JP2006061845A - Hydrogenation catalyst for heavy oil and manufacturing method thereof - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide a hydrogenation catalyst for heavy oil which has high activity, hardly causes deterioration, has high abrasion resistance of the catalyst and is optimized for recycling, to provide a manufacturing method of the hydrogenation catalyst for heavy oil, and to provide a hydrogenation method for the heavy oil which can be stably used for a long term even after the recycling by using the hydrogenation catalyst. <P>SOLUTION: In the manufacturing method of the hydrogenation catalyst for heavy oil, inorganic oxide carriers containing alumina and titania are prepared, are caused to carry at least three kinds of metal elements selected from among the fourth, sixth, ninth, tenth and fifteenth groups of the periodic table thereon in the presence of polyethylene glycol of molecular weight 200 or more and are calcined at a temperature of 400°C or more. <P>COPYRIGHT: (C)2006,JPO&NCIPI

Description

  The present invention relates to a hydrotreating catalyst and a method for producing the same, and more particularly, to a hydrotreating catalyst suitable for reusing a hydrotreated catalyst deteriorated by hydrotreating heavy oil, a method for producing the same, and a heavy product. The present invention relates to a method for hydrotreating oil.

  In general, it is said that the cause of the decrease in the catalyst performance in the hydrotreatment of light sulfur-containing hydrocarbons such as kerosene oil is the deposition of coke (carbon content) on the catalyst. On the other hand, in heavy oil hydrotreating, unlike light oil, in addition to coke precipitation, a large amount of metal impurities such as vanadium, nickel, etc. present in the feedstock are deposited on the catalyst during hydrotreating operation. Accumulation reduces catalyst performance. Further, in the hydrotreatment of heavy oil having a high boiling point, it is necessary to operate at a temperature higher than that of light oil, so that a catalytically active metal component such as molybdenum aggregates, and the catalytic performance further decreases. In addition, since heavy oil contains a lot of hard-to-desulfurize sulfur compounds, it is more easily affected by the accumulation of vanadium and the like than hydrogenation treatment of light sulfur-containing compounds.

Also, in recent years, due to increasing environmental problems, it is desired to recycle the hydrotreating catalyst in order to reduce catalyst waste. However, in the case of heavy oil hydrotreating, coke can be removed by calcination, but it is difficult to remove accumulated vanadium and nickel, so it is difficult to stably use the regenerated catalyst for a long time. In addition, the conventional heavy oil hydrotreating catalyst has a drawback in that the wear strength of the catalyst is reduced during regeneration. When the wear strength is reduced, there is a problem that the catalyst particle gap is clogged with pulverized material at the time of refilling after regeneration, and the operation becomes impossible at the time of reuse.
Furthermore, recently, a catalyst in which nickel oxide, molybdenum trioxide, magnesium oxide, and phosphorus pentoxide are supported on an alumina carrier has been proposed (Patent Document 1). However, even with this method, the problem of lowering the wear strength during catalyst regeneration has not been solved. For this reason, an improvement suitable for recycling is required.
Further, a hydrotreating catalyst characterized by adding titania (titanium oxide) to an alumina support has been proposed (Patent Document 2). However, the catalyst in which titania is supported on the alumina carrier has a low effect of suppressing the catalyst strength during regeneration, and further improvement has been desired.

JP 11-319567 A JP 2004-148139 A

  The present invention has been made to solve the above-mentioned problems, and is a hydrotreating catalyst that is highly active, has little deterioration, has a high catalyst wear strength, and can be easily regenerated after heavy oil treatment, and its production And a method for hydrotreating heavy oil that can be used stably for a long period of time after regenerating the catalyst after hydrotreating the heavy oil using the hydrotreating catalyst. With the goal.

  As a result of intensive studies to achieve the above object, the present inventors have found that it is effective to use a catalyst having a specific metal supported on a support containing alumina and titania, and have completed the present invention. is there.

