JP2003135969A - Catalyst for hydrotreating hydrocarbon oil, method for producing the same, and hydrorefining method using the same - Google Patents

Abstract

[57] [Summary] [Problem] Not only has excellent desulfurization activity, but also excellent denitrification activity, and hydrogen consumption does not become excessive at the time of hydrorefining. Provided is a hydrocarbon oil hydrotreating catalyst that can advantageously achieve low sulfur and low nitrogen content of a hydrocarbon oil, a method for producing the same, and a hydrorefining method using the same. SOLUTION: Composition formula HxTiOy · fH ₂ O (x = 0.46 to 1.99, y
= 2.23 ~ 2.99, f = 0.04 ~ 17.8) with the hydrous titanium oxide, the main catalyst component consisting of molybdenum and / or tungsten and the promoter component selected from cobalt, nickel, phosphorus and boron Let the ion exchange,
Next, it is a hydrotreating catalyst for hydrocarbon oil, which is dried and calcined. Moreover, it is a manufacturing method of such a hydroprocessing catalyst, and also is a hydrorefining method of hydrocarbon oil using this hydroprocessing catalyst.

Description

Detailed Description of the Invention

[0001]

TECHNICAL FIELD The present invention relates to a hydrotreating catalyst for hydrocarbon oils such as petroleum fractions and coal liquefied oil, a method for producing the same, and a hydrorefining method using the same. Specifically, titania (titanium dioxide) having a high specific surface area is used as a catalyst carrier, and the titania contains a catalyst component (main catalyst component and co-catalyst component, which may be simply referred to as “catalyst component”). A highly-distributed and highly-dispersed hydrotreating catalyst and a method for producing the same, and using this hydrotreating catalyst, the removal selectivity of the nitrogen component to the sulfur component from the hydrocarbon oil containing the sulfur component and the nitrogen component can be improved. The present invention relates to a method for hydrorefining a hydrocarbon oil, which is capable of removing both the sulfur component and the nitrogen component at a high removal rate and at the same time significantly reduces the hydrogen consumption.

[0002]

2. Description of the Related Art Sulfur and nitrogen components contained in hydrocarbon oils such as petroleum and coal liquefied oil produce sulfur oxides and nitrogen oxides when the hydrocarbon oil is burned as a fuel,
In addition to being emitted into the atmosphere and causing air pollution, it also becomes a catalyst poison for the decomposition reaction and conversion reaction of hydrocarbon oil, and also causes a decrease in the reaction efficiency of these reactions.

Conventionally, hydrorefining has been carried out to remove the sulfur and nitrogen components of hydrocarbon oils, and the hydrotreating catalyst used in this hydrorefining is also made of, for example, alumina, zeolite-alumina or alumina. -Many hydrotreating catalysts in which catalyst components such as molybdenum (Mo), tungsten (W), cobalt (Co) and nickel (Ni) are supported on a carrier composed mainly of alumina such as titania and phosphorus-silica-alumina. Has been proposed (for example,
6-106,061, JP 9-155,197, JP 9-164,334
No. 2000-79,343, 2000-93,804, 2000
-117,111, JP 2000-135,437, JP 2001-62,304, etc.).

Generally, when the main purpose is the removal (desulfurization) of sulfur components in hydrocarbon oils, a catalyst supporting molybdenum or tungsten and cobalt is mainly used, and in addition to desulfurization, removal of nitrogen components is also used. When (denitrogenation) is also intended, a catalyst supporting molybdenum or tungsten and nickel is mainly used, because nickel has a high hydrogenation ability for an aromatic compound.

Most of the nitrogen components in hydrocarbon oils are present as aromatic compounds, and when the nitrogen-containing aromatic compounds are removed by hydrorefining, hydrogenation of aromatic rings first occurs, and then C The denitrification reaction proceeds by cleavage of the -N bond and elimination of ammonia. Therefore, when hydrorefining a hydrocarbon oil with a focus on denitrification with a hydrotreating catalyst containing nickel having a large hydrogenation capacity, hydrogen consumption increases, which causes problems such as an increase in treatment cost. is there.

[0006] According to the fourth report of the Ministry of the Environment and Central Environment Council in November 2000, "Measures for Future Vehicle Emission Reduction Measures," the sulfur content of diesel fuel, which is fuel for diesel vehicles, is It is appropriate to reduce the current level from 500ppm to 50ppm by FY2016.
It is said that further reduction of sulfur content is expected in the future. Nitrogen components in hydrocarbon oils such as light oil also cause deterioration of product quality due to coloration of products, and also cause poisoning and deterioration of hydrotreating catalysts during hydrorefining. It is desirable to remove it as much as possible.

However, it cannot be said that the desulfurization activity and denitrification activity of the above-mentioned conventional hydrotreating catalyst are necessarily sufficient, and for example, in order to reduce the sulfur component in light oil to 50 ppm or less, hydrogenation is required. It is necessary to tighten the processing conditions for purification. For example, the oil passage amount is set to about 1/3 to triple the reaction time, or the catalyst amount is increased to about 3 times. In the case of lowering the amount of oil flow, it is necessary to significantly rethink the production plan of the refinery, and in the case of increasing the amount of catalyst, it is necessary to add two reactors. Further, in the case where the amount of oil passing and the amount of catalyst are not changed, it is necessary to raise the reaction temperature by 20 ° C. or more, and if it is attempted to raise the reaction temperature to cope with it, the life of the catalyst will be greatly sacrificed. As described above, when the conventional hydrotreating catalyst is used, there is a problem that a great economic burden is imposed. Also, regarding the nitrogen component,
It is difficult to perform hydrorefining with a removal rate similar to that of sulfur components, and attempting to hydrorefining this nitrogen component with a high removal rate will result in excessive hydrogen consumption, resulting in a new refinery with less excess hydrogen. There was a problem such as the need to increase the hydrogen production equipment.

