JPS5924661B2 - Method for producing catalyst for hydrotreating heavy oil - Google Patents

Description

DETAILED DESCRIPTION OF THE INVENTION The present invention relates to a method for producing a catalyst for hydrorefining heavy oil having a metal content such as iron, vanadium, or nickel, and more specifically, a catalyst having a pore diameter of 400 Å or less and a pore volume of 1.0 ffl/ The present invention relates to a method for producing a hydrorefining catalyst with high activity and long life that is J or higher.

Hydroprocessing of heavy oil, especially residual oil, has many problems, most of which are related to the significant deterioration of catalyst performance.

For example, since heavy oil contains large amounts of asphaltene, Conradson carbon, etc., these substances may be adsorbed onto the surface of the catalyst, causing a significant decrease in activity.

Moreover, since these substances tend to deposit on the catalyst as carbonaceous substances, permanent poisoning of the catalyst by carbonaceous substances is likely to occur unless the hydrogen pressure during the reaction is maintained much higher than in the treatment of light oil.

In addition, metals such as iron, vanadium, and nickel contained in heavy residual oil accumulate on the catalyst during the reaction process, causing a decrease in activity and physically clogging the catalyst pores. is also a major cause of shortening catalyst life.

In order to overcome these problems, various efforts have been made regarding catalysts for hydrotreating residual oil.

However, there is a trade-off relationship between catalyst activity and catalyst life, or between catalyst strength and catalyst life, and a catalyst with sufficient performance has not yet been completed.

For example, in order to increase the activity, it is necessary to increase the surface area and packing density of the catalyst, but to do so, the average pore diameter and pore volume of the catalyst must be decreased.

However, in such a catalyst, the metal content in the oil precipitates intensively on the surface of the catalyst pellet, resulting in the catalyst deteriorating in a short period of time.

Therefore, it is necessary to select a pore diameter that appropriately balances activity and life.

Furthermore, deterioration due to precipitation of metals can be reduced by reducing the particle size of the catalyst, but this method has its limitations.If the catalyst is made into fine particles, the strength of the catalyst will decrease and a pressure difference will occur in a fixed bed. This has the disadvantage that it is more likely to occur.

Due to various limitations such as slanting, catalysts for hydrotreating heavy oils generally have a surface area of 100 to 200 m/9, an average pore diameter of 100 to 200 m/9, and a particle size of 1/16 to 1/16 m/9.
A 1/32 inch spherical or extruded product is used,
In this case, the pore volume of the catalyst is usually 0.5-0.8 CI
/l/ remains at around 9.

On the other hand, one way to improve the performance of heavy oil hydrocracking catalysts is to increase the surface area and correspondingly increase the pore volume, thereby changing the size of the reactor. It is possible to increase the activity and extend the catalyst life without causing any damage.

Generally, catalyst activity is proportional to the total catalyst surface area (St) per unit volume within the reactor.

That is, if the specific surface area of the catalyst is S and the packing density is D, then
The formula is 5t=SXD, and in order to increase the catalytic activity, the value of SXD should be increased.

Here, if δ is the true specific gravity of the catalyst, ■ is the pore volume, and ε is the porosity in the reactor, then D=(1−ε)/(1/δ+■).

Also, if the average pore diameter of the catalyst is r, then the well-known Wh
From Eeler's formula, 5=2v/r, so 5t=
2v/rX(1-e)/(1/δ+V) holds true.

Here, δ and ε are constants, so from this equation, if the average pore diameter of the catalyst is fixed, St will increase as ■ becomes larger.

In other words, this means that as the surface area and pore volume of the catalyst are increased while keeping the average pore diameter constant, the catalytic activity per unit volume increases.

Moreover, it is advantageous here that the thicker () the larger the total pore volume in the reactor.

This indicates that the space in which metals precipitated from the oil are deposited is increasing, and therefore the catalyst life tends to be longer.

Therefore, it can be seen that keeping the average pore diameter constant and increasing the pore volume as much as possible is effective in producing a catalyst with high activity and long life.

However, catalysts with large pore volumes have a major drawback in that their compressive strength is significantly reduced.

In particular, an increase in pore size exceeding 1000λ significantly weakens the strength of the catalyst.

When catalysts are used industrially, the length ICI for extrudates is
It must be able to withstand a load of at least 2 kg per rL.

In addition, if it is spherical, it must be able to withstand a load of 1 kg.

