JP2000135438A - Hydrogenation catalyst and its production - Google Patents

Abstract

PROBLEM TO BE SOLVED: To produce a hydrogenation catalyst supported on a phosphorus- containing alumina carrier and having improved desulfurization activity when it is used in the hydrogenation of hydrocarbon oil. SOLUTION: At least one metal selected from the groups VIA and VIII metals of the periodic table is supported on an alumina carrier containing 0.5-10 wt.% phosphorus (expressed in terms of P2O5) to obtain the objective hydrogenation catalyst having >=250 m2/g specific surface area, >=0.45 ml/g total pore volume and 60-200 Å average pore diameter. In the catalyst, the volume of pores whose diameters are in the range of (the average pore diameter) ±30% accounts for >=70% of the total pore volume.

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

The present invention relates to a catalyst for hydrotreating hydrocarbon oils and a method for producing the same.
The present invention relates to a hydrotreating catalyst in which an active metal component is supported on a phosphorus-containing alumina carrier having high desulfurization activity and used for hydrotreating hydrocarbon oils, particularly heavy hydrocarbon oils and distillate hydrocarbon oils, and a method for producing the same.

[0002]

2. Description of the Related Art Heretofore, as catalysts for hydrotreating hydrocarbon oils, groups VIA and VIII of the periodic table have been used on an alumina carrier.
Catalysts supporting an active metal component selected from the group III are widely used, and various hydrotreating catalysts containing phosphorus or the like as a third component in addition to the above-mentioned catalyst components have been proposed.

For example, Japanese Patent Application Laid-Open No. 4-265158 discloses that a catalyst containing a porous carrier of an inorganic oxide, a phosphorus component, a cobalt component and a group VIB metal component is calculated based on 100 g of the catalyst, and the phosphorus component of the catalyst is calculated. content of _{P 2}
O ₅ calculated and as 2～28Mmol, the content of cobalt component, calculated as CoO 60～133Mmo
1, the content of the group VIB metal component is 132 to 208 mmol calculated as a trioxide, the specific surface area of the catalyst is 100 m ² / g or more, and the pore volume is 0.25 to 1 A catalyst is described which is in the range of 0.3 ml / g.

Japanese Patent Application Laid-Open No. 5-192578 discloses that a porous alumina carrier contains 1.0 to 6.0% by weight of a Group VIII metal oxide and a Group VIB metal oxide.
0-25.0% by weight, and oxides of phosphorus 1.0-6.
0% by weight supported catalyst, 160 to 210 m ² / g
, A total pore volume of 0.50 to 0.65 ml / g, and a pore size of 100 to 13 based on the total pore volume.
A catalyst characterized in that micropores of 0 ° are 70.0 to 85.0%, macropores of more than 160 ° are less than 7.5%, and macropores of more than 250 ° are less than 4.0%. A method for hydrotreating hydrocarbon oils using the same is described.

[0005] Further, a method for producing a phosphorus-containing alumina as a catalyst carrier is disclosed in Japanese Patent Publication No. 5-80256, Japanese Patent Publication No. 59-23860, and the like.

[0006]

DISCLOSURE OF THE INVENTION The present invention relates to a method for hydrodesulfurization of hydrocarbon oils, particularly heavy hydrocarbon oils and distillate hydrocarbon oils such as vacuum gas oil, gas oil and kerosene. Another object of the present invention is to provide a hydrotreating catalyst using a phosphorus-containing alumina carrier and a method for producing the same, which are further improved in point.

[0007]

Means for Solving the Problems The inventors of the present invention have conducted intensive studies on a conventional hydrogenation catalyst containing a phosphorus component, and as a result, have found that a specific fine catalyst in which a hydrogenation active metal component is supported on a phosphorus-containing alumina carrier. The inventors have found that a catalyst having a pore structure exhibits excellent desulfurization activity, and have completed the present invention.