This is because, for example, in a hydrotreating catalyst in which molybdenum as a main catalyst component and cobalt as a cocatalyst component are supported on a carrier composed mainly of alumina, the supported amount of molybdenum is usually 25 wt. % Or less, and if it is attempted to support more than that, aggregates of molybdenum are not formed on the carrier and highly dispersed, and the catalytic performance is not effectively exhibited. This is because the desired activity cannot be obtained because of adverse effects such as decrease.

[0009]

DISCLOSURE OF THE INVENTION The inventors of the present invention are not only excellent in desulfurization activity but also excellent in denitrification activity, and that hydrogen consumption becomes excessive during hydrorefining. As a result of diligent studies on a hydrotreating catalyst for hydrocarbon oils that can achieve low sulfurization and low nitrogen content of hydrocarbon oils industrially advantageously, the water content represented by the prescribed composition formula HxTiOy · fH ₂ O Titanium oxide is contacted with a main catalyst component and a co-catalyst component for ion exchange, and then dried and calcined to increase the nitrogen component removal selectivity with respect to the sulfur component while having high desulfurization activity. The present invention has been completed by finding that the hydrogen consumption can be reduced and the above-mentioned problems can be achieved.

The object of the present invention is not only excellent in desulfurization activity but also excellent in denitrification activity, and the amount of hydrogen consumed during hydrorefining does not become excessively large. It is an object of the present invention to provide a hydrocarbon oil hydrotreating catalyst which can advantageously achieve low sulfurization and low nitrogen content of a hydrocarbon oil.

Another object of the present invention is to provide a hydrotreating catalyst which is excellent in both desulfurization activity and denitrification activity and which does not cause excessive hydrogen consumption during hydrorefining. It is to provide a manufacturing method of.

Further, another object of the present invention is to provide a hydrocarbon oil which is excellent in both desulfurization activity and denitrification activity, and which does not cause excessive hydrogen consumption during hydrorefining. It is an object of the present invention to provide a hydrorefining method capable of removing a sulfur component and a nitrogen component from a hydrocarbon oil containing both the sulfur component and the nitrogen component at a high removal rate using a hydrotreating catalyst.

[0013]

The present invention provides a composition formula HxTiO
y ・ fH ₂ O (x = 0.46 to 1.99, y = 2.23 to 2.99, f = 0.04 to 17.
The hydrous titanium oxide represented by 8) is contacted with a main catalyst component composed of molybdenum and / or tungsten and a co-catalyst component selected from cobalt, nickel, phosphorus and boron for ion exchange, and then dried. It is a hydrocarbon oil hydrotreating catalyst obtained by calcination.

The present invention also provides a compositional formula HxTiOy.fH ₂ O (x
= 0.46 to 1.99, y = 2.23 to 2.99, f = 0.04 to 17.8) selected from among the main catalyst components composed of molybdenum and / or tungsten, and cobalt, nickel, phosphorus and boron. The co-catalyst component is contacted together or separately to carry out ion exchange to finally adjust the pH to 3
It is the manufacturing method of the hydroprocessing catalyst of the hydrocarbon oil which makes it into the range of -9, is dried at 100-300 degreeC, and is baked at 300-700 degreeC.

Furthermore, the present invention provides a composition formula HxTiOy.fH ₂ O (x
= 0.46 to 1.99, y = 2.23 to 2.99, f = 0.04 to 17.8), the hydrous titanium oxide is selected from the main catalyst component consisting of molybdenum and / or tungsten and cobalt, nickel, phosphorus and boron. It is added to a dipping solution containing a co-catalyst component, brought into contact with each other at pH 1 to 7 or pH 9 to 11 for ion exchange, then filtered and then molded, and the obtained molded product is dried at 100 to 300 ° C., then 300 ~
A method for producing a hydrotreating catalyst for hydrocarbon oil, which comprises calcination at 700 ° C.

Furthermore, in the present invention, the hydrotreating catalyst and the hydrocarbon oil are reacted at a reaction temperature of 280 to 4 in the presence of hydrogen.
00 ℃, reaction pressure 2 ~ 15MPa, LHSV 0.3 ~ 10hr
^-1, and a hydrogen / oil ratio of 50 to 500 Nl / l are brought into contact with each other to remove sulfur and nitrogen components in the hydrocarbon oil, and a hydrorefining method of the hydrocarbon oil.

In the present invention, the hydrous titanium oxide used for supporting the above-mentioned main catalyst component and co-catalyst component (hereinafter, both may be simply referred to as "catalyst component") on the titania of the catalyst carrier has a composition Formula HxTiOy ・ fH ₂ O
(X = 0.46 to 1.99, y = 2.23 to 2.99, f = 0.04 to 17.8).

Here, the hydrous titanium oxide represented by the above composition formula HxTiOy · fH ₂ O is a titanium hydroxide portion represented by HxTiOy and a titanium hydroxide represented by fH ₂ O. It can be divided into the coexisting free water part.
Here, the titanium hydroxide represented by HxTiOy is TiO (O
H) a or TiO ₂ · (H ₂ O) b can also be represented by the chemical formula form.Basically, hydrogen is chemically bonded to titanium oxide as structural water in the form of a hydroxyl group or in the form of water. is doing. In the present invention, the amount of this structured water is 1
It is defined as the amount of change in weight between the weight of dry titanium oxide after drying under the drying conditions of 20 ° C. for 3 hours and the weight of titanium oxide after firing the dry titanium oxide under the conditions of 500 ° C. for 3 hours. Also, the amount of free water expressed in fH ₂ O is
It is defined as the weight change between the weight of undried hydrous titanium oxide and the weight of dry titanium oxide.

