JP4515337B2 - Porous titania for hydrotreating and hydrotreating method - Google Patents

Description

(Technical field to which the invention belongs)
The present invention relates to a porous titania useful for uses such as a catalyst carrier, a catalyst, a desiccant, an adsorbent, and a filler, and to the use thereof. Particularly, hydrogenation having a high specific surface area and excellent thermal stability. The present invention relates to a porous titania for treatment and a hydrotreating method using the same.

(Conventional technology)
Conventionally, porous titania is, for example, a method of hydrolyzing a titanium sulfate (titanyl sulfate) solution, which is a general method for synthesizing titanium hydroxide in a liquid phase, and an aqueous solution such as titanium tetrachloride or titanium sulfate (titanyl sulfate). It is manufactured by drying and baking hydrous titanium oxide produced by a method of neutralizing with an alkali, a sol-gelation method of hydrolyzing titanium alkoxide, or the like.

  However, with regard to titania produced by such a conventional method, the thermal stability is poor, and when the relationship between the specific surface area and the firing temperature is seen, the specific surface area rapidly decreases as the firing temperature increases, and the high It was difficult to maintain the specific surface area. This is because particle growth occurs by so-called sintering or dehydration condensation during the high-temperature firing. For example, in the case of hydrous titanium oxide, crystallization or crystal transition from amorphous to anatase or rutile occurs due to sintering or dehydration condensation, and the specific surface area is drastically reduced.

  For this reason, for example, a titania support or a titania catalyst produced by a conventional technique is excellent in hydrotreating activity per unit specific surface area as a hydrocarbon hydrotreating catalyst, but is not limited to alumina or silica. It was not used industrially like the catalyst support or catalyst of the system. In addition, for example, when used as an alkylation catalyst, it is necessary to perform a high temperature treatment in order to develop the acidity as a super strong acid, but the conventional support has poor thermal stability and a low specific surface area. The absolute amount of the acid was reduced, and the required performance as a catalyst could not be ensured. In addition, when used as a catalyst for flue gas denitration, it is usually used only at a low specific surface area of 40 to 50 m @ 2 / g due to the problem of thermal stability, despite its excellent denitration activity per unit specific surface area. Since it is not possible, a large amount of catalyst is required at present. Further, there is a problem that the temperature range of application is narrow due to the problem of thermal stability. In addition, titania has a high wear strength, but when used as a Fischer-Tropsch (FT) reaction catalyst, only a low specific surface area can be obtained. The current situation is not. For this reason, the titania carrier and catalyst produced by the prior art cannot sufficiently satisfy the performance required depending on the purpose of use and conditions of use. That is, since the thermal stability is poor, a high specific surface area cannot be maintained at high temperatures, resulting in poor performance.

  In addition, it has been difficult to produce titania having a sharp pore size distribution by the conventional method described above. In general, it is necessary to control the pore diameter range of a catalyst having high performance to a pore diameter suitable for the target reactant. That is, it is important that there is no diffusion resistance of the reactants and that there are no small or too large useless pores that are not effective for the reaction. Therefore, it is ideal that the catalyst has a pore diameter controlled according to the purpose of the reaction. For example, the effective catalyst pore diameter for the reaction is 6 to 10 nm for the purpose of desulfurization of light oil, and 8 to 15 nm for the purpose of desulfurization of heavy oil. In the case of the purpose of deasphaltening, it is in the range of 20 to 40 nm. However, the titania catalyst produced by the conventional method has a problem that sufficient performance cannot be obtained in terms of reaction selectivity, activity, and catalyst life because the catalyst pore diameter optimum for the reaction is small. .

  Therefore, as a method for solving such problems and sharpening the pore size distribution and controlling the range of the pore size, for example, in Japanese Patent Publication No. 60-50,721, a step of obtaining a seed hydrosol, alternately changing the pH between the hydrosol dissolution region and the hydrosol precipitation region, thereby growing a crystal to obtain a hydrosol in which loose aggregates are formed, and drying the hydrosol having formed the loose aggregates; There has been proposed a method for producing a porous inorganic oxide having a step of firing to obtain a metal oxide.