The compressive strength of the catalyst can be increased by increasing the diameter of the catalyst, but when it comes to hydrotreating residual oil, the catalyst effectiveness coefficient for denitrification and desulfurization reactions decreases, resulting in a decrease in reaction activity. Metal content also tends to precipitate on the pellet surface, resulting in a shortened lifespan.

Therefore, for hydrorefining of residual oil, usually 1/16 to 1/32
A grain size of inches is chosen.

Conventionally, hydrotreating catalysts generally use pure alumina as a carrier with or without addition of acidifying substances such as silica, boria, phosphorus, and fluorine, and support metals from group VIA of the periodic table and metals from group IV of the periodic table. A type of metal support is used.

There are two main methods for producing these catalysts: one is an immersion method in which a metal is supported on a pure alumina molded carrier, and the other is a method in which alumina hydrate, which is the starting material for alumina, and a catalytic metal salt are used. This is a manufacturing method called the gel mixing method, in which the ingredients are mixed and then molded.

Among these methods, the dipping method is unsuitable for producing a catalyst with a large pore volume because the pore volume after the alumina is supported inevitably decreases compared to the pore volume of the alumina before being supported.

This decrease in pore volume is thought to be caused by the catalytic metal compound occupying or clogging some of the pores that the carrier already has.

Therefore, an alumina with a pore volume considerably larger than that required after metal loading is required.

On the other hand, in the gel mixing method, the catalyst metal is added in advance to the alumina before firing, so the pores of the catalyst created during the firing process can be used as they are.

Therefore, the gel mixing method is preferable for producing a catalyst with a large pore volume, but the catalyst produced by this method has several drawbacks.

One of them is that catalysts made by the gel mixing method have lower activity than catalysts made by the immersion method.

This is thought to be because the dipping method supports the metal compound on the alumina surface, whereas the gel mixing method results in a physical mixture of alumina and the metal compound, reducing the effective surface area of the metal.

Furthermore, the gel mixing method catalyst has lower strength than the catalyst made using the immersion method (G).

The present invention has a compressive strength sufficient for practical use, and the volume of pores of 400 Å or less that directly contribute to the reaction is 1 cd.
The present invention provides a completely new method for producing a catalyst for hydrotreating residual oil with a high activity of more than 200 g/g, and solves the drawbacks of the gel mixing method while employing a production method similar to the gel mixing method.

That is, the present invention provides an aqueous solution containing 100 parts by weight of a basic aluminum salt in terms of aluminum oxide and 1 to 30 parts by weight of a molybdenum compound or tungsten compound in terms of molybdenum or tungsten.
A gel is formed by hydrothermal treatment at 100 to 260°C for 1 hour or more, then the resulting gel is molded, and the water in the molded product is replaced with a water-soluble organic solvent having a surface tension lower than that of water. Dry for a short time, then calcined at 400 to 700°C, and then add one or more metals from Group Ⅰ of the periodic table or, if necessary, one or more compounds of silicon, phosphorus, boron, and fluorine. A method for producing a catalyst for hydrotreating heavy oil, which is characterized in that it supports 100 parts by weight of a basic aluminum salt in terms of aluminum oxide, and a molybdenum compound or tungsten compound of 1 to 100 parts by weight in terms of molybdenum or tungsten. An aqueous solution containing 30 parts by weight is hydrothermally treated at 100 to 260°C for 1 hour or more to form a gel, and then the resulting gel is treated with one or more metals from Group Ⅰ of the periodic table, or as necessary. After mixing one or more of silicon, phosphorus, boron, and fluorine compounds according to the requirements, the molded product is molded, and the water in the molded product is replaced with a water-soluble organic solvent whose surface tension is lower than that of water, followed by drying in a short time. The present invention provides a method for producing a catalyst for hydrorefining heavy oil, which is characterized in that the catalyst is then calcined at 400 to 700°C.

The raw material used in the method of the present invention is an aqueous solution containing a basic aluminum salt and a molybdenum compound or a tungsten compound.

This aqueous solution is prepared by mixing a powder or aqueous solution of a molybdenum compound or tungsten compound with an aqueous solution of a basic aluminum salt.

Here the basic aluminum salt has the formula Al(OH)mX(3
m)/a, in which X is C13s NO3-
s S 04 ” indicates a first-class acid radical, and α indicates the valence of each ion.

Moreover, m is a value called basicity, and is preferably 2.4 to 2.
．． The value shall be 8.

The content ratio of the basic aluminum salt and the molybdenum compound or tungsten compound in the raw material aqueous solution is 1 to 30 parts by weight of the molybdenum compound or tungsten compound (molybdenum or tungsten compound) to 100 parts by weight of the basic aluminum salt (converted to aluminum oxide). (converted to), and preferably 10 to 20 parts by weight.