In the hydrous titanium oxide used in the present invention,
The value of x represented by the composition formula HxTiOy · fH ₂ O is x = 0.46〜
1.99, preferably x = 0.67-1.56. When the value of x is less than 0.46, the number of hydroxyl groups that ion-exchange with the catalyst component supplied to the surface of the titanium hydroxide is small, and the catalyst component of the present invention can be uniformly dispersed in a high concentration. Becomes difficult. On the other hand, when the value of x is larger than 1.99, it is preferable from the viewpoint of supporting the catalyst component with a large number of hydroxyl groups that are ion-exchanged with the catalyst component-containing ion, but the titanium hydroxide crystal particles are small. , X-ray shows an amorphous form, and the pore structure of the catalyst obtained by drying and calcining becomes unsuitable, resulting in poor performance as a hydrotreating catalyst.

Further, y represented by the composition formula HxTiOy.fH ₂ O
The value of is different depending on whether hydrogen is bound in the form of a hydroxyl group or bound in the form of water, but in the present invention, it is determined in the form of water, and the value of y is y = 2. 23
˜2.99, preferably y = 2.33 to 2.78.

Furthermore, f represented by the composition formula HxTiOy.fH ₂ O
Has a value of f = 0.04 to 17.8, preferably f = 0.
The range is from 23 to 10.4. When the value of f is less than 0.04, the hydrous titanium oxide is in a substantially dry state, and in such a state, it is difficult to disperse the catalyst component uniformly and highly even if the catalyst component is added. Even if the solution containing the same is added and stirred, it is difficult to disperse the titanium hydroxide particles uniformly, and thus it is difficult to disperse evenly. As a result, when the catalyst component is supported on titanium oxide at a high concentration, the catalyst component cannot be uniformly and highly dispersed, and agglomerates or agglomerates of the catalyst component are formed, resulting in low catalytic activity. On the other hand, when the value of f is larger than 17.8, the amount of free water becomes too large to mold the hydrous titanium oxide, or it becomes difficult to maintain its shape even if molded.
In addition, when the solution is added to the solution containing the catalyst component, this solution is diluted, and most of the catalyst component is not ion-exchanged, resulting in a problem of waste.

In the present invention, the amount of the catalyst component finally supported on titanium oxide of the catalyst carrier is preferably 0.06 to 0.46 atom per molybdenum and / or tungsten as the main catalyst component per titanium atom. Cobalt, nickel, phosphorus and boron as co-catalyst components are 0.02 to 0.26 atom per 1 atom of titanium, and the total amount of these main catalyst component and co-catalyst component is 0.08 per 1 atom of titanium.
~ 0.82 atoms is preferred. If the amount of the main catalyst component and co-catalyst component supported per atom of titanium is smaller than the above value, the supported amount of the catalyst component will be insufficient, and the sulfur component in the hydrocarbon oil targeted by the present invention will be 50 ppm or less. The catalytic activity of the hydrotreating catalyst to be reduced to 1.0 becomes low. On the other hand, if the value is larger than the above value, the amount is too large to be ion-exchanged with the hydroxyl group existing on the surface of the titanium hydroxide, which is wasteful.

In the present invention, the ion exchange of the catalyst component into the hydrous titanium oxide is carried out by finally mixing the hydrous titanium oxide with the main catalyst component and the co-catalyst component simultaneously or separately by means such as kneading. It can be carried out by contacting in the range of pH 3 or more and pH 9 or less, preferably pH 4 or more and pH 8 or less (first method). In addition, hydrous titanium oxide is added to a dipping solution containing a main catalyst component and a co-catalyst component, and usually pH 1 or more and pH 7 or less, preferably pH 2 or more and pH 6 or less, or pH 9 or more and pH 11 or less under stirring.
Hereafter, it can be carried out preferably by uniformly dispersing in the range of pH 9 or higher and pH 10 or lower, and then filtering (second method).

In the ion exchange of the catalyst component to the hydrous titanium oxide by the above-mentioned first method, the free water content of the hydrous titanium oxide is f = 0.04 to 17.8, preferably f = 0.2.
3 to 10.4, and finally pH 3 to
By performing the treatment in the range of 9, preferably pH 4 to 8, the compound containing the catalyst component can be used as it is, and can be uniformly dispersed at a high concentration. Contact conditions such as kneading at this time are preferably a temperature of room temperature to 100 ° C. and a contact time of 10 minutes to 10 hours. Further, the ion exchange of the catalyst component to the hydrous titanium oxide by the second method is carried out by using the p-method of the immersion solution containing both the main catalyst component and the co-catalyst component.
H for pH 1 to 7, preferably pH 2 to 6 or pH 9
By adjusting the pH to -11, preferably pH 9 to 10, the main catalyst component and / or the co-catalyst component becomes a homogeneous solution in the dipping solution without forming a precipitate, thereby making these catalyst components titanium oxide. The catalyst can be highly dispersed evenly on the surface in a high concentration and a highly active catalyst can be prepared. The contact conditions at this time are preferably a temperature of room temperature to 100 ° C. and a contact time of 0.5 to 24 hours.