That is, the present invention
(1) An inorganic oxide support containing alumina and titania is prepared, and at least three or more metals selected from Groups 6, 9, 10, and 15 of the periodic table are prepared on the support. A method for producing a heavy oil hydrotreating catalyst, which is supported in the presence of polyethylene glycol having a molecular weight of 200 or more and calcined at 400 ° C. or higher;
(2) The heavy oil hydrogenation treatment as described in (1) above, wherein the inorganic oxide carrier containing alumina and titania is obtained by adding a water-soluble titanium complex to the alumina carrier and calcining at 400 ° C. or higher. Production method of catalyst,
(3) The method for producing a heavy oil hydrotreating catalyst according to (2), wherein the water-soluble titanium complex is an oxytitanium complex, a peroxytitanium complex, or a hydroxytitanium complex,
(4) The heavy oil hydrotreating catalyst according to (1) to (3) above, wherein the group 6 metal in the periodic table is molybdenum, the group 9 metal is cobalt, the group 10 metal is nickel, and the group 15 metal is phosphorus. Manufacturing method,
(5) The method for producing a hydrotreating catalyst according to the above (1) to (4), wherein the content of titania is from 0.1% by mass to 10% by mass based on the total amount of the catalyst,
(6) A heavy oil hydrotreating catalyst produced by the method of (1) to (5) above,
(7) A regenerated heavy oil hydrotreating catalyst obtained by subjecting heavy oil to hydrogenation using the catalyst of (6) above and then calcined,
(8) The regenerated heavy oil hydrotreating catalyst according to (7) above containing 0.1% by mass to 35% by mass of vanadium, and (9) the heavy oil according to any one of (6) to (8) above A method of hydrotreating heavy oil, characterized by hydrotreating in the presence of a catalyst;
Is to provide.

  In the present invention, the strength of the conventional catalyst is reduced during regeneration because vanadium impurities accumulated during the hydrotreating reaction of heavy oil react with the catalyst during calcination regeneration and destroy the catalyst structure. It was completed by paying attention to the fact that By adding a titanium compound having a strong bond with alumina at the time of preparing the support, the strength at the time of regeneration can be increased, and in particular, by adding a stable titanium compound at the stage of the alumina support at the time of preparing the catalyst support. And found that a strong bond can be obtained.

  That is, according to the present invention, a catalyst having a specific metal supported on a support containing alumina and titania prepared in advance can be used to obtain a highly active catalyst with improved wear strength. The use becomes much easier than the conventional catalyst, and the catalyst at the time of regeneration is higher in activity than the conventional catalyst.

  The hydroprocessing catalyst in the present invention is a processing catalyst for heavy oil such as residual oil containing sulfur, vanadium, nickel and other metals as impurities, and hydrodesulfurization, hydrodenitrogenation, hydrocracking, hydrodehydration. Although it can be used for a hydrotreating reaction of an aromatic or the like, it is particularly effective for a hydrodesulfurization reaction.

  The heavy oil hydrotreating catalyst in the present invention is produced by preparing an inorganic oxide support containing alumina and titania and supporting the specific active metal on the support. Here, the inorganic oxide used for the carrier may be one having an OH group on the surface and is not particularly limited. For the purpose of the present invention, alumina, silica, silica-alumina, magnesia, zinc oxide, Crystalline aluminosilicates, clay minerals and mixtures thereof are preferably used. Among these, alumina, particularly γ-alumina support is preferable from the viewpoint of metal dispersibility.

  In the present invention, it is necessary to support an active metal on an inorganic oxide support to which titania is added. Usually, titania is added at the time of preparing the support, which significantly increases the wear strength during catalyst regeneration. Can be increased.

  The amount of titania to be added is 0.1 to 10% by mass, preferably 0.3 to 5% by mass, and more preferably 0.5 to 3% by mass based on the final total mass of the catalyst. If it is 0.1% or less, sufficient strength cannot be obtained, and if it is 10% by mass or more, titania forms a composite oxide with molybdenum, nickel, etc., and the activity decreases.

  In general, titania is supported on a carrier of a molded article of a refractory inorganic oxide such as alumina. Generally, a titanium compound is added to a carrier gel, a kneading method, and a solution containing the titanium compound is adjusted to an amount that the carrier absorbs water. Then, there are a pore filling method in which the carrier is impregnated or a method in which the carrier is immersed in a solution containing a large excess of titanium compound. However, for recycling, it is desirable to add at the stage of an alumina carrier, for example. By adding the titanium-containing solution to the alumina molded support, the support can be uniformly coated with titania, and the strength of the catalyst can be improved.