  However, this method alone can, for example, have a sharp pore size distribution controlled for titania, but does not cause a decrease in activity even with respect to thermal history due to catalyst firing or reaction heat in the reaction system. It has been difficult to produce such a titania catalyst.

Therefore, as a result of intensive investigations on porous titania having excellent thermal stability and a large specific surface area and a method for producing the same, it was found that the general formula TiO ₂ · nH ₂ O (where n is 0.02). After adding one kind or two or more kinds of anions, or cations, or these anions and cations as a particle growth inhibitor to the hydrous titanium oxide hydrosol or hydrogel represented by The present inventors have found that a porous titania having excellent thermal stability, a high specific surface area of 80 m ² / g or more and having a highly dispersed catalyst metal can be obtained by firing.

  Therefore, an object of the present invention is to provide a porous titania for hydroprocessing in which thermal stability is excellent, a specific surface area is large, and a catalytic metal is highly dispersed, and its use.

  Another object of the present invention is, in particular, hydrogenation that has excellent thermal stability and a large specific surface area, and also has a high sharp dispersion of catalyst metal and excellent reaction selectivity in addition to high dispersion of catalyst metal. It is an object to provide a porous titania for treatment and a hydrotreatment method using the same.

That is, in the present invention, particle growth during firing is applied to hydrous or hydrogels of hydrous titanium oxide represented by the general formula TiO ₂ .nH ₂ O (where n is 0.02 or more) or dried products thereof. As a particle growth inhibitor to be suppressed, an oxyanion and / or metal carbonyl anion containing P and Mo and a metal cation of Ni and / or Co are added at a rate of 0.06 to 6 g equivalent per 100 g of titanium oxide. It is a porous titania for hydrotreatment having a specific surface area of 80 m ² / g or more obtained by ion-exchange, drying and firing. The present invention is also a hydroprocessing method using the titania for hydroprocessing as a catalyst or a catalyst carrier.

  In the present invention, the anion is added at a pH lower than the isoelectric point of titanium oxide, the cation is added at a pH higher than the isoelectric point of titanium oxide, and when an anion and a cation are added at the same time, lower than the isoelectric point of titanium oxide. The hydrous titanium hydrosol or hydrogel is preferably produced by swinging alternately between the precipitation region pH and the dissolution region pH of the hydrous titanium oxide more than once.

In the present invention method, hydrosol or hydrogel or its dried product of hydrous titanium oxide, n of those the hydrated titanium hydroxide, expressed as MO ₂ · nH ₂ O, may be those of 0.02 or more. The meaning that n defined here is 0.02 or more defines the lower limit of the OH group possessed by hydrosol or hydrogel of hydrous titanium oxide or its dried product. The OH groups of hydrous titanium oxide hydrosol or hydrogel or dried product thereof are shifted by thermal history, and particle growth occurs due to sintering or dehydration condensation. At this time, by substituting the substitutable OH group with another functional group or the like, the thermal stability can be increased and a high specific surface area can be obtained. Therefore, what was manufactured by methods, such as a conventionally used hydrolysis method, neutralization reaction method, sol gel method, can be used. In addition, in order to obtain a porous titania suitable for producing a catalyst having a controlled sharp pore size distribution and having excellent reaction activity and selectivity, hydrous titanium oxide hydrosol or hydrogel or dried product thereof is used. Manufacture can be performed by swinging the pH of the hydrosol more than once alternately between its precipitation and dissolution regions.

  Here, as the titanium compound used to produce hydrous titanium oxide hydrosol or hydrogel or dried product thereof, specifically, titanium (Ti) chloride, nitrate, sulfate, carbonate, acetate, phosphoric acid Group 4 metal salts such as salts, borates, oxalates, fluorides, silicates, iodates, etc., titanium oxoacid salts such as titanic acid, etc., and titanium alkoxides. In addition, it can be used as a mixture of two or more. Among these titanium compounds, particularly preferable in the case of titanium, for example, titanium tetrachloride, titanium sulfate, titanyl sulfate, titanium trichloride, titanium methoxide, titanium ethoxide, titanium propoxide, titanium isopropoxide, Examples include titanium butoxide.