The catalyst component for exchanging with the hydroxyl group of the hydrogel of hydrous titanium oxide is a main catalyst component composed of molybdenum and / or tungsten and a cocatalyst component selected from cobalt, nickel, phosphorus and boron. As a specific combination of the component and the cocatalyst component, for example,
Molybdenum-Cobalt, Molybdenum-Nickel, Molybdenum-Cobalt-Nickel, Molybdenum-Cobalt-Phosphorus, Molybdenum-Nickel-Phosphorus, Molybdenum-Cobalt-Boron, Molybdenum-Nickel-Boron, Molybdenum-Cobalt-Nickel-Phosphorus, Molybdenum-Cobalt- Examples thereof include nickel / boron, tungsten / nickel, tungsten / nickel / phosphorus, and tungsten / nickel / boron.

The ion exchange amount of the catalyst component to be exchanged with the hydroxyl group of the hydrous titanium oxide is preferably 0.06 atom to 0.46 atom per titanium atom, more preferably 0.46 atom or less. Is 0.07 atom or more and 0.40 atom or less, and the ion exchange amount of the co-catalyst component is 0.02 atom or more and 0.26 atom or less, more preferably 0.03 atom or more and 0.20 atom per 1 atom of titanium. The total ion exchange amount of the main catalyst component and the co-catalyst component is 0.08 atom or more and 0.82 atom per titanium atom.
The number of atoms is preferably at most 0.11, more preferably at least 0.75.

Here, as a raw material for producing a hydrogel of hydrous titanium oxide, titanium chloride, nitrate,
Salts such as sulfates and titanium compounds such as oxo salts and alkoxides can be used, and preferably titanium tetrachloride, titanium sulfate, titanyl sulfate, titanium trichloride,
Examples thereof include titanium methoxide, titanium ethoxide, titanium propoxide, titanium isopropoxide, and titanium butoxide.

Further, as the ionic species of the catalyst component which ion-exchanges with the hydroxyl group of the hydrous titanium oxide, specifically, PO ₄
^3- , MoO ₄ ²⁻ , WO ₄ ²⁻ , BO ₃ ³⁻ etc. Oxyanion having an ion form, metal carbonyl anion, Ni ²⁺ , Co ²⁺
And other metal cations. These can be used by repeating each one several times, and can also be used as a mixture of two or more kinds.

As a compound which provides a particularly suitable oxyanion, for example, ammonium molybdate [(NH ₄ )]
₆ Mo ₇ O ₂₄・ 4H ₂ O, (NH ₄ ) ₂ MoO ₄ , (NH ₄ ) Mo ₂ O ₇ ], sodium molybdate (Na ₂ MoO ₄・ 2H ₂ O), molybdic acid (H ₂ MoO ₄ , H
₂ MoO ₃ · H ₂ O), molybdenum pentachloride (MoCl ₅ ), silicomolybdic acid (H ₂ SiMo ₁₂ O ₄₀ · nH ₂ O), tungstic acid (H ₂ W
O ₄ ), ammonium tungstate [(NH ₄ ) ₂ · WO ₄ , 5 (NH
₄ ) ₂ O ・ 12WO ₃・ 4H ₂ O, 3 (NH ₄ ) ₂ O ・ 12WO ₃・ nH ₂ O], sodium tungstate (Na ₂ WO ₄・ 2H ₂ O), etc., as well as H ₃ P
O ₄ , HPO ₃ , H ₄ P ₂ O ₇ , P ₂ O ₅ , NH ₄ H ₂ PO ₄ , (NH ₄ ) ₂ HPO ₄ , (N
_{H 4) 3 PO 4 · H} 2 O, H 3 BO 3, HBO 2 further include a heteropoly acid salt to _{(PO 4 W 12 O 36)} · 5H 2 O , molybdenum, tungsten polyacid .

Suitable compounds of polyvalent metal salts which supply metal carbonyl anions include, for example, (NEt ₄ ) [M
o (CO) ₅ (OOCCH ₃ )], Mo (CO) ₆ -NEt ₃ -EtSH, W (CO) ₆ -NEt ₃ -Et
Examples include SH, W (CO) ₆ , (η-C ₅ H ₄ Me) ₂ Mo ₂ Co ₂ S ₃ (CO) _{4, and the} like. Further, a preferable compound of the polyvalent metal salt that supplies the polyvalent metal cation is a divalent or higher valent metal salt, and examples thereof include nickel nitrate [Ni (NO ₃ ) ₂ .6H ₂ O] and nickel sulfate (NiSO ₄ · 6H ₂ O), nickel chloride (NiCl _2), nickel acetate _{[Ni (CH 3 CO 2)} 2 · 4H 2 O], cobalt acetate [Co (CH ₃ CO _2)
2 · 4H ₂ O], there can be mentioned cobalt nitrate _{[Co (NO 3) 2 ·} 6H 2 O], cobalt sulfate _{(CoSO 4 · 7H 2 O)} , cobalt chloride (CoCl ₂ · 6H ₂ O), etc. .

Next, a method for producing the hydrotreating catalyst of the present invention will be described. First, the hydrous titanium oxide can be prepared by a method such as hydrolysis of the above-mentioned titanium compound or alkali neutralization. Here, as the alkali neutralizing agent,
Use alkali such as ammonia (NH ₃ ), sodium hydroxide (NaOH), potassium hydroxide (KOH), sodium carbonate (Na ₂ CO ₃ ), potassium carbonate (K ₂ CO ₃ ), sodium hydrogen carbonate (NaHCO ₃ ). be able to.