  As the titanium-containing solution, an aqueous solution containing only titanium (ion) as a metal and an organic titanium compound solution dissolved in an organic solvent are used. Since an aqueous solution containing titanium tends to be specifically hydrolyzed, strong acidic solutions such as titanium tetrachloride and titanium sulfate are known. On the other hand, alkoxide compounds, acetylacetonate compounds, and the like are known as organic titanium compounds. However, these compounds have the following disadvantages.

  In addition to being strongly acidic and difficult to handle, aqueous solutions of titanium tetrachloride and titanium sulfate need to be supported in an extremely low pH range of pH 1 or lower because they are easily hydrolyzed. However, even in such a titanium-containing aqueous solution such as titanium tetrachloride having a pH of 1 or less, when it comes into contact with an inorganic oxide or gel such as alumina, a hydrolysis reaction occurs rapidly, and the alteration of alumina occurs. Since it is difficult to be uniformly supported thereon, the effect of titanium is not exhibited remarkably. In addition, chlorine ions and sulfate ions may adversely affect the catalytic activity, and further, chlorine ions cause corrosion for industrial equipment, so it is preferable that none of them be included.

  On the other hand, organotitanium compounds such as alkoxide compounds and acetylacetonato compounds are preferable to titanium tetrachloride and titanium sulfate because they do not contain chloride ions or sulfate ions, but they have a drawback that they are easily hydrolyzed even with a small amount of water. When the organic solvent solution comes into contact with moisture contained in the inorganic oxide at the time of impregnation or immersion, titanium hydroxide is precipitated, so that titanium is not uniformly supported. Furthermore, such an organic titanium compound is expensive, and it is extremely difficult to economically apply it to a hydroprocessing catalyst for a hydrocarbon oil that is required in large quantities.

  As a result of intensive studies to achieve the above object, the present inventors have used an aqueous solution of a water-soluble titanium complex such as oxytitanium, peroxytitanium, hydroxy (hydroxycarboxylato) titanium, and the like. It has been found that titanium can be supported on an inorganic oxide in a highly dispersed manner, and further, it is very effective for suppressing a decrease in catalyst strength during regeneration of the catalyst. Examples of such water-soluble titanium complexes include titanium peroxohydroxycarboxylic acid, titanium oxohydroxycarboxylic acid, and ammonium salts thereof, and examples of the hydroxycarboxylic acid include citric acid, malic acid, lactic acid, and tartaric acid.

As a method for adding the aqueous solution of the titanium compound to the alumina gel, a normal impregnation method or the like can be used. The temperature to add is normally room temperature-90 degreeC, More preferably, it is 40-80 degreeC. After adding the titanium compound, it is usually fired at room temperature to 600 ° C, preferably 200 to 500 ° C.
The support shape of the hydrotreating catalyst of the present invention is not particularly limited, but a shape suitable for a desired reaction mode such as a cylinder, a sphere, three to six leaves, and a honeycomb can be freely selected. In particular, in the fixed bed direct hydrodesulfurization reactor, a cylindrical shape, a three-leaf shape, and a four-leaf shape are preferably used.

  The inorganic oxide containing alumina and titania obtained as described above is fired to obtain a carrier. The calcination temperature is preferably 400 to 700 ° C., and more preferably 500 to 650, in the air or oxygen atmosphere under the condition that the residual carbon content in the catalyst with polyethylene glycol is 1.0% by mass or less. ° C. The firing time is usually 0.5 to 100 hours.

  Next, the hydrotreating catalyst in the present invention is an inorganic oxide carrier containing alumina and titania, and at least three or more selected from Group 6, Group 9, Group 10 and Group 15 of the periodic table. This metal is supported in the presence of polyethylene glycol having a molecular weight of 200 or more.

  That is, the metal (supported metal) supported on the catalyst carrier is preferably molybdenum, tungsten, or the like as the Group 6 metal of the periodic table, and molybdenum is particularly preferably used. As the molybdenum compound, molybdenum trioxide, ammonium paramolybdate and the like are suitable. As the tungsten compound, tungsten trioxide, ammonium tungstate and the like are suitable.