That is, the hydrotreating catalyst according to the first aspect of the present invention is a method for preparing a hydrogenation catalyst on an alumina carrier containing 0.5 to 10% by weight of phosphorus as P ₂ O ₅ .
A hydrotreating catalyst carrying at least one metal component selected from the group consisting of:
m ² / g or more, the total pore volume (PV _o ) is 0.45 ml /
g or more, the average pore diameter (PD) is in the range of 60 to 200 °, and the proportion of the pore volume (PV _p ) of the average pore diameter (PD) ± 30% of the pore diameter is fine. It is characterized by being at least 70% of the pore volume (PV _o ).

Further, in the above-mentioned method for producing a hydrotreating catalyst according to the second aspect of the present invention, an aqueous solution of an aluminum salt containing a phosphate ion and a neutralizing agent are adjusted to have a pH of 6.5 to 9.5. To obtain a phosphorus-containing alumina hydrate, and washing, molding, drying, and calcining the hydrate to obtain an alumina carrier having a P ₂ O ₅ content of 0.5 to 10% by weight. VI
At least one metal component selected from Group A and Group VIII is supported by a conventional means.

The above-mentioned aqueous aluminum salt solution is preferably a basic aluminum salt aqueous solution or an acidic aluminum salt aqueous solution, and the above-mentioned neutralizing agent is an acidic aluminum salt aqueous solution or a basic aluminum salt aqueous solution. It is preferably an aqueous solution.

[0011]

DETAILED DESCRIPTION OF THE PREFERRED EMBODIMENTS Preferred embodiments of the present invention will be described below in detail.

The phosphorus-containing alumina support of the present invention contains 0.5 to 10% by weight (based on the support) of phosphorus as P ₂ O ₅ . If the phosphorus content is less than 0.5% by weight,
The effect of adding a phosphorus component is smaller than in the case of an alumina carrier, and the resulting catalyst cannot obtain the desired desulfurization activity. When the phosphorus content is more than 10% by weight, the total pore volume (PV _o ) and the average pore diameter (P
D) becomes small, and the desired desulfurization activity cannot be obtained. Preferred phosphorus content of the phosphorus-containing alumina _support, 1 to 8 wt% as P 2 _{O 5,} more preferably from 1 to 5% by weight is desirable.

[0013] The hydrotreating catalyst of the present invention can be obtained by adding the phosphorus-containing alumina support described above to a group VIA or VIII of the periodic table.
It carries at least one metal component selected from the group. Preferred metal components selected from Groups VIA and VIII of the periodic table include MoO ₃ , WO ₃ , and Co.
O, NiO, etc. are exemplified, and the loading amount of these metal components is in the range of 1 to 35 wt%, preferably, in the range of 10 to 30 wt% of MoO ₃ and / or WO ₃ and in the range of ₁ to 10 wt% of CoO and / or NiO. Is desirable.

The hydrotreating catalyst has a specific surface area (SA)
Is 250 m ² / g or more, and the total pore volume (PV _o ) is 0.4
At 5 ml / g or more, average pore diameter (PD) is 60 to 20
It is in the range of 0 °. If the SA, PV _o , and PD of the catalyst are out of the above ranges, a desired desulfurization activity may not be obtained, which is not desirable. Preferably, the specific surface area of the catalyst (S
A) is in the range of 260-350 m ² / g, the total pore volume (PV _o ) is in the range of 0.50-1.0 ml / g, and the average pore diameter (PD) is in the range of 70-150 °. Is desirable. The specific surface area (SA) in the present invention
Is the value measured by the BET method, and the total pore volume (PV _o ) and the average pore diameter (PD) are the mercury intrusion method (mercury contact angle: 13).
5 °, surface tension: 480 dyn / cm), the total pore volume (PV _o ) represents pores having a pore diameter of 41 ° or more, and the average pore diameter (PD) is the total pore volume (P
Represents the pore diameter corresponding to 50% of V _o ).