The conditions for producing this hydrous titanium oxide are as follows: when the concentration of hydrous titanium oxide is titanium dioxide (TiO ₂ ).
5 wt% to 10 wt%, preferably 1 wt% to 1
0% by weight or less, the reaction temperature is from room temperature to 300 ° C, preferably from room temperature to 100 ° C, and the reaction pressure is from atmospheric pressure to 3.0.
MPa, preferably normal pressure to 0.1 MPa, and pH is in the range of 0.5 or more and 11 or less, preferably 1 or more and 10 or less. Titanium oxide can be obtained. Further, in order to produce the preferred hydrous titanium oxide of the present invention, it is preferable to swing the titanium hydroxide between the pH of the precipitation region and the pH of the dissolution region more than once, and the pH of the precipitation region is 1. 0-10, and the pH of the dissolution region is preferably 0-2.

The hydrous titanium oxide obtained by the neutralization reaction or hydrolysis reaction of this titanium compound with an alkali has a composition formula HxTiOy · fH ₂ O of x = 0.46 to 1.9.
9, preferably x = 0.67 to 1.56, y = 2.2
3 to 2.99, preferably y = 2.33 to 2.78, f
= 0.04 to 17.8, preferably f = 0.23 to 1
It is filtered in the range of 0.4 or dehydrated. The structural water of hydrous titanium oxide can be easily adjusted by changing the synthesis conditions of hydrous titanium oxide, and the free water can be easily adjusted by changing filtration conditions, heating and drying at a relatively low temperature, dehydration under reduced pressure, and the like. be able to.

Next, the hydrous titanium oxide thus obtained is dispersed in the immersion solution by preparing the above-mentioned first method in which it is sufficiently brought into contact with the catalyst components by using a mixer or the like, or by preparing an immersion solution. By the above-mentioned second method, the hydroxyl group is ion-exchanged with the catalyst component. The ion exchange amount of the catalyst component that is exchanged with the hydroxyl group of the hydrogel of hydrous titanium oxide is preferably titanium ion exchange amount of the main catalyst component.
0.06 atom or more and 0.46 atom or less per atom, more preferably 0.07 atom or more and 0.40 atom or less,
Ion exchange amount of co-catalyst component is 0.02 per 1 atom of titanium
Atoms or more and 0.26 atoms or less, more preferably 0.03 atoms or more and 0.20 atoms or less, and the total ion exchange amount of these main catalyst component and co-catalyst component is 0.08 atoms or more and 0.1. 82 atoms or less, more preferably 0.11 atom or more and 0.75 atom or less.

The hydrous titanium oxide ion-exchanged with the catalyst component in this manner is then molded into a desired shape, and the obtained molded product has a temperature of 80 ° C. to 300 ° C., preferably 100 ° C. to 200 ° C. And a drying time of 0.5 hours or more and 24 hours or less, preferably 1 hour or more and 15 hours or less, and further baked under the conditions of 300 ° C. or more and 1200 ° C. or less, preferably 400 ° C. or more and 700 ° C. or less, and hydrogen. It is used as a chemical treatment catalyst.

The hydrotreating catalyst of the present invention is characterized in that the main catalyst component, molybdenum and / or tungsten, is contained in a conventional alumina-supported molybdenum / cobalt-supported catalyst, etc. (usually 6 to 25 on an oxide basis). weight
%) Compared to 15% on the oxide basis in the titania of the catalyst carrier.
~ 45 wt% (corresponding to 0.06 to 0.46 per 1 atom of titanium) is loaded at a high loading amount, and
In spite of such a high main catalyst component loading amount, it is loaded uniformly in a highly dispersed state without waste. This is presumably because the hydroxyl groups of the hydrous titanium oxide are ion-exchanged with the ions containing the catalyst component in advance before the drying and firing, so that the catalyst component is highly concentrated and uniformly dispersed on the surface of the titanium oxide.

[0037]

BEST MODE FOR CARRYING OUT THE INVENTION Preferred embodiments of the present invention will be specifically described below based on Examples and Comparative Examples.

Example 1 (Preparation of Titanium Tetrachloride Aqueous Solution) 1 kg of cooled titanium tetrachloride (TiCl ₄ ) was gradually added to ice-containing water to prepare an aqueous titanium tetrachloride solution having a titanium oxide conversion concentration of 210 g / l. Prepared. (Preparation of Ammonia Aqueous Solution) A 28 wt% -ammonia aqueous solution (NH ₄ OH aqueous solution) was diluted to 2 times to prepare a 14 wt% -ammonia aqueous solution.

(Step of synthesizing hydrous titanium oxide) Next, 10 liters of water was placed in a 30 liter vessel equipped with a stirrer.
While stirring at a temperature of 60 ° C., the titanium tetrachloride aqueous solution 1.
5 liters were added and the pH was lowered to 0.5. To this solution, 2.3 liters of the above 14 wt% -ammonia aqueous solution was added, the pH was raised to 7.0, and the mixture was stirred for about 5 minutes. By repeating this operation, the titanium hydroxide-containing titanium oxide was obtained by swinging the titanium hydroxide-dissolving pH region (pH = 0.5) and the precipitation pH region (pH = 7.0) three times in total.

(Filtration, Washing, Dehydration) After that, the hydrous titanium oxide was filtered, washed with pure water, and this washing operation was repeated until chlorine ions (Cl ⁻ ) were not confirmed in the filtrate by silver nitrate titration. Dehydrated titanium oxide hydroxide was obtained by pressure filtration. The composition of the hydrous titanium oxide obtained here was H _1.33 TiO _2.66 · 5.75H ₂ O.

