JP2000135437A - Hydrogenation catalyst and its production - Google Patents

Abstract

PROBLEM TO BE SOLVED: To produce a hydrogenation catalyst supported on a phosphorus-silica- alumina carrier and having improved desulfurization activity and cracking activity when it is used in the hydrogenation of distilled hydrocarbon oil. SOLUTION: At least one metal selected from the groups VIA and VIII metals of the periodic table is supported on a phosphorus-silica-alumina carrier to obtain the objective hydrogenation catalyst having >=200 m2/g specific surface area, >=0.35 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-silica-alumina carrier having high desulfurization activity and used for hydrotreating hydrocarbon oils, particularly 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 silica or phosphorus as a third component in addition to the above-mentioned catalyst components have been proposed.

[0003] For example, JP-A-7-204512 discloses that as a catalyst used in a hydrocarbon conversion process, 5 to 50% by weight of Al ₂ O ₃ , 10 to 90% by weight of SiO ₂ , and 5 to 40% by weight are used. Phosphorus containing P ₂ O ₅ by weight,
A catalyst composite comprising an amorphous solid solution of silicon and aluminum oxide is described.Also, a mixture of an alumina hydrosol, a silica hydrosol and a phosphorus compound is formed, and the mixture is gelled to form particles. A method for preparing the catalyst composite is disclosed which comprises the steps of calcination and calcination of the particles to produce phosphorus, silicon and aluminum oxides.

Japanese Patent Application Laid-Open No. 7-286184 discloses that an oxide of a non-noble metal of Group VIII has an oxide content of 2.5 to 6% by weight.
Group VIB metal oxide 13 to 24% by weight, silica 0 to 0
Carrying 2% by weight and 0 to 2% by weight of phosphorus oxide, 1
70-220 m ² / g total surface area, 0.6-0.8 cm
³ / g total pore volume, and less than about 33% of the total pore volume is present as primary micropores less than about 100 ° in diameter;
At least about 41% of the total pore volume is between about 100-20 diameters
Present as 0 ° secondary micropores, about 1% of the total pore volume
A process is described for hydrotreating a hydrocarbon feedstock in the presence of a porous alumina carrier catalyst having a pore size distribution such that 6-26% is present as mesopores with a diameter ≧ 200 °.

However, conventional hydrotreating catalysts are not always satisfactory in terms of desulfurization activity and the like, and there is room for improvement.

[0006]

The present invention has been further improved in terms of desulfurization activity and the like when used in the hydrotreating of hydrocarbon oils, especially distillate hydrocarbon oils such as vacuum gas oils, gas oils and kerosene. Another object of the present invention is to provide a hydrotreating catalyst using a phosphorus-silica-alumina carrier and a method for producing the same.

[0007]

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

[0008] That is, the hydrotreating catalyst according to the first aspect of the present invention comprises a phosphorus-silica-alumina carrier on the periodic table VIA.
A hydrotreating catalyst carrying at least one metal component selected from Group III and Group VIII, having a specific surface area (SA) of at least 200 m ² / g and a total pore volume (P
V _o ) is 0.35 ml / g or more and the average pore diameter (P
D) is in the range of 60 to 200 °, and the ratio of the pore volume (PV _p ) of the average pore diameter (PD) ± 30% to 70% of the total pore volume (PV _o ) The above is the feature.

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 mixing the slurry and silica sol obtained by washing the hydrate,
Characterized in that at least one metal component selected from Groups VIA and VIII of the Periodic Table is supported on a phosphorus-silica-alumina carrier obtained by molding, drying and calcining by a conventional means. It is.

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-silica-alumina support of the present invention preferably contains 0.5 to 10% by weight of phosphorus as P ₂ O ₅ (based on the support). When 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 or a silica-alumina carrier, and the resulting catalyst may not have 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 (PD) of the obtained catalyst become small, and a desired desulfurization activity may not be obtained. . Of phosphorus over silica-alumina carrier, more preferably the phosphorus content of 1-8% by weight _P 2 _{O 5,} more preferably from 1 to 5% by weight it is desirable.

The phosphorus-silica-alumina carrier of the present invention preferably contains silica in an amount of 3 to 25% by weight as SiO ₂ (based on the carrier). When the silica content is less than 3% by weight, the effect of adding the silica component is small,
The resulting catalyst may not have the desired desulfurization activity. When the silica content is more than 25% by weight, the obtained catalyst has a small total pore volume (PV _o ) and a small average pore diameter (PD), so that a desired desulfurization activity may not be obtained. . Of phosphorus over silica-alumina carrier, more preferably a silica content of 5 to 20 wt% as SiO _2, more preferably is preferably in the range of 10 to 20 wt%.