Further, the hydrotreating catalyst of the present invention has a sharp pore distribution and an average pore diameter (PD) of -30%
An average pore diameter (PD) + percentage relative to the total pore volume (PV _o) 30% of the pore volume between the pore diameter _{(PV p) (PV p /} PV o) is 70% from There is a feature. If PV _p / PV _o is less than 70%, the pore distribution of the catalyst becomes broad, and the desired desulfurization activity may not be obtained. It is desirable that PV _p / PV _o is preferably at least 75%.

Next, the method for producing the hydrotreating catalyst according to the second aspect of the present invention will be described in detail. In the present invention, an aqueous solution of an aluminum salt containing phosphate ions and a neutralizing agent are pH adjusted.
To obtain a phosphorus-containing alumina hydrate, but the phosphate ions also include phosphite ions. Phosphate compounds that produce ions can be used. As the phosphoric acid compound, H ₃ PO ₄ , H ₃ PO ₃ , (NH ₄ ) H ₂
PO ₄ , (NH ₄ ) ₂ HPO ₄ , K ₃ PO ₄ , K ₂ HP
O ₄ , KH ₂ PO ₄ , Na ₃ PO ₄ , Na ₂ HPO ₄ ,
NaH ₂ PO ₄ and the like.

As the aqueous solution of an aluminum salt containing phosphate ions, an aqueous solution of a basic aluminum salt such as sodium aluminate or potassium aluminate or an aqueous solution of an acidic aluminum salt such as aluminum sulfate, aluminum nitrate or aluminum chloride is preferably used. Is done. When the above-mentioned phosphate compound is alkaline or neutral, it is mixed with a basic aluminum salt aqueous solution, and when the phosphate compound is acidic or neutral, it is mixed with an acidic aluminum salt aqueous solution. Phosphate ions can be contained in a basic aluminum salt aqueous solution and / or an acidic aluminum salt aqueous solution.

When the aqueous aluminum salt solution is a basic aluminum salt aqueous solution, the neutralizing agent used in the present invention is a mineral acid such as sulfuric acid, nitric acid or hydrochloric acid, an organic acid such as acetic acid, or an acidic aqueous solution such as an acidic aluminum salt aqueous solution. And an aqueous solution of an acidic aluminum salt is particularly preferred. When the aluminum salt aqueous solution is an acidic aluminum salt aqueous solution, an alkaline aqueous solution such as caustic soda, caustic potassium, ammonia or a basic aluminum salt aqueous solution is used, and a basic aluminum salt aqueous solution is particularly preferable.

In the method of the present invention, for example, a predetermined amount of the above-mentioned basic aluminum salt aqueous solution containing a phosphate ion is charged into a tank equipped with a stirrer, heated to 40 to 90 ° C. and maintained. An aqueous solution of an acidic aluminum salt heated to ~ 90 ° C was continuously added over a period of 5 to 20 minutes so that the pH became 6.5 to 9.5 to form a precipitate of phosphorus-containing alumina hydrate, which was aged as desired. After washing, the resulting washed product is aged as necessary, molded into a desired shape, dried, and calcined at 400 to 800 ° C. for 0.5 to 10 hours to obtain a phosphorus-containing alumina carrier. . The addition time of the acidic aluminum salt aqueous solution is preferably 15 minutes or less, because if it becomes long, undesired crystals such as bayerite may be formed in addition to pseudo-boehmite.

Using the above-mentioned phosphorus-containing alumina carrier,
The catalyst can be produced by carrying at least one metal component selected from Groups VIA and VIII of the Periodic Table by conventional means. For example, as a raw material of the metal component, nickel nitrate, nickel carbonate, cobalt nitrate, cobalt carbonate, molybdenum trioxide, ammonium molybdate, ammonium paratungstate and the like are used. Carried by The catalyst is usually calcined at 400 to 800 ° C for 0.5 to 10 hours.

