strong possibility that a harmful gas such as hydrogen cyanide is generated during the pre-sulfidation treatment.

[0005]

SUMMARY OF THE INVENTION It is an object of the present invention to reduce the sulfur content of light oil to 0.05% or less, and there is no danger of generating harmful gases such as hydrogen cyanide during pre-sulfidation. An object of the present invention is to provide a method for producing a highly active hydrotreating catalyst.

[0006]

The method of the present invention to solve the above problems SUMMARY OF THE INVENTION may, either one of an inorganic oxide or a hydrate thereof, or the periodic table in the catalyst carrier material mainly composed of both group 6 metal and the group 8 metal, 0.3, relative to the total molar amount of the one or both of the phosphoric acid or carboxylic acid, group 6 of the periodic table and a group 8 metal adding an aqueous solution containing a quantity of polyalcohol to be 5.0 times the molar amount, and kneaded, molded, and then are those dried at 200 ° C. or less, preferably group 6 metal of the periodic table in the catalyst support One or both of molybdenum and tungsten are used as the metal, and one or both of nickel and cobalt are used as the Group VIII metal.

In the present invention, at least one of citric acid, tartaric acid, glycolic acid, malonic acid, gluconic acid, glyceric acid, malic acid, acetic acid, succinic acid, and glyoxal is used as the carboxylic acid. Preferred examples of the polyalcohol include ethylene glycol, diethylene glycol, triethylene glycol, glycerin, 2,2-diethyl-1,3-propylene glycol, butanediol, and an average molecular weight of 400.
It is preferable to use at least one of the following polyethylene alcohols.

[0008]

In the present invention, oxides and / or hydrates of alumina, silica, titania, zirconia and the like can be used as a carrier for the medium. The amount of the active metal supported is a value generally used as a hydrotreating catalyst, that is, the Group 6 metal is 5 to 30% as an oxide, and the Group 8 metal is 1 to 8% as an oxide. It is preferable that

In carrying these metals, for example, molybdenum oxide and cobalt carbonate are suspended in water and then dissolved and impregnated by boiling. However, such an impregnating water solution often contains unreacted water. Dissolved material easily remains. Such undissolved substances can be completely dissolved by adding an acid to the aqueous solution. Therefore, the amount of the acid used depends on the acidity of the acid, and a smaller amount is required for a strongly acidic substance.

For the above reasons, the acid used may be a mineral acid such as nitric acid, sulfuric acid, hydrochloric acid or the like. However, since these mineral acids generate corrosive gas upon activation of the catalyst, the purpose of the present invention is Not fit.

In the present invention, the use of carboxylic acids such as phosphoric acid, citric acid, tartaric acid, glycolic acid, malonic acid, gluconic acid, glyceric acid, malic acid, acetic acid, succinic acid and glyoxal achieves the above object. This is because that.

In the present invention, when phosphoric acid is used, P ₂ O ₅
It is preferable to adjust the addition amount so that it becomes about 1 to 8% in the catalyst. When a carboxylic acid is used, if the addition amount is small, the active metal may not be completely dissolved. During activation, the excess carboxylic acid is not decomposed but is discharged as it is, which may lead to corrosion of the device. Therefore, the amount of the carboxylic acid to be added is preferably 0.05 to 1.0 times the total number of moles of the active metal in moles.

In the hydrotreating catalyst of the present invention, it is considered that the active metal forms a complex compound with the polyalcohol and is stably supported on the catalyst carrier. It is not clear why the selection of polyalcohol as a complexing agent results in a higher activity than that using the nitrogen-containing organic compound as a complexing agent.
The present inventor presumes that basic compounds such as ammonia and amines generated by decomposition of the nitrogen-containing organic compound at the time of preliminary sulfurization are not completely removed from the catalyst, and the active sites are poisoned by these basic compounds. Further, since the value of the active metal surface area of the catalyst produced by the method of the present invention is extremely large, it is presumed that the stability and decomposition behavior of the complex compound formed prevent aggregation of the active metal during presulfurization. doing.