In addition, the particle growth inhibitor used in the present invention may include P and Mo oxyanions and / or metal carbonyl anions and Ni and / or Co metal cations. More specifically, an oxy anion and / or a metal carbonyl anion having an ion form such as PO ₄ ³⁻ , MoO ₄ ²⁻ , and a metal cation such as Ni ²⁺ and / or Co ²⁺ .

Compounds that provide particularly suitable oxyanions include ammonium molybdate {(NH ₄ ) 6Mo ₇ O ₂₄ · 4H ₂ O, (NH ₄ ) 2MoO 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 ₄ SiMo ₁₂ O ₄₀ · nH ₂ O _{), H 3 PO 4, HPO} 3, H 4 P 2 O 7, P 2 O 5, NH 4 H 2 PO 4, (NH 4) 2 HPO 4, (NH 4) 3 PO 4 · H 2 O, further H ₃ [PO ₄ W ₁₂ O ₃₆ ] · Heteropolyacid salt containing 5H ₂ O or Mo as a polyacid can be used. These can be used alone or in a mixture of two or more.

Examples of the polyvalent metal salt compound that supplies the metal carbonyl anion include (NEt ₄ ) [Mo (CO) ₅ (OOCCH ₃ )], Mo (CO) ₆ -NEt ₃ -EtSH, (η-C ₅ H ₄ Me) ₂ Mo ₂ Co ₂ S ₃ (CO) ₄ etc.

The polyvalent metal salt compound for supplying the polyvalent metal cation is a salt of a metal having a valence of 2 or more. For example, nickel nitrate {Ni (NO ₃ ) ₂ · 6H ₂ O}, 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}, cobalt nitrate {Co (NO ₃ ) ₂ · 6H ₂ O}, cobalt sulfate (CoSO ₄ · 7 H ₂ O), cobalt chloride (CoCl ₂ · 6 H ₂ O), manganese phosphate (MnPO ₄ ) and the like.

  The particle growth inhibitor used in the present invention can be used alone or in a mixture of two or more. Further, the metals Mo, Ni, Co, and P constituting the ions used as the particle growth inhibitor all have hydrotreating catalyst activity.

In addition, a compound suitable as a pH adjuster that alternately changes the pH of the hydrosol between the precipitation region and the dissolution region multiple times is titanium tetrachloride, titanium sulfate, titanyl sulfate, titanium tetrachloride, titanium trichloride as raw materials. Ferrous sulfate, ferric sulfate, ferrous chloride, ferric chloride, ferrous nitrate, ferric nitrate, nickel nitrate, nickel sulfate, nickel chloride, cobalt nitrate, cobalt sulfate, cobalt chloride, manganese nitrate , Manganese sulfate, manganese chloride, yttrium nitrate, yttrium sulfate, yttrium chloride, nitric acid (HNO ₃ ), hydrochloric acid (HCl), sulfuric acid (H ₂ SO ₄ ), carbonic acid (H ₂ CO ₃ ), formic acid (HCOOH), acetic acid (CH ₃ COOH) with an acid such as ammonia (NH _3), sodium hydroxide (NaOH), potassium hydroxide (KOH), sodium carbonate (Na ₂ CO _3), potassium carbonate (K ₂ CO _3), bicarbonate sodium NaHCO _3), potassium bicarbonate (KHCO _3), and alkali such as sodium bicarbonate potassium (KNaCO _3). In addition, these can be used alone or in a mixture of two or more.

[Method for Producing Porous Group 4 Metal Oxide]
(Production of Group 4 metal hydrated oxide)
The conditions for producing hydrous titanium oxide hydrosols, hydrogels, or dried products thereof with hydrous titanium oxide expressed as TiO ₂ · nH ₂ O of 0.02 or more are the porous titania (TiO ₂ ). The concentration is 1 to 20% by weight, preferably 3 to 15% by weight, the reaction temperature is from room temperature to 300 ° C., preferably from room temperature to 180 ° C., more preferably from room temperature to 100 ° C., the reaction pressure is from normal pressure to 3.0 MPa, Preferably, the pressure is from normal pressure to 0.9 MPa, more preferably from normal pressure to 0.1 MPa, and the pH is in the range of 0.5 to 11, preferably 1.0 to 10. Hydroxylation by alkali neutralization or hydrolysis. Titanium is produced.