The hydrotreating catalyst of the present invention is not only suitable for use in hydrotreating distillate hydrocarbon oils such as vacuum gas oil, gas oil and kerosene, but also crude oil, normal pressure residue oil, and vacuum residue oil. It is also suitable for use in heavy oils such as hydrocarbon oils. The hydrogenation treatment using the catalyst can be performed under ordinary hydrogenation treatment conditions. Preferred reaction conditions include a reaction temperature of 330 ° C.
４５０450 ° C., hydrogen pressure 10１０〜250 kg / cm ² , liquid space velocity 0.05０．０５10 hr ⁻¹ are employed.

Hereinafter, the present invention will be described in more detail with reference to examples, but the present invention is not limited to these examples.

EXAMPLE 1 A 8.9% aqueous solution of sodium aluminate 8.9% in terms of Al ₂ O ₃ concentration was placed in a 100 L tank equipped with a steam jacket.
Add 1 kg, dilute with 40 kg of ion-exchanged water, and add trisodium phosphate (Na ₃ PO _4
2 O) was heated to 60 ° C. with stirring was added 0.32kg of. On the other hand, 7 wt% in the concentration of _Al 2 _{O 3} converted to 50L vessel
14.29 kg of aluminum sulfate aqueous solution of
Diluted to 40 kg with ion-exchanged hot water at ℃. Then
The above-mentioned diluted solution of aluminum sulfate was added at a constant rate to the above-mentioned diluted solution of sodium aluminate containing phosphate ions using a rotary pump, and the pH was adjusted to 7.
Thus, a phosphorus-containing alumina hydrate slurry was prepared so as to be 2. After the obtained phosphorus-containing alumina hydrate slurry was aged at 60 ° C. for 1 hour while stirring, the slurry was dehydrated using a flat plate filter and washed with 150 L of a 0.3 wt% aqueous ammonia solution. After the washing, the cake-like slurry is diluted with ion-exchanged water to obtain an Al ₂ O ₃ concentration of 10
After that, the pH of the slurry was adjusted to 10.5 with 15 wt% aqueous ammonia. This was transferred to an aging tank equipped with a reflux machine and aged at 95 ° C. for 10 hours while stirring. After the aging, the slurry was dewatered, concentrated and kneaded to a predetermined amount of water with a double-arm kneader equipped with a steam jacket, and then cooled and further kneaded for 30 minutes. The obtained kneaded product was molded into a 1.8 mm cylindrical shape by an extrusion molding machine, and dried at 110 ° C. The dried molded product was fired in an electric furnace at a temperature of 550 ° C. for 3 hours to obtain a phosphorus-containing alumina carrier. The amount of P ₂ O ₅ in the carrier was 2% by weight. Next, 143.4 g of molybdenum trioxide and 86.6 g of basic nickel carbonate are suspended in 650 ml of ion-exchanged water, and the suspension is heated at 95 ° C. for 5 hours by performing appropriate reflux measures so that the solution volume does not decrease. After that, the impregnating solution in which malic acid was added and dissolved was added to the above-mentioned phosphorus-containing alumina carrier 1
000 g was spray impregnated. The impregnated product was dried and calcined at 550 ° C. for 1 hour in an electric furnace to obtain a catalyst (A). Metal component of the catalyst (A) is, MoO ₃ is 12wt
% Of NiO is 3 wt%, and the properties of the catalyst (A) are shown in Table 1.

Example 2 In Example 1, the amount of the aqueous sodium aluminate solution was 8.82 kg, and the amount of trisodium phosphate was 0.49 kg.
A phosphorus-containing alumina carrier having a P ₂ O ₅ content of 3 wt% was obtained in exactly the same manner as in Example 1 except that 13.86 kg of the aluminum sulfate aqueous solution was used. Further, using this carrier, a catalyst (B) was obtained in the same manner as in Example 1. Table 1 shows the properties of the catalyst (B).