The amount of the polyalcohol to be added in a molar number of 0.3 to 5.0 times the total molar amount of the active metal is 0.3 to 5.0 times.
If it is less than 2 times, the active metal cannot be sufficiently complexed. If it exceeds 5.0 times, the complexing agent will not be completely decomposed and removed at the time of pre-sulfurization, and carbon will precipitate on the active metal and interfere with sulfidation, reducing the activity. It is because it will be done.

Further, the drying temperature of the catalyst of the present invention is set to 200 ° C.
The following is to prevent the decomposition and volatilization of polyalcohol as a complexing agent.

[0016]

Embodiments will be described below with reference to embodiments.

Example 1 1000 g of alumina hydrate
(Moisture content: 60%) molybdenum trioxide (124 g), cobalt carbonate (39.4 g), 85% phosphoric acid (27 g), citric acid (3)
6.6 g, 600 ml of an active metal aqueous solution prepared from 308.3 g of diethylene glycol and water were added, and
The mixture was heated and kneaded at, and a cylindrical molded product having a diameter of 1.6 mm was obtained using an extruder.
It dried at 16 degreeC for 16 hours, and obtained catalyst A. MoO _{3 of} catalyst A
Was 22%, the content of CoO was 4%, and the content of P ₂ O ₅ was 3%. The amount of diethylene glycol added was 2.5 times the total molar amount of Mo and Co, and the amount of citric acid was 0.15 times the total molar amount of Mo and Co. Next, a hydrodesulfurization reaction test was carried out using Catalyst A under the following conditions using quat normal pressure gas oil having the following properties and a flow reactor.

(Properties of Kuwait atmospheric gas oil) Specific gravity (15/4 ° C) 0.844 Sulfur (%) 1.55 Distillation properties (initial boiling point ° C) 231 (50 Vol% ° C) 313 (End point ° C) 390

(Test conditions) Catalyst amount (ml) 15 Raw material oil liquid space velocity (Hr ^-1 ) 2 Reaction hydrogen pressure (Kg / cm ² G) 30 Reaction temperature (° C) 330 Hydrogen / oil flow rate ratio (Nl / l) ) 300 Oiling time (hr) 88

The resulting hydrodesulfurization activity and be represented by a relative value of the reaction rate constant, the rate constant was calculated as the desulfurization reaction rate is proportional to the 1.75 power of the sulfur concentration of atmospheric gas oil feedstock. The reaction rate constant of the catalyst K was set to 100 as a reference.

Example 2 Catalyst B was obtained in the same manner as in Example 1 except that the amount of diethylene glycol added was 124 g and the amount of the active metal aqueous solution was 400 ml.
The catalytic activity was determined in the same manner as described above. Catalyst B had a MoO ₃ content of 22%, a CoO content of 4%, and a P ₂ O ₅ content of 3%. The amount of diethylene glycol added was Mo and C.
It was 1.0 times the total molar amount of o and the amount of citric acid added was 0.15 times the total molar amount of Mo and Co.

Example 3 A catalyst C was obtained in the same manner as in Example 1 except that ethylene glycol was used as the polyalcohol, the addition amount was 186 g, and the amount of the active metal aqueous solution was 400 ml. The catalyst activity was determined. Catalyst C had a MoO ₃ content of 22%, a CoO content of 4%,
The P ₂ O ₅ content was 3%. The amount of ethylene glycol added was 2.5 times the total molar amount of Mo and Co, and the amount of citric acid added was 0.1 times the total molar amount of Mo and Co.
It was 15 times.

Example 4 1000 g of alumina hydrate
(Moisture content 60%) 124 g of molybdenum trioxide, 39.4 g of cobalt carbonate, 27 g of 85% phosphoric acid, glycerin 1
400 m of an active metal aqueous solution prepared from 08.6 g and water
The mixture was heated and kneaded at 80 ° C., and further, a cylindrical molded product having a diameter of 1.6 mm was obtained using an extruder. The molded product was dried at 100 ° C. for 16 hours to obtain a catalyst D.
Catalyst D has a MoO ₃ content of 22% and a CoO content of 4
% And P ₂ O ₅ content was 3%. The amount of glycerin added was 1.0 times the total molar amount of Mo and Co.