If it is less than 1 part by weight, there is no effect of adding a molybdenum compound or tungsten compound, while if it exceeds 30 parts by weight, all of the molybdenum and tungsten cannot be bonded to the boehmite produced by hydrothermal treatment of basic aluminum salt, and some of the molybdenum and tungsten are left in a free state. This is not desirable.

Here, suitable molybdenum compounds include ammonium paramolybdate, molybdic acid, molybdenum trioxide, ammonium phosphomolybdate, and sodium molybdate, and examples of tungsten compounds include ammonium paratungstate, phosphotungstic acid, and phosphotungsten. Ammonium acid, tungstic acid, ammonium tungstate silicate, potassium tungstate, sodium tungstate, etc. are preferably used.

In the method of the present invention, a raw material aqueous solution prepared as described above is hydrothermally treated at 100 to 260° C. for 1 hour or more to form a gel.

Hydrothermal treatment is usually carried out in an autoclave.

In this hydrothermal treatment, the compound or tungsten compound participates in the boehmite production reaction accompanying the dehydration condensation of the basic aluminum salt.

A molybdenum compound or a tungsten compound binds to the surface of boehmite and suppresses the growth of boehmite.

In this process, in order to adjust the shape and size of boehmite particles to be suitable for highly active and long-life catalysts, the temperature of the hydrothermal treatment is 100-260°C, preferably 150-260°C.
00°C, and the treatment time is usually 1 hour or more, preferably 2 hours or more.

However, in hydrothermal treatment, if an equilibrium state is reached, it does not change over time, so selection may be made to obtain an equilibrium state.

For example, 7 parts by weight of a molybdenum compound is added to 100 parts by weight of a basic aluminum salt (calculated as aluminum oxide).
．． According to an electron micrograph, the barite particles in the gel made by adding 5 parts by weight (calculated as molybdenum) and hydrothermally treating it at 200°C have an elliptical disk shape with a length of about 300 mm, a width of 100 mm, and a thickness of about 20 mm. The alumina molybdena produced by firing this crystal has a surface area of 330 mj/g.

On the other hand, when only an aqueous solution of a basic aluminum salt is hydrothermally treated at 200°C without adding a molybdenum compound, the boehmite particles take on a plate shape of approximately 1000 mm in width and several microns in length; Alumina molybdena produced by adding 7.5 parts by weight of molybdenum to 100 parts by weight of basic aluminum salt (converted to aluminum oxide), drying and firing, has a surface area of only 110 m/9.

Alumina made from boehmite which has developed into a plate shape is not suitable as a catalyst raw material for hydrotreating as the object of the present invention for two reasons.

One of them is that the catalytic activity is low due to the small surface area.
The second problem is that when the pore volume is increased, the pore diameter becomes too large, which tends to generate carbonaceous substances in the hydrogenation treatment of heavy residual oil, resulting in a rapid decline in activity.

Therefore, microcrystals of boehmite are desirable in the method of the present invention.

However, even if boehmite microcrystals produced in advance are mixed with a molybdenum compound or a tungsten compound, it is not possible to cause bonding between boehmite and these metals.

The present invention provides an outstanding technique in bonding boehmite microcrystals with these metals.

Furthermore, the advantage of bonding molybdenum or tungsten to boehmite microcrystals in advance is that the effective surface area of molybdenum or tungsten becomes larger and the catalytic activity becomes higher.

In addition, it has the following advantages of extremely convenient handling in catalyst production.

That is, compared to a simple mixed gel of boehmite and a molybdenum compound or a tungsten compound, the boehmite gel according to the present invention does not need to worry about outflow of molybdenum or tungsten during washing, filtration, or dehydration steps.

Moreover, the alumina molybdena or alumina tungstena produced according to the present invention after firing is much more water resistant.

That is, the alumina molybdena or alumina tungstena according to the present invention does not cause pore shrinkage even if it is soaked in water and then dried and fired again.

On the other hand, alumina carriers made from pure boehmite or mixtures of boehmite and molybdenum compounds or tungsten compounds, alumina molybdena, and alumina tungstena, which have a firing temperature of 700°C or lower, are significantly damaged by soaking in water, drying, and firing. Causes pore contraction.

A feature of the alumina molybdena or alumina tungstena according to the present invention is that it is extremely convenient in that it can support other metals necessary as a catalyst by immersing it in an aqueous solution.