(Ion exchange with catalyst component) In the hydrous titanium oxide obtained above, ammonium paramolybdate ((NH ₄ ) ₆ Mo ₇ O ₂₄
4H ₂ O), phosphoric acid (H ₃ PO ₄ ) equivalent to 0.05 atom per titanium atom, and cobalt nitrate ((Co (NO ₃ ) ₂ .6H ₂ ) equivalent to 0.06 atom per titanium atom. O) was added and the mixture was kneaded at room temperature for 2 hours with a kneader to obtain a pH of 6.5.

(Molding, Drying, Firing) Next, hole diameter 2.4 mm
Using a die of, the hydrous titanium oxide ion-exchanged with the catalyst component was molded into a cylindrical shape, and the obtained molded product was heated at 120 ° C.
After being dried under the condition of 3 hours, it was calcined under the condition of 500 ° C. for 3 hours to obtain the hydrotreated catalyst of Example 1. The physical properties of this hydrotreating catalyst are shown in Table 1.

Example 2 The hydrous titanium oxide obtained in Example 1 was treated with ammonium paramolybdate ((NH ₄ ) ₆ Mo ₇ O ₂₄ .4H ₂ O) corresponding to 0.47 atom per titanium atom, 0.0 per atom of titanium
And phosphoric acid (H ₃ PO _4), which corresponds to 6 atoms, cobalt nitrate ((Co (NO ₃ corresponding to 0.10 atom per titanium 1 atom) ₂ · 6H
₂ O) was dissolved in a large amount of a solution of pH 9, and the mixture was stirred for 3 hours to disperse and ion-exchange.

Thereafter, the ion-exchanged hydrous titanium oxide was filtered and dehydrated, and then a hydrotreating catalyst of Example 2 was obtained in the same manner as in Example 1. Table 1 shows the physical properties of the obtained catalyst.

Example 3 In the process of synthesizing hydrous titanium oxide, the number of times of alternate swinging between the dissolution pH region (pH = 0.5) and the precipitation pH region (pH = 7.0) of titanium hydroxide was set to 7 times. A hydrous titanium oxide was synthesized in the same manner as in Example 1 except for the above. The composition of the obtained hydrous titanium oxide is H _0.99 TiO _2.49
It was 0.39H ₂ O.

[0046] The hydrous titanium oxide, and ammonium paramolybdate corresponding to titanium per atom 0 · 16 atoms _{((NH 4) 6 Mo 7} O 24 · 4H 2 O), titanium per atom 0 - 11
Phosphoric acid (H ₃ PO ₄ ) equivalent to atoms and 0 per titanium atom
- 06 cobalt nitrate corresponding to atoms _{((Co (NO 3) 2} · 6H 2 O)
Were added to obtain a hydrotreating catalyst of Example 3 in the same manner as in Example 1. The physical properties of this catalyst are shown in Table 1.

Example 4 Hydrous titanium oxide was synthesized in the same manner as in Example 1, and filtration and dehydration after washing were performed with a vacuum filter. The composition of the obtained hydrous titanium oxide was H _1.95 TiO _2.97 · 17.74H ₂ O.
To this hydrous titanium oxide, ammonium paramolybdate ((NH ₄ ) ₆ Mo ₇ O equivalent to 0.16 atoms per titanium atom was added.
₂₄・ 4H ₂ O), phosphoric acid (H ₃ PO ₄ ) equivalent to 0.12 atom per titanium atom, and nickel nitrate (Ni (NO ₃ ) ₂・ 6H equivalent to 0.05 atom per titanium atom) ₂ O) was added and the hydrotreating catalyst was obtained in the same manner as in Example 1. The physical properties of this catalyst are shown in Table 1.

EXAMPLE 5 Ammonium tungstate (NH ₄ ) ₂ WO ₄ corresponding to 0.12 atom per titanium atom and nickel nitrate (Ni (NO) corresponding to 0.08 atom per titanium atom) were added to hydrous titanium oxide.
_{3) 2} · 6H ₂ O) except for adding, in the same manner as in Example 1 to prepare a hydrotreating catalyst. The physical properties of this catalyst are shown in Table 1.

The ammonium paramolybdate corresponding to titanium per atom 0.38 atom to Example 6 hydrous titanium oxide _{((NH 4) 6 Mo 7} O 24 · 4H
₂ O), boric acid (H ₃ BO ₃ ) equivalent to 0.16 atoms per titanium atom, and cobalt nitrate ((Co (NO ₃ ) ₂ .6H ₂ ) equivalent to 0.06 atoms per titanium atom. A hydrotreating catalyst was prepared in the same manner as in Example 1 except that O) was added, and the physical properties of this catalyst are shown in Table 1.

Also, the hydrotreatment obtained in this Example 6
Regarding touch, JEOL JXA-8900 type X-ray microanalyzer
Line analysis was performed using a riser (EPMA). The result is a figure
As shown in Fig. 1, the amount of molybdenum supported is 1 titanium original.
Even though it is 0.38 atoms per child, it is uniform in the pores.
It was found to be supported. Furthermore, in this Example 6,
The resulting hydrotreated catalyst and molybdenum oxide (MoO₃) And
X-ray using a PW3710 type X-ray diffractometer manufactured by Philip
The diffraction pattern was measured. The results are the hydrogenation treatment of Example 6.
The texture is as shown in Fig. 2, and molybdenum oxide (MoO ₃) Is a figure
There are three. The odor of this Example 6 hydrotreatment
Molybdenum oxide (MoO₃)age
Supported by MoO₃The diffraction pattern of
However, it is observed with the catalyst of Example 6 shown in FIG.
Not done. This is because molybdenum is distributed on the titanium oxide crystals.
This is because it is positioned on the surface and is simply carried in a layer on the surface.
It is not what was done.