[0014] The hydrotreating catalyst of the present invention can be prepared by adding the above-mentioned phosphorus-silica-alumina carrier to the group VIA and V
It carries at least one metal component selected from Group III. Preferred metal components selected from Groups VIA and VIII of the Periodic Table include MoO ₃ , WO ₃ ,
CoO, NiO, etc. are exemplified, and the loading amount of these metal components is in the range of 1 to 35 wt%, preferably 10 to 30 wt% of MoO ₃ and / or WO ₃ , CoO and / or
Alternatively, NiO is desirably in the range of 1 to 10 wt%.

The hydrotreating catalyst has a specific surface area (SA)
Is 200 m ² / g or more, and the total pore volume (PV _o ) is 0.3
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 230-350 m ² / g, the total pore volume (PV _o ) is in the range of 0.40-1.0 ml / g, and the average pore diameter (PD) is in the range of 60-150 °. 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%
And the ratio (PV _p / PV) of the pore volume (PV _p ) between the average pore diameter (PD) and the pore diameter of 30% to the total pore volume (PV _o ) is 70% or more. 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 a 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 aluminum salt solution 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.

In the present invention, when the aqueous aluminum salt solution is a basic aluminum salt aqueous solution, the neutralizing agent may be 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 phosphate ions 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. Then, a phosphorus-containing alumina hydrate slurry from which by-product salts have been removed by washing is obtained. 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.

Next, the obtained phosphorus-containing alumina hydrate slurry is mixed with a predetermined amount of silica sol. The phosphorus-containing alumina hydrate slurry can be aged, if desired, before or after mixing with the silica sol. The phosphorus-containing alumina hydrate slurry mixed with the silica sol is heated and kneaded into a moldable kneaded material, molded into a desired shape by extrusion molding and the like, dried, and then dried at a temperature of 400 to 800 ° C. for 0.5 to 0.5 μm. Calcination is performed for 10 hours to obtain a phosphorus-silica-alumina carrier. The silica sol used in the present invention is not particularly limited, and a commercially available aqueous silica sol can be used. In particular, the average particle diameter of the colloidal silica particles is 10 nm.
Less than the silica sol is preferred.

Using the above-mentioned phosphor-silica-alumina carrier, a group VIA and group VII of the periodic table can be prepared by conventional means.
A catalyst can be produced by supporting at least one metal component selected from Group I. 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, and the metal component is supported by a known method such as an impregnation method or an immersion method. 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, kerosene, etc., but also crude oil, normal pressure residue oil, 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 intended to limit the present invention.

Example 1 A 8.8% aqueous solution of sodium aluminate of 22 wt% in terms of Al ₂ O ₃ concentration was placed in a 100 L tank equipped with a steam jacket.
2 kg, and diluted with 42.5 kg of ion-exchanged water. Trisodium phosphate (Na ₃ PO ₄ 1
2H ₂ O) was added and heated to 60 ° C. while stirring. On the other hand, in a 50L container, 7w in terms of Al ₂ O ₃ concentration
13.86 kg of an aluminum sulfate aqueous solution of t% is added,
It was diluted with ion-exchanged hot water at 60 ° C. to 40 kg. Next, the above-mentioned diluted solution of aluminum sulfate is added at a constant rate to the above-mentioned diluted solution of sodium aluminate containing phosphate ions by using a rotary pump, and the pH is adjusted to 7.2 in 10 minutes. A hydrate slurry was prepared. 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. Silica sol (catalyst 20L, manufactured by Catalyst Chemical Industry Co., Ltd.) having a SiO ₂ concentration of 20 wt% was added to the cake-like slurry after the completion of the washing.
After adding 85 kg, the mixture was diluted with ion-exchanged water so that the Al ₂ O ₃ concentration became 10 wt%, and the pH of the slurry was adjusted to 10.5 with 15 wt% ammonia water. This was transferred to an aging tank equipped with a reflux machine, and stirred at 95 ° C for 10 minutes.
Aged for hours. After the ripening, the slurry was dehydrated, concentrated and kneaded to a predetermined water content while kneading with a double-arm kneader equipped with a steam jacket, and then cooled and kneaded for another 30 minutes. The obtained kneaded material is extruded 1.8 m using an extruder.
m, 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-silica-alumina carrier. The amount of P ₂ O ₅ in the support was 2.67 wt%, and the amount of SiO ₂ was 11 wt%.
Next, 240.1 g of molybdenum trioxide and 131.0 g of basic nickel carbonate are suspended in 600 ml of ion-exchanged water, and the suspension is heated at 95 ° C. for 5 hours by performing a suitable reflux treatment so as not to reduce the solution volume. After that, the impregnating solution in which malic acid was added and dissolved was spray-impregnated into 1000 g of the above-mentioned phosphor-silica-alumina carrier. This impregnated product
After drying, the mixture was calcined at 550 ° C. for 1 hour in an electric furnace to obtain a catalyst (A). As for the metal component amounts of the catalyst (A), MoO ₃ was 18.5 wt% and NiO was 4.1 wt%. Table 1 shows the properties of the catalyst (A).