(Addition of particle growth inhibitor)
In the hydrosol or hydrogel of hydrous titanium oxide represented by the above general formula TiO ₂ · nH ₂ O (where n is 0.02 or more) or one or more of them as a particle growth inhibitor In this case, when the particle growth inhibitor is an anion, it is preferably added at a pH lower than the isoelectric point of titanium oxide. When the particle growth inhibitor is a cation, it is preferably added at a pH equal to or higher than the isoelectric point of the titanium oxide. Further, when the particle growth inhibitor is an anion or a cation, the isoelectric point of the titanium oxide is preferably added. It is better to add at a pH below. This is because substitution by ion exchange or the like proceeds more effectively. And about the addition amount of these particle growth inhibitors, 0.06-6g equivalent with respect to 100g of titanium oxides, Preferably 0.1-5g equivalent is added, A temperature is normal temperature to 100 degreeC, Aging time 0.1-5 hours , Preferably 0.2 to 3 hours.
In addition, it is effective to add a particle growth inhibitor to the hydrosol in the production stage and the hydrogel in the production stage.

  For example, the hydrous titanium oxide is washed and one or more anions are added at a pH below 6.1 which is the isoelectric point of anatase of titanium oxide as a particle growth inhibitor, or one or more at a pH above the isoelectric point When an anion and a cation are added simultaneously, 0.06 to 6 g equivalent, preferably 0.1 to 5 g equivalent per 100 g of titanium oxide is added at a pH lower than the isoelectric point. Aging time is 0.1 to 5 hours, preferably 0.2 to 3 hours.

  As a method for adding the particle growth inhibitor, a direct kneading method can also be used. In this method, a particle growth inhibitor is directly added to a gel or a dried product in an amount of 0.05 to 5 g equivalent, preferably 0.1 to 4 g equivalent, per 100 g of titanium oxide, and a temperature range from room temperature to 100 ° C. And kneading for 0.1 to 5 hours, preferably 0.2 to 3 hours.

(Drying and firing conditions)
Filtered and dehydrated to a water content of 30 to 900% by weight, preferably 50 to 700% by weight, based on titanium oxide, molded into the required shape, dried at a drying temperature of 40 to 350 ° C, preferably 80 to 200 ° C. It is dried for 0.5 to 24 hours, preferably at 80 to 200 ° C, and calcined at a temperature of 350 to 1200 ° C, preferably 400 to 700 ° C.

As a method for producing a hydrous titanium oxide hydrosol having a seed production step and a hydrosol synthesis step, a method described in JP-B-60-50,721 can be specifically exemplified.
That is, for the seed production step, conventional methods such as a heterogeneous precipitation method, a uniform precipitation method, a coprecipitation method, an ion exchange method, a hydrolysis method, and a metal dissolution method can be employed. As for the hydrosol synthesis step, an aqueous solution of a titanium compound and / or a pH adjuster are alternately added to the hydrous titanium oxide hydrosol obtained in the seed production step, and a hydrosol dissolution pH region and a hydrosol precipitation pH region are obtained. The hydrosol dissolution pH region refers to the pH region where the fine particle hydrosol can be solubilized, and the hydrosol precipitation pH region causes the growth and aggregation of the hydrosol particles. It refers to the pH range. Further, in this hydrosol synthesis step, treatments such as aging, washing, and solid content adjustment are performed as necessary to obtain hydrous titanium oxide hydrosol or hydrogel having desired properties.

  In the production of the titanium oxide, the conditions for producing the hydrous titanium oxide include: the pH of the precipitation region at each stage of swinging the pH is 0.5 to 11, the concentration is 0.1 to 20% by weight, and the temperature is from room temperature to 300 ° C. The holding time is 0.01 to 0.5 hours, preferably 0.02 to 0.3 hours. The pH of the hydrous titanium oxide dissolution region is preferably 0 to 3, the concentration is 0.1 to 20% by weight, the temperature is from room temperature to 300 ° C., and the holding time is 0.02 to 5 hours. In addition, the number of times of holding alternately in the precipitation region and the dissolution region is preferably in the range of 2 to 20 times.