  As the Group 9 metal, cobalt is preferably used. As the cobalt compound, cobalt carbonate or cobalt nitrate is preferably used. Nickel is preferably used as the Group 10 metal. As the nickel compound, basic nickel carbonate, nickel nitrate and the like are preferable.

  Furthermore, phosphorus can be suitably used as the Group 15 metal. As this phosphorus compound, phosphorus pentoxide, orthophosphoric acid, or the like is used. When this is added, the stability of the aqueous solution of the metal compound supported on the catalyst is improved, and at the same time, the catalytic activity is improved as a catalyst component. Has an effect. Moreover, since the carrying | support state of nickel and cobalt which is a promoter component is improved and desulfurization activity and denitrogenation activity improve, it is preferable.

  Preferable metal compounds used in the impregnation liquid for the supporting treatment include oxides, sulfates, nitrates, carbonates, basic carbonates, oxalates, acetates, ammonium salts and the like as aqueous solutions.

The supported metal compound is usually supported on a carrier by an impregnation method. Although the above Group 6, Group 9, Group 10 and Group 15 compounds may be impregnated separately, it is efficient to carry out them simultaneously. Usually, the contents of Group 6, Group 9, Group 10 and Group 15 compounds in the impregnating solution are calculated from the target loading amount. Regarding the amount of active metal compound supported, Group 9 and Group 10 are 0.1 to 10% by mass, preferably 0.2 to 8% by mass as oxides, based on the weight of the final catalyst. Again, it is 0.1-25 mass% as an oxide, Preferably it is 0.2-20 mass%. The total supported amount of active metal is usually preferably 2 to 35% by mass, more preferably 3 to 25% by mass as an oxide, based on the final catalyst weight.
After these metals are dissolved in deionized water, the amount of the impregnating liquid is adjusted to be equal to the water absorption amount of the carrier used, and then impregnated. In consideration of the stability of the impregnating solution, the pH at the time of impregnation is generally 1 to 4, preferably 1.5 to 3.5 in the acidic region, and 9 to 12, preferably 10 to 11 in the alkaline region. The pH can be adjusted using an organic acid or ammonia.

Further, when supporting the supported metal on the support, it is necessary to carry out in the presence of polyethylene glycol having a molecular weight of 200 or more. The molecular weight of polyethylene glycol is preferably 200 to 1,000, more preferably 350 to 600. When it is 200 or more, the catalytic activity is secured, and when it is 1,000 or less, handling is easy from the viewpoint of solubility and time of the supporting step.
The amount of polyethylene glycol added is preferably 0.5 to 30 parts by mass, more preferably 1 to 15 parts by mass with respect to 100 parts by mass of the carrier. When the amount is 0.5 part by mass or more, the effect of addition is exhibited, and when it is 30 parts by mass or less, the loading can be easily performed.

  It is known that when nickel is used as one of the supported metals, spinel is formed and deactivated with alumina as a carrier component. Phosphorus compounds have the effect of suppressing the spinelization of nickel and improve the catalytic activity. However, if a large amount of phosphorus compound is used without using polyethylene glycol, a composite oxide of nickel-molybdenum-phosphorus is formed. On the contrary, the catalytic activity is lowered. When the metal compound aqueous solution to which polyethylene glycol is added as in the present invention is used, the addition amount of the phosphorus compound can be increased to 3 to 5% by mass, and the catalytic activity can be greatly improved. .

The hydrotreating catalyst in the present invention preferably supports 1 to 10% by mass of nickel oxide, 5 to 20% by mass of molybdenum trioxide, and 3 to 5% by mass of phosphorus pentoxide based on the total amount of the catalyst. When the nickel oxide content is 1% by mass or more, sufficient activity is exhibited, and when the nickel oxide content is 10% by mass or less, the activation is not reduced due to metal aggregation. When molybdenum trioxide is 5% by mass or more, sufficient activity is exhibited, and when it is 20% by mass or less, low activation due to metal aggregation is preferable. If the phosphorus pentoxide is 3% by mass or more, the effect of suppressing spinel is sufficiently exhibited, and if it is 5% by mass or less, a composite oxide with molybdenum, nickel and the like is not formed and the activation is low.
The supporting method is not particularly limited, and a known supporting operation such as an atmospheric pressure impregnation method, a vacuum impregnation method, a coating method, or a combination of these is used.