Example 2 Using the phosphorus-silica-alumina carrier of Example 1, the active metal component was 20.0 wt% of MoO _{3 and} 5.0 w of NiO.
t% of catalyst (B) was prepared in the same manner as in Example 1.
Table 1 shows the properties of the catalyst (B).

COMPARATIVE EXAMPLE 1 In a 100 L tank equipped with a steam jacket, a 22 wt% aqueous solution of sodium aluminate in terms of Al ₂ O ₃ concentration 88.
82 kg was added and diluted with 40 kg of ion-exchanged water. 0.22 kg of 26 wt% sodium gluconate aqueous solution was added to the diluted solution, and the mixture was heated to 60 ° C. while stirring.
On the other hand, 13.86 kg of an aluminum sulfate aqueous solution of 7 wt% in terms of Al ₂ O ₃ concentration was placed in a 50 L container, and diluted with hot ion-exchanged water at 60 ° C. 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. . The resulting alumina hydrate slurry was aged at 60 ° C. for 1 hour with stirring,
The slurry was dehydrated using a flat filter, and 0.3 w
Washing was performed with 150 L of a t% aqueous ammonia solution. A silica sol having a SiO ₂ concentration of 20% by weight (catalyst 20L, manufactured by Catalyst Chemical Industry Co., Ltd.) is added to the cake-like slurry after the washing.
After adding 1.85 kg of Al, diluted with ion exchanged water
_The concentration of ₂ O ₃ was adjusted to 10 wt%, and the pH of the slurry was adjusted to 10.5 with 15 wt% aqueous ammonia. This was transferred to an aging tank with a reflux machine, and stirred for 9 hours.
Aged at 5 ° C. for 10 hours. After the ripening, the slurry was dehydrated, concentrated and kneaded to a predetermined water content while kneading with a double-arm kneader equipped with a steam jacket, and then cooled and kneaded for another 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 at 550 ° C. for 3 hours in an electric furnace to obtain a silica-alumina carrier. The amount of SiO ₂ in the carrier was 11% by weight. Using this silica-alumina carrier, a catalyst (C) was obtained in exactly the same manner as in Example 1. The amount of the metal component of the catalyst (C) was 18.5 w for MoO ₃ .
At t%, NiO was 4.1 wt%. Table 1 shows the properties of the catalyst (C).

Example 3 Using the catalysts A to C of Examples 1 and 2 and Comparative Example 1, a hydrotreating reaction was carried out using a feedstock oil having the following properties, and the desulfurization activity (HDS) was compared. This was compared with the catalyst (C) of Example 1 (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 Straight run gas oil (SR-LGO) Density 0.8500 g / ml Sulfur content 1.327 wt% Nitrogen content 85 wtppm Reaction conditions: Reaction temperature 380 ° C Liquid space velocity 2.0 hr ^-1 Hydrogen pressure 50 kg / cm ² hydrogen / oil ratio 250 Nm ² / kl The hydrogenation reaction results were obtained by measuring the sulfur content in the reaction product oil, obtaining the sulfur removal rate as the desulfurization rate, and using the reference catalyst at a reaction temperature of 380 ° C. Table 1 shows relative activity values comparing the activities.
It was shown to. It can be seen that the catalysts A and B of the present invention have better desulfurization activity than the reference catalyst C (Comparative Example 1).

[0029]

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

[0030]

[Table 1]

 ──────────────────────────────────────────────────続 き Continued on front page F term (reference) 4G069 AA03 AA08 BA03A BC02B BC16A BC49A BC65A BC68B BC69A BD07A BD07B CB02 EC03X EC04X EC05X EC06X EC07X EC08X EC09X FB09 FC09 4H029 CA00 DA00

Claims (4)

[Claims] 1. A hydrotreating catalyst comprising a phosphorus-silica-alumina carrier carrying at least one metal component selected from Groups VIA and VIII of the periodic table, comprising a specific surface area (SA) Is not less than 200 m ² / g, the total pore volume (PV _o ) is not less than 0.35 ml / g, the average pore diameter (PD) is in the range of 60 to 200 °, and the average pore diameter (PD) ± 30% pore diameter pore volume (P
A hydroprocessing catalyst, wherein the proportion of V _p ) is at least 70% 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. A phosphorus-silica-alumina carrier obtained by mixing a slurry obtained by washing with a silica sol, molding, drying, and calcining is mixed with at least one metal component selected from Groups VIA and VIII of the periodic table. The method for producing a hydrotreating catalyst according to claim 1, wherein is carried by conventional means. 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.