  For example, the production conditions of each stage for swinging the pH of the hydrous titanium oxide are as follows: the pH of the precipitation region is 1.0 to 10, the concentration is 0.1 to 15% by weight, the temperature is from room temperature to 180 ° C., and the holding time is 0. 0.01 to 0.5 hours, preferably 0.02 to 0.3 hours, the pH of the dissolution region is 0 to 2, the concentration is 0.1 to 15% by weight, the temperature is from room temperature to 180 ° C., and the holding time is 0.00. A range of 02-5 hours is preferred. In addition, the number of times of alternately holding in the precipitation region and the dissolution region is preferably in the range of 2 to 10 times.

The porous titania obtained by the method of the present invention is useful for uses such as a catalyst carrier, a catalyst, a desiccant, an adsorbent, and a filler. In particular, the porous titania obtained by the method of the present invention is 80 m ^2. Hydroprocessing (desulfurization, denitrogenation, demetallization, asphaltene decomposition, aromatic hydrogenation) due to the characteristics such as high specific surface area of over / g and pore sharpness degree (definition is described later) 30% or more. , Hydrocracking, alkylation, Fischer-Tropsch, flue gas denitration, photoreaction and the like can be used as a high-performance catalyst carrier or catalyst. In the following a specific surface area of 80 m ² / g, it becomes difficult to exhibit the desired reaction activity. Further, when the degree of pore sharpness is 30% or less, the selectivity of the reaction is lowered.

[Measurement of physical properties]
(Pore sharpness)
Regarding the cumulative pore distribution curve measured by the mercury porosimeter, first, the vertical axis indicating the cumulative pore volume and the horizontal axis indicating the pore diameter (Å), at (1/2) PV of the total pore volume (PVT) The pore diameter (median diameter) is determined. Next, the pore volume (PVM) within a pore diameter range of ± 5% in the logarithmic value of the median diameter is obtained, and the fine volume is calculated from the pore volume (PVM) and total pore volume (PVT) by the following formula. The degree of pore sharpness representing the degree of sharpness of the pore distribution is obtained.
Pore sharpness = {pore volume (PVM) / total pore volume (PVT)} * 100
The pore sharpness degree defined here is a factor for evaluating the optimum degree of pores for the reaction with respect to the total pore volume. The larger the pore sharpness degree, the sharper the pore distribution. This is preferable.

(Measurement method of specific surface area)
The specific surface areas of the catalyst and the carrier were measured by the BET three-point method, and Macsorb Model-1201 manufactured by Mountec Co., Ltd. was used.

(Measurement method of pore distribution)
The pore volume and pore distribution of the catalyst and the carrier were measured by a mercury intrusion method at a measurement pressure of 414 MPa, and Autopore 9200 model manufactured by Shimadzu Corporation was used as the measurement instrument.

(Measurement method of crystal structure)
The crystal structure of the catalyst and the carrier was measured by X-ray diffraction, and PW3710 manufactured by PHILIPS was used as a measuring instrument.

  The porous titania for hydrotreatment of the present invention not only has a large specific surface area, but also has excellent thermal stability, and has a controlled sharp pore size distribution, and has excellent reaction selectivity. In addition to having a large specific surface area and excellent catalytic activity, it also has excellent thermal stability, and can be used as a catalyst or catalyst support particularly useful for the purpose of hydrotreatment.

  Hereinafter, preferred embodiments of the present invention will be described in detail based on examples and comparative examples.

[Reference Example 1]
[Preparation of hydrosol]
(Preparation of titanium tetrachloride aqueous solution)
Ice pure water to the cooled titanium tetrachloride (TiCl ₄₎ 1 kg was gradually added to prepare an aqueous titanium tetrachloride solution of the titanium oxide concentration in terms 210g / l was added.
(Preparation of 14wt% NH ₄ OH aqueous solution)
28 wt% NH ₄ OH was diluted 2 times to prepare a 14 wt% NH ₄ OH aqueous solution.