  The raw material containing an impurity metal such as vanadium is hydrogenated using the inorganic oxide carrier containing alumina and titania carrying the active metal obtained as described above. At this time, the allowable accumulation amount of vanadium is 1.5 to 50% by mass, preferably 2 to 30% by mass as the metal accumulation amount based on the new catalyst. The hydrotreating of the present invention can be applied to a wide range of heavy oils from atmospheric residue, reduced residue, asphaltene oil and tar sand oil.

  When hydrotreating using the catalyst of the present invention, it is preferable to perform a presulfidation treatment as a catalyst activation or stabilization treatment before the hydrotreating reaction. This preliminary sulfidation treatment is performed in a temperature range of 200 to 400 ° C. using hydrogen sulfide, carbon disulfide, thiophene, dimethyl disulfide (DMDS) or the like as a preliminary sulfiding agent.

Although the reaction conditions for the hydrotreating in the present invention vary depending on the type of the target feedstock, the reaction temperature is selected in the range of 200 to 500 ° C, preferably 300 to 450 ° C. The reaction pressure is preferably selected in the range of 1.47 to 24.5 MPa (15 to 250 kg / cm ² ).

The reaction format is not particularly limited, but usually, various processes such as a fixed bed, a moving bed, a boiling bed, and a suspension bed are adopted, and a flow system using a fixed bed is preferably adopted from the viewpoint of economy. The When these distribution schemes, LHSV (liquid hourly space velocity) of 0.01~45hr ^-1, and it is preferably selected in the range of 0.1 to 10 ^-1,.

Feed rate of the hydrogen gas and the oil (hydrogen / oil ratio) is usually, 50～2,000Nm ³ / kl, preferably preferably is to select a range 300～1,000Nm ³ / kl, of.
As described above, hydrodesulfurization treatment of heavy oil can be efficiently performed using the hydrotreating catalyst of the present invention.

  Hereinafter, the present invention will be described more specifically with reference to examples of the present invention and comparative examples thereof, but the present invention is not limited to these examples.

Example 1
Preparation of catalyst A (supporting titania after molding of carrier)
70 g of sodium hydroxide was dissolved in 2 liters of pure water, and 200 g of sodium aluminate was further added to obtain a uniform alumina solution (B1). Further, 1,000 g of aluminum nitrate was dissolved in 2 liters of pure water to obtain an alumina solution (A1). First, 4 liters of pure water was heated to 70 ° C., and the alumina solution (A1) was added to pH 3.6 while stirring. Next, the alumina solution (B1) was added until pH 9.0 and aged with stirring for 5 minutes. Subsequently, the alumina solution (B1) was added again to adjust the pH to 3.6 and aged for 5 minutes while stirring. Thus, the operation of changing the pH between 3.6 and 9.0 was repeated 9 times in total to obtain a boehmite gel aqueous solution.

  500 g of titanium tetrachloride and 1 liter of pure water were cooled with ice. Pure water was stirred, and titanium tetrachloride was gradually added dropwise while cooling to obtain a colorless titania sol hydrochloric acid solution. To this titania sol solution, 1.2 times equivalent of ammonia water (concentration: 1 mol / liter) was added dropwise and stirred for 1 hour to obtain a titanium hydroxide gel. The gel was separated by suction filtration, redispersed in about 1 liter of pure water, and washed by filtration. This operation was repeated 4 times until the washing solution became neutral, and the chlorine roots were removed.

The water content of the obtained titanium hydroxide gel was measured, and 11 g of titania was collected. 50 cm ^{3 of} 25% by mass aqueous ammonia was added and stirred for 30 minutes. Furthermore, 38 cm ³ of 30% by mass hydrogen peroxide water was gradually added to dissolve the titanium hydroxide gel to obtain a titanium peroxotitanium solution. 29 g of citric acid monohydrate was gradually added thereto, and the temperature was gradually raised while stirring to remove excess hydrogen peroxide at 50 ° C. Further, the solution was concentrated at 80 ° C. until the total amount became 117 cm ³ , and yellow-orange transparent titanium peroxocitrate ammonium (T1) was obtained.