Example 5 1000 g of alumina hydrate
(Moisture content 60%), molybdenum trioxide 124 g,
39.4 g of nickel, 27 g of 85% phosphoric acid, 34.tartaric acid.
Activity prepared from 9 g, 181.4 g of glycerin and water
Add 500 ml of an aqueous metal solution, heat knead at 80 ° C,
Furthermore, using an extruder, a 1.6 mm diameter
And then dried at 100 ° C for 16 hours
Then, a catalyst E was obtained, and the catalytic activity was determined in the same manner as in Example 1.
MoO of catalyst E_ThreeContent is 22% and NiO content is 4%.
%, P_TwoO The content of 5 was 3%. Also, glycerin
The amount added is 1.67 times the total molar amount of Mo and Ni,
The amount of tartaric acid added is 0.2 times the total molar amount of Mo and Ni.
there were.

Example 6 1000 g of alumina hydrate
(Moisture content: 60%) was added to molybdenum trioxide (124 g), nickel carbonate (39.4 g), tartaric acid (34.9 g), an active metal aqueous solution (450 ml) prepared from triethylene glycol (187.6 g) and water, and the mixture was heated and kneaded at 80 ° C. further,
Using an extruder, a cylindrical molded product having a diameter of 1.6 mm was obtained, and dried at 100 ° C. for 16 hours to obtain a catalyst F. The catalyst activity was determined in the same manner as in Example 1. Catalyst F had a MoO ₃ content of 22% and a NiO content of 4%. The amount of triethylene glycol added was Mo and N.
1.0 times the total molar amount with i, and the amount of tartaric acid added is M
It was 0.2 times the total molar amount of o and Ni.

Example 7 1000 g of alumina hydrate
(Moisture content 60%) and an active metal aqueous solution 50 prepared from 124 g of molybdenum trioxide, 39.4 g of nickel carbonate, 27 g of acetic acid, 180.3 g of 1,4-butanediol and water.
0 ml was added, and the mixture was heated and kneaded at 80 ° C., and further, a cylindrical molded product having a diameter of 1.6 mm was obtained using an extruder, and dried at 100 ° C. for 16 hours to obtain a catalyst G. The catalyst activity was determined in the same manner as in Example 1. Mo of catalyst G
The O ₃ content was 22% and the NiO content was 4%. The amount of 1,4-butanediol added was 1.67 times the total molar amount of Mo and Ni, and the amount of acetic acid added was Mo and N.
It was 0.4 times the total molar amount with i.

Example 8 Silica-alumina hydrate 87
0 g (containing 10% as SiO ₂ , water content 54%) was added with 124 g of molybdenum trioxide, 39.4 g of cobalt carbonate, 34.9 g of tartaric acid, 400 ml of an active metal aqueous solution prepared from 99 g of diethylene glycol and water, and 80 ° C.
The mixture was heated and kneaded at, and a cylindrical molded product having a diameter of 1.6 mm was obtained using an extruder.
It dried at 16 degreeC for 16 hours, and obtained catalyst H, and the catalyst activity was calculated | required similarly to Example 1. MoO ₃ content of catalyst H is 22%, C
The content of oO was 4%. The amount of diethylene glycol added was 0.8 times the total molar amount of Mo and Co, and the amount of tartaric acid added was 0.2 times the total molar amount of Mo and Co.
It was twice.

Example 9 Instead of diethylene glycol, 375 g of polyethylene glycol having an average molecular weight of 200
The catalyst I was obtained in the same manner as in Example 1 except that the amount of the active metal aqueous solution was changed to 650 ml, and the catalytic activity was determined in the same manner as in Example 1. Catalyst I had a MoO ₃ content of 22% and C
The content of oO was 4% and the content of P ₂ O ₅ was 3%. Further, the addition amount of polyethylylene glycol is 1.6 times the total molar amount of Mo and Co, and the addition amount of citric acid is Mo.
And 0.15 times the total molar amount of Co.