(Hydrosol synthesis process)
Next, 10 liters of pure water was placed in a 30 liter vessel equipped with a stirrer, and 1.5 liters of the titanium tetrachloride aqueous solution was added while stirring to lower the pH to 0.5 or lower.
To this solution, 2.3 liters of the above 14 wt% NH ₄ OH aqueous solution was added, the pH was raised to 7, and left for about 5 minutes.

(Filtering and washing)
After completion of the hydrosol synthesis step, filtration was performed, and the resulting cake was washed with pure water, and the washing operation was repeated until chlorine (Cl ⁻ ) was not confirmed in the filtrate by silver nitrate titration to obtain a titania hydrosol.

(Preparation of dried product)
The titania hydrosol obtained as described above was subjected to suction filtration, dehydrated to a water content of about 50% by weight, and then molded using a die having a hole diameter of 1.5 mmφ. And dried for 3 hours to obtain a titania dry molded product.

(Particle growth inhibitor addition process)
The titania dry molding obtained above was immersed in an aqueous solution containing 16.3% by weight of ammonium paramolybdate on an oxide basis per titanium oxide, allowed to stand at room temperature for 2 hours, and then filtered with 5C filter paper. As a result, a molybdenum support was obtained.

(Dry firing process)
The obtained molybdenum-supported product was dried at 120 ° C. for 3 hours and then calcined at 500 ° C. for 3 hours to obtain a molybdenum-supported titania catalyst.
Table 1 shows the physical properties of the obtained molybdenum-supporting titania catalyst.

[Reference Example 2]
Hydrosol was synthesized by the same method as in Reference Example 1, 1.5 liter of titanium tetrachloride aqueous solution was added with further stirring to lower the pH to 0.5 again, and then allowed to stand for 5 minutes, then 14 wt% NH ₄ 2.8 liters of OH aqueous solution was added to raise the pH to 7 again and left for another 5 minutes.
These operations were repeated three more times, and the hydrosol dissolution pH range (pH 0.5) and the hydrosol deposition pH range (pH 7) were alternately changed 5 times in total.
The subsequent washing, filtration, molding, drying, particle growth inhibitor addition step, and drying and firing step were the same as in Reference Example 1.
Table 1 shows the physical properties of the obtained molybdenum-supporting titania catalyst.

[Reference Example 3]
A phosphorus-supported titania catalyst was obtained in the same manner as in Reference Example 2 except that 8% by weight of phosphoric acid on an oxide basis per titanium oxide was used as the particle growth inhibitor.
The physical properties of the obtained catalyst are shown in Table 1.

[Reference Example 4]
The washed hydrosol of Reference Example 2 was immersed in an aqueous solution containing 16.3% by weight of ammonium paramolybdate based on oxide per titanium oxide, allowed to stand at room temperature for 2 hours, suction filtered, and water content Dehydrated to 50 wt%. Subsequently, it was molded using a die having a hole diameter of 1.5 mmφ, and the obtained molded product was dried at 120 ° C. for 3 hours and then calcined at 500 ° C. for 3 hours to obtain a molybdenum-supporting titania catalyst.
Table 2 shows the physical properties of the obtained catalyst.

[Reference Example 5]
The filtered hydrogel of Reference Example 2 was immersed in an aqueous solution containing 8% by weight of phosphoric acid on an oxide basis per titanium oxide, left at room temperature for 2 hours, and then suction filtered to a water content of 50% by weight. Until dehydrated. Subsequently, it shape | molded using the die | dye of hole diameter 1.5mm (phi), and after drying the obtained molded object at 120 degreeC for 3 hours, it baked at 500 degreeC for 3 hours, and obtained the phosphorus carrying | support titania catalyst.
Table 2 shows the physical properties of the obtained catalyst.

[Reference Example 6]
A tungsten-supported titania catalyst was obtained in the same manner as in Example 4 except that 20.6 wt% ammonium metatungstate based on oxide per titanium oxide was used as the particle growth inhibitor.
Table 2 shows the physical properties of the obtained catalyst.