  The boehmite gel was filtered, washed with deionized water, dried, and extruded into a cylindrical shape having a diameter of 1.5 mm. The extruded boehmite gel was dried at 120 ° C. for 160 hours and then calcined at 550 ° C. for 2 hours to obtain an alumina carrier (A1). To this alumina support (A1), the amount of titanium peroxocitrate ammonium (T1) with a titanium content of 3% by mass based on the support is diluted and constant volume with pure water so as to match the water absorption of A1, and normal pressure So as to impregnate A1. Then, after drying at 120 ° C. for 160 hours, baking was performed at 450 ° C. for 16 hours to obtain a titania-supported alumina carrier (C1).

Next, 69.5 g of nickel carbonate (39.7 g as NiO), 220 g of molybdenum trioxide and 31.5 g of orthophosphoric acid (purity 85%, 19.5 g as P ₂ O ₅ ) were added to 250 cm ³ of pure water, It melt | dissolved at 80 degreeC, stirring, after cooling to room temperature, the pure water was added again and it made constant volume to 250 cm < ³ >, and the impregnation liquid (S1) was adjusted. 50 cm ^{3 of} impregnating liquid (S1) was sampled, 6 g of polyethylene glycol (molecular weight 400) was added, diluted and constant volume with pure water to meet the water absorption of 100 g of carrier (C1), and impregnated at normal pressure. Then, after vacuum drying at 70 ° C. for 1 hour, heat treatment was performed at 450 ° C. for 16 hours to prepare Catalyst A.
The catalyst composition and physical properties are shown in Table 3.

Comparative Example 1
Preparation of catalyst B (titania supported on alumina carrier gel)
In Example 1, the boehmite gel was filtered, washed with deionized water, and after adding and kneading ammonium peroxocitrate (T1) to the dried boehmite gel so that the amount of titanium was 3% by weight based on the carrier. In the same manner as in Example 1, extrusion molding, drying and firing were carried out to obtain a titania-supported alumina carrier (C2).
The C2 carrier was impregnated with the impregnation liquid S1 in the same manner as in Example 1, dried and calcined to obtain Catalyst B.

Comparative Example 2
Preparation of catalyst C (without titania addition)
A catalyst C was obtained in the same manner as in Example 1 except that ammonium peroxocitrate was not added to the alumina support A1.

<Hydrodesulphurization treatment performance evaluation experiment 1> (initial activity)
For each of Catalysts A, B, and C, initial desulfurization using atmospheric residual oil obtained from Middle Eastern heavy crude oil shown in Table 1 using a high-pressure fixed-bed flow reactor with a catalyst filling amount of 50 cm ³ The performance was evaluated, and the titania addition effect and the influence of the addition method were compared and evaluated. Incidentally, the catalyst of the present invention was evaluated by combining a demetalization catalyst for a desulfurization catalyst (1.5% by weight and a MoO ₃ 4.5 wt% on the NiO).

(1-1) Pretreatment Prior to reaction, as a pretreatment, DMDS is added to LGO (light oil) to adjust the sulfur concentration to 2.5% by mass with hydrogen gas at 250 ° C. for 24 hours. Through the catalyst, the catalyst was presulfided.

(1-2) Desulfurization test The raw oil shown in Table 1 was passed through the catalyst together with hydrogen gas, and hydrodesulfurization treatment was performed under the following conditions.
Reaction conditions Hydrogen partial pressure: 135 kg / cm ²
Liquid space velocity: 0.2 hr ^-1
Hydrogen / oil ratio: 700 Nm ³ / kiloliter Table 2 shows the evaluation results. It can be seen that high hydrodesulfurization performance can be obtained in the initial stage by adding titanium. In addition, at the initial stage, there was not much difference due to the addition method.