Comparative Example 1 In the process of synthesizing hydrous titanium oxide, the synthesis temperature was 95.
A hydrous titanium oxide was synthesized in the same manner as in Example 1 except that the number of times of alternately swinging the titanium hydroxide dissolution pH region (pH = 0.5) and the precipitation pH region (pH = 7.0) at 9 ° C. was 9 times. The obtained hydrous titanium oxide was washed and filtered, and then 1
It was dried at 20 ° C. for 10 hours.

The composition of the obtained hydrous titanium oxide after drying is
Was _{H 0.27 TiO 2.14 · 0.02H 2 O} . A hydrotreating catalyst was prepared in the same manner as in Example 1, using the hydrous titanium oxide thus obtained. Table 2 shows the physical properties of this catalyst.
Shown in.

Comparative Example 2 10 liters of water was placed in a 30 liter vessel equipped with a stirrer, and 1.5 liters of the aqueous titanium tetrachloride solution prepared in Example 1 was added while stirring at room temperature to lower the pH to 0.5. . 2.3 liter of 14 wt% -ammonia aqueous solution was added to this solution, the pH was raised to 7.0, and the mixture was stirred for about 5 minutes. The precipitated hydrous titanium oxide was washed and filtered to obtain hydrous titanium oxide. This hydrosol was amorphous and its composition was H _2.22 TiO _3.11 · 27.1H ₂ O. Further, when the hydrosol was tried to be molded, it could not be molded because the water content was too large.

Comparative Example 3 In hydrous titanium oxide, ammonium tungstate (NH ₄ ) ₂ WO ₄ corresponding to 0.05 atom per titanium atom and nickel nitrate (Ni (Ni ( NO ₃₎ is ₂ · 6H ₂ O) and except for adding the above example 1
A hydrotreating catalyst was prepared in the same manner as in. Table 2 shows the physical properties of the obtained catalyst.

Comparative Example 4 Ammonium paramolybdate ((NH ₄ ) ₆ Mo ₇ O ₂₄
4H ₂ O) and cobalt nitrate ((Co (NO ₃ ) ₂ .6H ₂ O) corresponding to 0.27 atom per titanium atom were added, and the hydrogenation treatment was carried out in the same manner as in Example 1 above. A catalyst was prepared and the physical properties of the obtained catalyst are shown in Table 2.

Comparative Example 5 A molybdenum-cobalt-supported alumina catalyst industrially used for deep desulfurization of light oil was used as Comparative Example 5. The physical properties are shown in Table 2.

Comparative Example 6 A molybdenum-nickel-supported alumina catalyst industrially used for deep desulfurization of light oil and having a higher denitrification activity than the molybdenum-cobalt-supported catalyst was designated as Comparative Example 6. The physical properties are shown in Table 2.

Test Example 1: Hydrorefining of light oil Using the hydrotreating catalysts of Examples 1 to 6 and Comparative Examples 1 and 3 to 6, specific gravity (15/4 ° C): 0.850, sulfur Component: 1.37% by weight, nitrogen component: 101 ppm, and distillation properties: initial distillation 232 ° C, 50% distillation 295 ° C and 90% distillation 3
Hydrolysis of Middle East straight-run light oil having the property of 48 ° C was carried out and the performance of the hydrotreating catalyst was investigated.

The hydrorefining of light oil is carried out using a flow reactor with a reaction pressure of 5.0 MPa, a reaction temperature of 350 ° C., a liquid hourly space velocity of 2.01 / h, and a hydrogen / raw material ratio of 250 N1 / 1. It was carried out under the conditions. In carrying out this hydrorefining test, pre-sulfurization was carried out by a conventional method using light oil in which dimethyldisulfide was added to adjust the concentration of the sulfur component to 2.5% by weight.

The results of the hydrorefining reaction were 1.
The reaction constant was determined by using the secondary reaction as the secondary reaction and the denitrification reaction as the primary reaction, and the result of Comparative Example 1 was represented as a relative value, and the results are shown in Tables 1 and 2.

[0061]

[Table 1]

[0062]

[Table 2]

Test Example 2: Relationship between denitrification rate and hydrogen consumption amount Next, the hydrotreating catalyst (titania catalyst) of Examples 1 and 2 and the industrial catalyst (alumina catalyst) of Comparative Examples 5 and 6 were used.
Was used and the liquid hourly space velocity was changed in the range of 1 to 31 / h, and the relationship between the denitrification rate and the hydrogen consumption was investigated. The results are as shown in FIG. 4, and it was found that the titania catalysts of Examples 1 and 2 can significantly reduce the hydrogen consumption amount.

(Explanation of Examples and Comparative Examples) Test Example 1
As is clear from the results shown in Tables 1 and 2, the hydrotreating catalysts of Examples 1 to 6 have a desulfurization activity improved about twice or more as compared with the industrial catalyst of Comparative Example 5. In addition, the denitrification activity is improved more than 3 times. Even when the hydrotreating catalysts of Examples 1 to 6 were compared with the industrial catalyst of Comparative Example 6, the desulfurization activity was improved by about 1.8 times or more, and the denitrification activity was also increased. It shows an improvement of 1.5 times or more, and the hydrogen consumption is shown in FIG. 4 of Test Example 2 to Comparative Examples 5 and 6.
You can see that it is less than.

