JP3230585B2 - Method for producing hydrotreating catalyst - Google Patents

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

The present invention relates to a method for producing a hydrotreating catalyst for a hydrocarbon oil.

[0002]

2. Description of the Related Art Hydrogenation, desulfurization of hydrocarbon oils using hydrogen,
Catalyst in which a group 6 metal and a group 8 metal of the periodic table are supported as an active metal on a porous catalyst carrier such as alumina, titanium, silica, or activated carbon as a catalyst used in a hydrogenation treatment for denitrification or decomposition. 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 no activity has been carried by the oxide state on the catalyst support . Therefore, it is used after being subjected to an appropriate preliminary sulfurization treatment to form a sulfide state.

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 total number of active sites increases as the exposed surface area of the metal sulfide increases, and as a result, high catalytic activity is obtained. The increase in the exposed surface area of the metal sulfide can be achieved by increasing the dispersion of the metal sulfide carried on the catalyst carrier, or reducing the crystallite size of the metal sulfide. For this reason, several catalyst production methods have been developed and proposed for obtaining finely divided metal sulfides and obtaining highly dispersed catalysts in order to obtain more active catalysts.

For example, Japanese Patent Application Laid-Open No. 59-102442,
Japanese Patent Application No. 9-69147 discloses a method in which a mixed solution of a carboxylic acid such as citric acid or malic acid and an active metal is impregnated into a catalyst carrier such as alumina, 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 sufficiently prevented from agglomerating active metal.

[0005] Further, EP 0 810 35 A2 discloses that an organic compound having a nitrogen-containing ligand (such as an amino group or a cyano group) such as nitrilotriacetic acid, ethylenediaminetetraacetic acid or diethylenetriamine is used as a complexing agent.
A method is disclosed in which a mixed solution of the complexing agent and the active metal is impregnated and supported on an alumina or silica carrier, and then the catalyst is dried at a temperature of 200 ° C. or less. In this method molybdenum,
Since active metal ions such as nickel are strongly coordinated by the nitrogen-containing compound, the active metal is supported in a highly dispersed state. This state is maintained by setting the drying temperature to 200 ° C. or lower. As a result, the above-mentioned EP0181035
The catalyst obtained by the method disclosed in JP-A (A) has definitely higher catalytic activity than the conventional one.

[0006] However, even with such a catalyst, there is a demand for lowering the sulfur content of light oil, which is a problem in connection with the recent emission regulations, that is, a report that the sulfur content in light oil is reduced to 0.05% or less. Does not have high catalytic activity.
Further, it has been pointed out that since the complexing agent used in the method contains nitrogen, the complexing agent may be decomposed during the pre-sulfurization treatment to generate toxic gas such as hydrogen cyanide.

[0007]

SUMMARY OF THE INVENTION It is an object of the present invention to provide a method for producing a hydrotreating catalyst having a sufficiently high activity to realize the above-mentioned report.

[0008]

According to the method of the present invention for solving the above-mentioned problems, molybdenum and metal as active metals are deposited on a catalyst carrier .
One or both of nickel and nickel
Impregnating with an impregnating liquid containing one or both of the Baltic , drying at less than 200 ° C., and then carbonic acid in an amount of 0.5 to 5.0 times the total number of moles of the impregnated metal. Either one or both of ethylene and propylene carbonate are added , and the mixture is dried at a temperature lower than 200 ° C. Preferably, molybdenum or tungsten as an active metal is added to the catalyst support.
One or both of nickel and cobalt
A catalyst carrier containing an impregnating liquid containing either one or both and one or both of ethylene carbonate and propylene carbonate in an amount of 0.5 to 5.0 times the total number of moles of the confining metal. , And dried at less than 200 ° C., and more preferably, phosphoric acid coexisting in the impregnating liquid.

The catalyst carrier of the present invention refers to a general porous substance such as alumina, silica, titania, zirconia, activated carbon, etc., and an active metal (such as molybdenum or tungsten).
Nickel or cobalt with one or both
The loading amount of one or both) is a value generally used as a hydrotreating catalyst, that is, molybdenum,
Ngustene is 5-30% as oxide, nickel, copper
Belt 1-8 percent oxides, it is preferred phosphorus is 0.1 to 8% by _P 2 _{O 5.}

[0010]

In the method of the present invention, no organic compound containing nitrogen is used as a complexing agent. Therefore, the catalyst prepared by the method of the present invention does not generate toxic gas such as hydrogen cyanide during the pre-sulfidation treatment.

[0011] or indicate higher-activity activity of the catalyst using a nitrogen-containing compound of why such nitrilotriacetic acid or ethylenediaminetetraacetic acid or diethylenetriamine Using ethylene carbonate and propylene carbonate is not clear. The present inventors have compared the BET specific surface area values of these catalysts and the catalyst prepared by the method of the present invention, and found that those obtained by the method of the present invention are on average 30 to 40 m ² / g larger, Since the compound generates an adsorbable gas such as ammonia or cyan, which becomes a catalyst poison when decomposed, the catalyst obtained by the method of the present invention supports the active metal with higher dispersion and has more active sites. It is presumed that high activity is exerted because of this.