Example 3 In a 100 L tank equipped with a steam jacket, an aqueous solution of sodium aluminate 9.0 wt% of 22 wt% in terms of Al ₂ O ₃ concentration was added.
0kg and 26wt% sodium gluconate 0.22kg
Was diluted with 40 kg of ion-exchanged water, and heated to 60 ° C. with stirring. On the other hand, an aluminum sulfate aqueous solution 14.14 k of 7 wt% in terms of Al ₂ O ₃ concentration was placed in a 50 L container.
g and 48 g of 85 wt% phosphoric acid were added and diluted with warm water at 60 ° C. to make 40 kg. Next, the above-mentioned aluminum sulfate solution containing phosphoric acid was added to the above-mentioned sodium aluminate solution at a constant rate by using a rotary pump, and the pH was adjusted to 7.2 in 10 minutes, so that the phosphorus-containing alumina hydrate was used. A slurry was prepared. This phosphorus-containing alumina hydrate slurry was treated in the same manner as in Example 1 so that the amount of P ₂ O ₅ was 1
A wt% phosphorus-containing alumina support was obtained. Further, using this carrier, a catalyst (C) was obtained in the same manner as in Example 1. Table 1 shows the properties of the catalyst (C).

Example 4 Example 3 was repeated except that the amount of the sodium aluminate aqueous solution was 8.91 kg, the amount of phosphoric acid was 97 g, and the amount of the aluminum sulfate aqueous solution was 14.00 kg.
In exactly the same manner, a phosphorus-containing alumina support having a P ₂ O ₅ content of 2 wt% was obtained. In addition, using this carrier, Example 1
Catalyst (D) was obtained in the same manner as described above. Table 1 shows the properties of the catalyst (D).

Example 5 The procedure of Example 3 was repeated except that the amount of the sodium aluminate aqueous solution was 8.62 kg, the amount of phosphoric acid was 146 g, and the amount of the aluminum sulfate aqueous solution was 13.86 kg. A phosphorus-containing alumina support having a P ₂ O ₅ content of 3 wt% was obtained. Using this carrier, a catalyst (E) was obtained in the same manner as in Example 1. Table 1 shows the properties of the catalyst (E).

Example 6 A 8.9% aqueous solution of sodium aluminate 8.9% in terms of Al ₂ O ₃ concentration was placed in a 100 L tank equipped with a steam jacket.
Add 1 kg, dilute with 40 kg of ion-exchanged water, and add trisodium phosphate (Na ₃ PO _4
2 O) was heated to 60 ° C. with stirring was added 0.16kg of. On the other hand, 7 wt% in the concentration of _Al 2 _{O 3} converted to 50L vessel
14.00kg and 85wt% of aluminum sulfate aqueous solution
48 g of phosphoric acid was added and diluted with warm water of 60 ° C. to make 40 kg. Next, the above-mentioned aluminum sulfate solution containing phosphoric acid was added to the above-mentioned sodium aluminate solution at a constant rate by using a rotary pump, and the pH was 7.
Thus, a phosphorus-containing alumina hydrate slurry was prepared so as to be 2. This phosphorus-containing alumina hydrate slurry was treated in the same manner as in Example 1 to obtain a phosphorus-containing alumina support having a P ₂ O ₅ content of 2 wt%. Furthermore, using this carrier,
A catalyst (F) was obtained in the same manner as in Example 1. Table 1 shows the properties of the catalyst (F).

Example 7 In Example 6, the amount of the aqueous sodium aluminate solution was 8.82 kg, and the amount of trisodium phosphate (Na ₃ PO ₄ 12
H ₂ O) to 0.24 kg, and aluminum sulfate aqueous solution 13.86Kg, except that the amount of phosphoric acid was used 73g is in the same manner in Example _6, P 2 _{O 5} amount of 3 wt% of the phosphorus-containing alumina carrier Obtained. Using this carrier, a catalyst (G) was obtained in the same manner as in Example 1. Table 1 shows the properties of the catalyst (G).