Reference Example 5 except that 2.0% by weight phosphoric acid, 8.0% by weight ammonium paramolybdate and 2.0% by weight cobalt nitrate were simultaneously used as grain growth inhibitors on an oxide basis per titanium oxide. In the same manner as above, a phosphorus / molybdenum / cobalt-supported titania catalyst was obtained.
Table 3 shows the physical properties of the obtained catalyst.

Reference Example, except that 2.0% by weight phosphoric acid, 8.0% by weight ammonium paramolybdate and 2.0% by weight nickel nitrate were simultaneously used as grain growth inhibitors on an oxide basis per titanium oxide. In the same manner as in Example 5, a phosphorus / molybdenum / nickel-supported titania catalyst was obtained.
Table 3 shows the physical properties of the obtained catalyst.

Using a small flow reactor, starting from vacuum gas oil (nitrogen concentration 0.2 wt%), reaction temperature 370 ° C, reaction pressure (hydrogen partial pressure) 8.0 MPa, LHSV2 ^-1 , H ₂ / oil ratio Hydrogenation was carried out using the phosphorus / molybdenum / nickel-supported titania catalyst of Example 2 (BET specific surface area of 167 m ² / g) under the reaction conditions of 500 Nm ³ / Kl. The resulting product oil had a nitrogen concentration of 0.022% by weight.

(Comparative Example 1)
Except that a commercially available titania was catalyzed as a catalyst and a Ni / Mo supported titania catalyst having a BET specific surface area of 42 m ² / g (Ni: 2.4 wt% / Mo: 16.7 wt%) was used, the same as in Example 3 above. Hydrogenation treatment was performed. As a result of this hydrogenation treatment, the nitrogen concentration of the product oil was 0.10% by weight.
When the denitrification reaction rate was determined using the denitrification reaction as the primary reaction, the catalyst of Example 2 showed about 3.5 times the denitrification activity as compared with the catalyst of Comparative Example 1.

Using a small-sized flow-type reactor, normal pressure light oil (sulfur concentration 1.3% by weight) as a raw material, reaction temperature 350 ° C., reaction pressure (hydrogen partial pressure) 5.0 MPa, LHSV2 ⁻¹ , H ₂ / oil in the reaction conditions the ratio 200 Nm ³ / Kl, phosphorus, molybdenum, cobalt supported titania catalyst of example 1 as a catalyst (BET specific surface area 149m ² / g) was subjected to hydrotreating using. The resulting product oil had a sulfur concentration of 80 ppm.

(Comparative Example 2)
As in Example 4, except that commercially available titania was catalyzed and a Co / Mo-supported titania catalyst having a BET specific surface area of 40 m ² / g (Co: 3.9 wt% / Mo: 13.3 wt%) was used. The hydrogenation treatment was performed. As a result of this hydrogenation treatment, the sulfur concentration of the product oil was 450 ppm. When the desulfurization reaction rate was determined using the desulfurization reaction as the 1.5th order reaction, the catalyst of Example 1 showed about 3.8 times the desulfurization activity as compared with the catalyst of Comparative Example 2.

Claims (4)

Particle growth inhibitor that suppresses particle growth during firing in hydrosol or hydrogel of hydrous titanium oxide represented by general formula TiO ₂ · nH ₂ O (where n is 0.02 or more) as, after the oxyanion and / or metal carbonyl anions containing P and Mo, and a metal cation of Ni and / or Co, it was added by ion exchange in a ratio of titanium oxide per 100g 0.06~6g equivalents, Porous titania for hydrogenation treatment having a specific surface area of 80 m ² / g or more obtained by drying and firing. Anion is added at a pH lower than the isoelectric point of titanium oxide , cation is added at a pH higher than the isoelectric point of titanium oxide , and an anion and a cation are added at a pH lower than the isoelectric point of titanium oxide. The porous titania for hydroprocessing according to claim 1 . Hydrosol or hydrogel of the titanium oxide, hydrotreating porous titanium dioxide according to claim 1 or 2 are prepared by swinging over a plurality of times alternately between the sedimentation zone pH and dissolution zone pH of hydrous titanium oxide . A hydrotreating method using the porous titania for hydrotreating according to any one of claims 1 to 3 as a catalyst or a catalyst carrier.