The reason why the drying temperature is set to less than 200 ° C. in the present invention is to prevent aggregation of the active metal and to prevent decomposition of the added ethylene carbonate or propylene carbonate. The amount of active metal supported is preferably within a range where sufficient activity is obtained, and further increase in the amount of supported metal does not further increase the activity. Is 5 to 30%, and the loading amount of nickel and cobalt is 1 to 8% as an oxide,
The supported amount of phosphorus is set to 8% or less as P2O5.

If the amount of ethylene carbonate and propylene carbonate is too small, high stiffness cannot be obtained, and if too large, carbonaceous material remains in the catalyst during the pre-sulfurization or precipitates, and sulfurization of the sulphate metal may occur. It is disturbed, and its activity is rather low.
Therefore, the amount of ethylene carbonate and propylene carbonate to be added is either molybdenum or tungsten, or
It is necessary that the total number of moles is 0.5 to 5.0 times the total number of moles of any one of nickel and cobalt, or both .

[0014]

DESCRIPTION OF THE PREFERRED EMBODIMENTS The present invention will be described below based on embodiments.

Example 1 Molybdenum trioxide 96.2 was added to 500 g of a γ-alumina carrier having a specific surface area of 280 m ² / g and a pore volume of 0.75 ml / g.
g, 41 g of cobalt carbonate, 30.8 g of 85% phosphoric acid, and 600 ml of an aqueous solution of an active metal prepared with water and dried at 110 ° C. for 5 hours. This was repeated to obtain a raw material catalyst.

Next, this raw material catalyst was fractionated into 250 g portions, and 83 g, 50 g, and ethylene carbonate were respectively added thereto.
Impregnated with 190 ml of an aqueous solution containing 25 g, 96 g, 58 g and 29 g of propylene carbonate, and dried at 110 ° C. for 10 hours to obtain catalysts A, B, C, D, E and F.

The catalysts A, B, C, D, E and F are all M
o content is 15% as MoO ₃ , Co content is Co
O was 4%, and P content was 3% as P ₂ O ₅ . The amounts of ethylene carbonate and propylene carbonate added to the active metal were 2.5 times the total moles of the active metal, 2.5 times for A and D, 1.5 times for B and E, and 0.1 times for C and F, respectively.
It is 75 times.

Next, 250 g of the above-mentioned raw material catalyst was fractionated at a time, and 69.7 g of EDTA and 5 mL of nitrilotriacetic acid were added.
Each of the catalysts G was impregnated with 190 ml of an aqueous solution containing 9.3 g, 96.2 g of diethylenetriamine, and 57.2 g of ethylenediamine, and dried at 110 ° C. for 10 hours.
H, I and J were obtained.

The catalysts G, H, I and J all have a Mo content of 15% as MoO ₃ and a Co content of 4% as CoO.
%, And the P content was 3% as P ₂ O ₅ . The amounts of EDTA, nitrilotriacetic acid, diethylenetriamine and ethylenediamine added to the active metal are 0.6 times, 0.85 times and 2.5 times, respectively, the total number of moles of the active metal.
2.5 times.

The catalysts A, B, C, D, E, F, G,
Preliminary sulfurization was performed using H, I, and J under the following conditions, and a hydrodesulfurization test of Kuwait atmospheric gas oil having the following properties was performed. (Preliminary sulfurization conditions) Sulfurized oil Kuat atmospheric pressure gas oil containing 2.5% dimethyl disulfide The following properties Sulfurized oil flowing liquid space velocity (Hr ^-1 ) 2 Catalyst amount (ml) 15 Atmosphere (Kg / cm ² -H ₂ ) 30 Hydrogen / sulfurized oil flow ratio (Nl / l) 300 Sulfurization temperature (° C) 330 Heating time (Hr) 10 Sulfurization time (Hr) 10 (Properties of Kuwait atmospheric gas oil) Specific gravity (15/4 ° C) 0.844 Sulfur (wt%) 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 Oil flow time ( Hr ) 88 The obtained hydrodesulfurization activity is indicated by the relative value of the reaction rate constant. That , The rate constant K was calculated as a desulfurization reaction rate is proportional to the 1.75 power of the sulfur concentration of atmospheric gas oil feedstock.

Next, relative reaction rate constants of the respective catalysts obtained by setting the rate constant of the catalyst O to 100 were determined. As a result, the relative reaction rates of the respective catalysts were as follows. Amount of catalyst complexing agent added Relative reaction rate constant A ethylene carbonate 2.5 185 B ethylene carbonate 1.5 162 C ethylene carbonate 0.75 145 D propylene carbonate 2.5 188 E propylene carbonate 1.5 165 F propylene carbonate 0.75 146 G EDTA 0.6 132 H Nitrilotriacetic acid 0.85 138 I Diethylenetriamine 2.5 121 J Ethylenediamine 2.5 100 Here, the amount of addition is shown by the ratio to the total number of moles of Mo and Co.