<Hydrodesulphurization bibliographic performance evaluation experiment 2> (Activity after regeneration)
(2-1) (Production of spent catalyst)
Using the catalysts A, B, and C, hydrodesulfurization treatment of atmospheric residue shown in Table 1 was performed for 4000 hours using a fixed bed reactor. The desulfurization treatment was continued while adjusting the reaction temperature so that the sulfur content of the product oil was constant. After completion of the reaction, washing is performed by passing light oil through the catalyst in the reactor, and further, nitrogen gas is circulated to remove the dried catalyst, and the demetalized catalyst is separated by sieving, and used catalysts A, B and C was obtained.

(2-2) (Production of regenerated catalyst)
Each used catalyst obtained above was treated at 300 ° C. for 1 hour while supplying 100% nitrogen gas at 100 cm ³ / min in a rotary calciner (rotation speed: 5 rpm). Then, it baked at 450 degreeC for 3 hours, supplying the mixed gas of 50% nitrogen gas and 50% air at 100 cm < ³ > / min. After cooling the obtained catalyst, the lump and powder were removed by sieving to obtain regenerated catalysts A, B and C, respectively.

(2-3) (Measurement method of powdering rate)
As for the pulverization rate of each catalyst, 35 g of the catalyst is put on a 20 mesh sieve and shaken 100 times. 30 g of the catalyst remaining on the sieve is weighed and placed in a cylindrical rotator having a diameter of 30 cm and a width of 20 cm, and rotated at 60 rpm for 180 minutes. The obtained sample is put on a 20 mesh sieve and shaken 100 times. Measure the amount of flour. Also put all powder on the container into the sieve using a brush. The reduction amount of the catalyst weight was determined as the powdering rate. The smaller this value, the greater the wear strength.

(2-4) (Measurement results of composition and wear strength)
Table 3 shows the composition, physical properties, and wear strength of the new catalyst and the regenerated catalyst.

(2-5) (Evaluation of regenerated catalyst)
For each of the regenerated catalysts A, B and C, a small high pressure fixed bed reactor was packed with 50 cm ³ . Hydrodesulfurization reaction was performed under the same reaction conditions as the new catalyst. Table 4 shows the properties of the raw material oil used, and Table 5 shows the evaluation results.

  Catalyst A and regenerated catalyst A of the present invention using a titania-supported alumina support prepared by adding titania to an alumina support have higher wear strength than catalyst B, catalyst C, regenerated catalyst B and regenerated catalyst C, and desulfurization The performance is also highly active. This is considered that the reaction of vanadium and alumina in heavy oil is suppressed by adding titania to the carrier in advance and uniformly coating titania on the alumina carrier.

The hydrotreating catalyst in the present invention is used for hydrotreating heavy oil, and is particularly suitable for use as a regenerated catalyst.

Claims (9)

  An inorganic oxide support containing alumina and titania is prepared, and at least three or more metals selected from Groups 6, 9, 10, and 15 of the periodic table are prepared on the support, and a molecular weight of 200 or more. A method for producing a heavy oil hydrotreating catalyst, which is supported in the presence of polyethylene glycol.   2. The production of a heavy oil hydrotreating catalyst according to claim 1, wherein the inorganic oxide support containing alumina and titania is obtained by adding a water-soluble titanium complex to the alumina support and calcining at 400 ° C. or higher. Method.   The method for producing a heavy oil hydrotreating catalyst according to claim 2, wherein the water-soluble titanium complex is an oxytitanium complex, a peroxytitanium complex, or a hydroxytitanium complex.   The heavy oil hydrotreating catalyst according to any one of claims 1 to 3, wherein the Group 6 metal of the periodic table is molybdenum, the Group 9 metal is cobalt, the Group 10 metal is nickel, and the Group 15 metal is phosphorus. Production method.   The method for producing a hydrotreating catalyst according to any one of claims 1 to 4, wherein the content of titania is from 0.1% by mass to 10% by mass based on the total amount of the catalyst.   A heavy oil hydrotreating catalyst produced by the method according to claim 1.   A regenerated heavy oil hydrotreating catalyst obtained by subjecting heavy oil to hydrogenation treatment using the catalyst according to claim 6 and then calcining.   The regenerated heavy oil hydrotreating catalyst according to claim 7, comprising 0.1 mass% to 35 mass% of vanadium. A method for hydrotreating heavy oil, comprising hydrotreating heavy oil in the presence of the catalyst according to any one of claims 6 to 8.