Example 10 As a comparative example, molybdenum trioxide was added to 1000 g of alumina hydrate (water content: 60%).
24 g, cobalt carbonate 39.4 g, 85% phosphoric acid 27
g, EDTA 222 g, an active metal aqueous solution 450 ml prepared from 28% ammonia water 8 g and water,
The mixture was heated and kneaded at a temperature of 100 ° C., and a cylindrical molded product having a diameter of 1.6 mm was obtained using an extruder.
It dried at 16 degreeC for 16 hours, and obtained catalyst J, and the catalyst activity was calculated | required similarly to Example 1. Catalyst J had a MoO ₃ content of 22% and C
The content of oO was 4% and the content of P ₂ O ₅ was 3%. Further, the amount of EDTA added was 0.1% of the total molar amount of Mo and Co.
It was 65 times.

Example 11 As a comparative example, molybdenum trioxide was added to 1000 g of alumina hydrate (water content: 60%).
24 g, cobalt carbonate 39.4 g, 85% phosphoric acid 27
g, 234 g of ethylenediamine and 500 ml of an aqueous active metal solution prepared from water, and kneaded at 80 ° C. by heating,
Further, a cylindrical molded product having a diameter of 1.6 mm was obtained using an extruder, and this was dried at 100 ° C. for 16 hours to obtain a catalyst K. The catalyst activity was determined in the same manner as in Example 1.
Catalyst K has a MoO ₃ content of 22% and a CoO content of 4%.
% And P ₂ O ₅ content was 3%. The amount of ethylenediamine added was 2.5 times the total molar amount of Mo and Co. Table 1 shows the obtained results. In Examples 1 to 7 using the catalyst of the present invention, decomposition products generated during activation were lower hydrocarbons such as methane and ethane and alcohols, and carboxylic acids and amines were not detected.

[0031]

[Table 1]

Table 1 shows that the catalyst A prepared according to the present invention
~ I have extremely high activity compared to the conventional catalysts J and K to which a nitrogen-containing organic compound is added.

[0033]

According to the present invention, when a hydrotreating catalyst is prepared by the method of the present invention, the active metal can be extremely dispersed, and as a result, a highly active catalyst can be obtained. The use of the hydrotreating catalyst obtained by the method of the present invention enables advanced hydrotreating such as deep desulfurization and denitrification of hydrocarbon oil.

Claims (4)

(57) [Claims] 1. A catalyst carrier material containing one or both of an inorganic oxide and a hydrate thereof as a main component.
And Table Group 6 and Group 8 metal, and either or both of the phosphoric acid or carboxylic acid, based on the total molar amount of the periodic table Group 6 and Group 8 metal in a molar amount 0 3. A method for producing a hydrotreating catalyst, comprising adding an aqueous solution containing a polyalcohol in an amount of 3 to 5.0 times the amount, kneading, molding, and then drying at 200 ° C. or lower. 2. Using one or both of molybdenum or tungsten as the periodic table Group 6 metal, 8
The method for producing a hydrotreating catalyst according to claim 1, wherein one or both of nickel and cobalt are used as the group metal. 3. Citric acid, tartaric acid, carboxylic acid,
Glycolic acid, malonic acid, gluconic acid, glyceric acid,
The method for producing a hydrotreating catalyst according to claim 1, wherein at least one of malic acid, acetic acid, succinic acid, and glyoxal is used. 4. The polyalcohol used is at least one of ethylene glycol, diethylene glycol, triethylene glycol, glycerin, 2,2-diethyl-1,3-propylene glycol, butanediol, and polyethylene alcohol having an average molecular weight of 400 or less. The method for producing a hydrotreating catalyst according to any one of claims 1 to 3, wherein