Example 2 Molybdenum trioxide 9 was added to 520 g of the γ-alumina carrier.
6.2 g, cobalt carbonate 41 g, ethylene carbonate 222 g
Impregnated with 620 ml of an active metal aqueous solution prepared from water and water, and dried at 110 ° C. for 10 hours to obtain a catalyst K. The activity of the catalyst K was measured in the same manner as in Example 1. I asked. As a result, the relative reaction constant is 1
75.

Example 3 Pseudo boehmite alumina support (Al ₂ O ₃ 92.8%) 2
3 g of molybdenum trioxide and 1 part of cobalt carbonate
Impregnated with 200 g of an aqueous active metal solution prepared from 5.2 g, 11.4 g of 85% phosphoric acid and water,
Dried for hours. This was repeated to obtain a raw material catalyst.

Next, this raw material catalyst was separated into 100 g portions, impregnated with 75 ml of an aqueous solution containing 33.3 g of ethylene carbonate and 38.4 g of propylene carbonate, and dried at 110 ° C. for 10 hours to obtain a catalyst. L and M were obtained.

Each of the catalysts L and M has a Mo content of Mo.
O ₃ as 15%, Co content as CoO 4%, P
The content was 3% as P ₂ O ₅ . The amount of ethylene carbonate and propylene carbonate added to the active metal is 2.5 times the total number of moles of the active metal.

The activity was measured in the same manner as in Example 1 using the catalysts L and M, and the relative reaction constant was determined by setting the catalyst J to 100. As a result, the relative reaction constants were 178 and 19, respectively.
It was 0.

Example 4 Silica-alumina carrier (SiO ₂ 10%, specific surface area 3
(25 m ² / g, pore volume 0.69 ml / g) 200 g of 38.5 g of molybdenum trioxide, 16.2 of nickel carbonate
g, 85% phosphoric acid, 12.3 g of phosphoric acid, and 160 ml of an aqueous solution of an active metal prepared from water and dried at 110 ° C. for 5 hours. This was repeated to obtain a raw material catalyst. Next, this raw material catalyst was taken in 100 g portions, and impregnated with 75 ml of each aqueous solution containing 33.3 g of ethylene carbonate and 38.4 g of propylene carbonate, dried at 110 ° C. for 10 hours, and dried to obtain catalysts N and O. I got

Both the catalysts L and M have a Mo content of Mo.
15% as O ₃ , Ni content 4% as NiO, P
The content was 3% as P ₂ O ₅ . The amount of ethylene carbonate and propylene carbonate added to the active metal is 2.5 times the total number of moles of the active metal. Catalyst N,
The activity was measured in the same manner as in Example 1 using O.
And the relative reaction constant was determined as 100. As a result, the relative reaction constants were 191 and 197, respectively.

From the above results, it is clear that according to the method of the present invention, it is possible to produce a hydrotreating catalyst having extremely high activity compared to the conventional one.

[0030]

The method of the present invention does not use a nitrogen-containing organic compound as a complexing agent, so there is no danger of generating harmful substances such as cyan at the time of pre-sulfurization. There is no aggregation. As a result, according to the method of the present invention, it is possible to produce an extremely high activity hydrotreating catalyst.

Claims (4)

(57) [Claims] 1. A catalyst support comprising molybdenum as an active metal ,
One or both of tungsten and nickel,
Ethylene carbonate in an amount of 0.5 to 5.0 times the total number of moles of active metal impregnated with an impregnating liquid containing one or both of cobalt and dried at less than 200 ° C. A method for producing a hydrotreating catalyst, comprising adding one or both of propylene carbonate and propylene carbonate, and drying the mixture at less than 200 ° C. 2. Molybdenum as an active metal on a catalyst carrier ;
One or both of tungsten and nickel,
Any one or both of cobalt and ethylene carbonate in an amount of 0.5 to 5.0 times the total number of moles of the active metal;
A method for producing a hydrotreating catalyst, comprising impregnating a catalyst support with an impregnating liquid containing one or both of propylene carbonate and drying at less than 200 ° C. 3. Molybdenum, tungsten as an impregnating liquid
Nickel or cobalt with one or both
The method for producing a hydrotreating catalyst according to claim 1, wherein an aqueous solution containing one or both of them and phosphoric acid is used. 4. Molybdenum, tungsten as an impregnating liquid
Nickel or cobalt with one or both
An aqueous solution containing one or both of phosphoric acid and ethylene carbonate or propylene carbonate in an amount of 0.5 to 5.0 times the total number of moles of the encapsulating metal, 3. The method for producing a hydrotreating catalyst according to claim 2, wherein the catalyst is used.