COMPARATIVE EXAMPLE 1 In a 100 L tank equipped with a steam jacket, a 22 wt% sodium aluminate aqueous solution 9.0 in terms of Al ₂ O ₃ concentration was added.
9 kg was added and diluted with 40 kg of ion-exchanged water. 0.22 kg of a 26 wt% sodium gluconate aqueous solution was added to the diluted solution, and the mixture was heated to 60 ° C. with stirring. On the other hand, 14.29 kg of an aluminum sulfate aqueous solution of 7 wt% in terms of Al ₂ O ₃ concentration was put in a 50 L container, and diluted with 60 ° C. ion exchanged hot water to 40 kg. Next, the above-mentioned diluted solution of aluminum sulfate was added to the above-mentioned diluted solution of sodium aluminate at a constant rate using a rotary pump, and an alumina hydrate slurry was prepared by adjusting the pH to 7.2 in 10 minutes. . Thereafter, using this alumina hydrate slurry, a catalyst (H) comprising an alumina carrier (containing no phosphorus) was obtained in exactly the same manner as in Example 1. Table 1 shows the properties of the catalyst (H).

Example 8 Using the catalysts A to H of Examples 1 to 7 and Comparative Example 1, a hydrotreating reaction was carried out using a feedstock oil having the following properties to obtain a desulfurization activity (HDS), The metal activity (HDM) was compared with the catalyst of Comparative Example 1 (H) (reference catalyst). The reaction was carried out using a fixed bed flow reactor, and the reaction conditions were as follows. Properties of feed oil: Feed oil Atmospheric residual oil (AR) Density 0.9868 g / ml Sulfur content 4.127 wt% Ni + V content 109 wtppm Reaction conditions: Reaction temperature 380 ° C Liquid space velocity 0.30 hr ^-1 Hydrogen pressure 135 kg / cm ² hydrogen / oil ratio 800 Nm ² / kl The result of the hydrotreating reaction is the sulfur content in the reaction product oil and N
The i + V content was measured, and the removal rates of sulfur and Ni + V were determined as desulfurization rates and demetallation rates.
Table 1 shows relative activity values obtained by comparing the activities at 80 ° C. It can be seen that the catalysts A to G of the present invention have better desulfurization activity and demetallation activity than the reference catalyst H (Comparative Example 1).

[0032]

[Table 1]

[0033]

The catalyst of the present invention is extremely effective in practical use because it exhibits high desulfurization activity and high demetallation activity when used for hydrotreating hydrocarbon oils.

 ──────────────────────────────────────────────────続 き Continued on the front page F term (reference) 4G069 AA01 AA03 AA08 AA12 BA01A BA01B BA01C BB04A BB04B BB13A BB13B BC57A BC59A BC59B BC65A BC68A BC68B CC02 EC03X EC03Y EC04X EC04Y EC05X EC08 EC08 EC08 EC08 EC08 EC08 EC08 EC08 EC08 EC08 EC08 DA00

Claims (4)

[Claims] 1. Hydrogen obtained by supporting at least one metal component selected from Groups VIA and VIII of the Periodic Table on an alumina carrier containing 0.5 to 10% by weight of phosphorus as P ₂ O _5. Surface treatment catalyst, specific surface area (SA)
Is 250 m ² / g or more, and the total pore volume (PV _o ) is 0.4
At 5 ml / g or more, average pore diameter (PD) is 60 to 20
0 ° and average pore diameter (PD) ± 30
% Of the pore volume (PV _p ) occupying 70% or more of the total pore volume (PV _o ). 2. A phosphoric acid-containing alumina hydrate is obtained by mixing an aluminum salt aqueous solution containing a phosphate ion and a neutralizing agent so as to have a pH of 6.5 to 9.5. washing, molding, drying, _P 2 _{O 5} content 0.5 obtained by firing
2. The hydrotreating catalyst according to claim 1, wherein at least one metal component selected from Groups VIA and VIII of the periodic table is supported on 10% by weight of an alumina carrier by a conventional means. Production method. 3. The method for producing a hydrotreating catalyst according to claim 2, wherein the aluminum salt aqueous solution is a basic aluminum salt aqueous solution or an acidic aluminum salt aqueous solution. 4. The process for producing a hydrotreating catalyst according to claim 2, wherein the neutralizing agent is an aqueous solution of an acidic aluminum salt or an aqueous solution of a basic aluminum salt.