Further, looking at the results of Comparative Examples 1 to 4, when the structured water and free water of the hydrous titanium oxide are small (Comparative Example 1), ion exchange with the catalyst component is not sufficiently carried out, Both the desulfurization activity and the denitrification activity are not the same as in Comparative Example 6 and are not sufficient, and when the structured water and free water of the hydrous titanium oxide are too much (Comparative Example 2), the catalyst cannot be molded at the time of catalyst preparation, and When the amount of supported tungsten in the main catalyst component and the amount of supported nickel in the cocatalyst component are insufficient (Comparative Example 3), no improvement in desulfurization activity is observed, and furthermore, the amount of molybdenum supported in the main catalyst component is too large. It was also found that the case (Comparative Example 4) was not effective in improving the desulfurization activity and denitrification activity.

[0066]

EFFECTS OF THE INVENTION The hydrotreating catalyst of the present invention has particularly high selectivity of denitrification activity, is not only excellent in desulfurization activity but also excellent in denitrification activity, and moreover, it consumes less hydrogen. In addition to the deep desulfurization and deep denitrification of gas oil, for which quality improvement is required in the future, it is industrially applicable to hydrorefining treatment for reducing sulfur and nitrogen in other hydrocarbon oils. Can be used advantageously.

[Brief description of drawings]

FIG. 1 is a graph showing the results of line analysis of the hydrotreating catalyst obtained in Example 6 with an X-ray microanalyzer (EPMA).

FIG. 2 is a graph showing an X-ray diffraction pattern of the hydrotreating catalyst obtained in Example 6.

FIG. 3 is a graph showing an X-ray diffraction pattern of molybdenum oxide (MoO ₃ ).

FIG. 4 shows a liquid hourly space velocity of 1 using the titania catalysts of Examples 1 and 2 and the alumina catalysts of Comparative Examples 5 and 6.
It is a graph which shows the result of having examined the relationship between the denitrification rate and the amount of hydrogen consumption by performing the test changed in the range of -3.01 / h.

─────────────────────────────────────────────────── ─── Continuation of front page (51) Int.Cl. ⁷ Identification code FI theme code (reference) C10G 45/08 C10G 45/08 A (72) Inventor Hidehiko Kudo 2892 Shinyoshida-cho, Kohoku-ku, Yokohama-shi, Kanagawa Esperanza Tsunashima 206 (72) Inventor Akihiro Mutoh 2-1-32 Sakurayama, Zushi City, Kanagawa Prefecture A-2F (72) Inventor Takeo Ono 1-38 F Term, Kawasaki City, Kanagawa Prefecture (reference) 4G069 AA02 AA08 BA04A BA04B BB04A BB04B BB05C BC50C BC59A BC59B BC60A BC60B BC67A BC67B BC68A BC68B BD03A BD03B BD07A BD07B CC02 DA05 EA06 EC22Y EC25 FA01 FB08 FB26 FB30 FB57 FB61 FC02 FC0 FC08 FC08 FC29 FC07 FC08 FC09 FC29

Claims (5)

[Claims] 1. A composition formula HxTiOy.fH ₂ O (x = 0.46 to 1.99, y
= 2.23 to 2.99, f = 0.04 to 17.8), the main catalyst component consisting of molybdenum and / or tungsten and the co-catalyst component selected from cobalt, nickel, phosphorus and boron are contacted Let me exchange ions,
A catalyst for hydrotreating hydrocarbon oil, characterized by being dried and calcined. 2. The main catalyst component has an ion exchange amount of 0.06 to 0.46 atoms per titanium atom, and the co-catalyst component has an ion exchange amount of 0.02 to 0.26 atoms per titanium atom. The hydrotreating catalyst for hydrocarbon oil according to claim 1, wherein the total ion exchange amount of the main catalyst component and the cocatalyst component is 0.08 to 0.82 atom per 1 atom of titanium. 3. A composition formula HxTiOy.fH ₂ O (x = 0.46 to 1.99, y
= 2.23 to 2.99, f = 0.04 to 17.8) together with a main catalyst component composed of molybdenum and / or tungsten and a cocatalyst component selected from cobalt, nickel, phosphorus and boron. Or separately and contacting them for ion exchange to finally bring the pH to a range of 3 to 9 and then molding, and the resulting molded product is heated to 100 to 300 ° C.
And then calcining at 300 to 700 ° C., a method for producing a hydrocarbon oil hydrotreating catalyst. 4. A composition formula HxTiOy.fH ₂ O (x = 0.46 to 1.99, y
= 2.23 to 2.99, f = 0.04 to 17.8) Immersion of hydrous titanium oxide containing a main catalyst component composed of molybdenum and / or tungsten and a promoter component selected from cobalt, nickel, phosphorus and boron Add to solution, pH 1
~ 7 or pH 9 ~ 11 to contact for ion exchange, followed by filtration and molding.
A method for producing a hydrotreating catalyst for hydrocarbon oil, which comprises drying at 0 to 300 ° C and then calcining at 300 to 700 ° C. 5. The hydrotreating catalyst according to claim 1 or 2 and a hydrocarbon oil in the presence of hydrogen at a reaction temperature of 280 to 4
00 ° C, reaction pressure 2-15MPa, LHSV 0.3-10h
A hydrorefining method for a hydrocarbon oil, which comprises contacting under hydrotreatment conditions of r ^-1 and a hydrogen / oil ratio of 50 to 500 Nl / l to remove the sulfur component and the nitrogen component in the hydrocarbon oil.