Next, in the present invention, the gel obtained by the above-described operation is molded into a molded article.

Molding can be carried out by various methods, but for example, a molded product can be obtained by adjusting the water content of the gel in advance and extruding it through the holes of a die using a suitable extruder.

In addition, when molding the gel, one or more metals from group Ⅰ of the periodic table that have hydrogenation ability, such as cobalt and nickel, as well as silicon, phosphorus, boron, and fluorine, which combine with alumina to develop acidity, are added as necessary. It is also effective to mix one or more compounds into the gel.

If this molded product is then dried and fired as it is,
Only extremely poor pore volume and surface area can be obtained.

This is because when the water in the molded product evaporates, its surface tension causes the gel structure of the molded product to contract.

In order to prevent this shrinkage of the boehmite gel, in the method of the present invention, the water in the molded boehmite gel is replaced with an organic solvent whose surface tension is lower than that of water, and this is rapidly dried to obtain the best pore properties. It is possible to create a catalyst with

Normally, when a mixture of boehmite gel and a molybdenum compound or tungsten compound is molded and washed with an organic solvent, the solid content of the molded product must be kept at 20% or more, otherwise it will swell with the organic solvent and lose its shape. Furthermore, when the boehmite gel is dried or filtered under pressure to reach a solid content of 20% or more, the physical properties of the molded product change due to the arrangement of its crystals.

It is still unclear why the molded product according to the present invention does not lose its shape during the process of dehydration and dehydration by immersing it in an organic solvent with a solid content of about 20% or less, but ordinary boehmite microcrystals are In contrast, in the present invention, the boehmite microcrystals bonded to molybdenum or tungsten have an ellipsoidal shape, or the molybdenum or tungsten bonded to the surface of boehmite has some effect. It is also possible that this is due to the reason.

The water-soluble organic solvent used in the present invention, which has a surface tension lower than that of water, can be almost any liquid substance that is miscible with water.

However, desirably, it is thermally stable, inexpensive, less toxic, has a low viscosity, and has a high vapor pressure.

In that respect, alcohols having 1 to 6 carbon atoms such as methanol, ethanol, n-furopanol, i-propanol,
Preferred are alcohol, n-butanol, i-butanol, amyl alcohol, hexyl alcohol, acetone, glacial acetic acid, and the like.

All of these have a surface tension of 20 dyne/cm, which is significantly lower than that of water.

The boehmite according to the present invention is preliminarily added with compounds containing Group I metals of the periodic table such as nickel and cobalt, as well as silicon, boron, phosphorus, fluorine, etc., and these compounds have extremely low solubility in water. Preference is given to selecting organic solvents.

The reason for this is to prevent these compounds from being separated from the gel molding during the process of washing the gel molding with a large amount of organic solvent.

Next, it is necessary to pay sufficient attention to the drying of the molded product substituted with the organic solvent in this manner.

When a gel molded product substituted with an organic solvent is left in the air to air dry, the molded product undergoes significant shrinkage, and the resulting alumina molybdena or alumina tungsten has extremely poor surface area and pore volume. It becomes a thing.

As a result of various studies on the effect of drying rate on physical properties, the present inventors found that if the organic solvent is rapidly scattered by exposing the molded product to an atmosphere in which a large amount of heat is applied, the pore volume of the molded product increases. was found to be significantly large.

If the pore volume of the final alumina molybdena or alumina tungsten is to be 1 crit/g or more, the time required for drying must be within 60 minutes, and preferably drying is completed within 20 minutes. .

The faster the drying rate, the larger the pore volume and surface area of the resulting catalyst, but the lower the compressive strength, so it is necessary to control the drying rate as necessary.

Regarding the drying method, it is necessary that the weight reduction rate of each pellet be the same and continuous in order to eliminate variations in the physical properties of individual pellets.

Therefore, it is preferable to use a method in which the molded product is dropped from the top of a hot-blast stove or a method in which the molded product is moved at a constant speed in a rotary kiln.

Next, when replacing with an organic solvent, the amount of water dissolved in the organic solvent also greatly affects the physical properties.

As the water content increases, the physical properties of the finally obtained catalyst deteriorate.

However, if the water content is extremely reduced, the catalyst becomes 6
Because the large pores of 00 Å or more increase, the compressive strength becomes significantly smaller.

Therefore, the water content in the organic solvent is kept within the range of 0.91% to 20%, preferably 1% to 10%.

Furthermore, in order to finalize the catalyst from the molded product dried in the method of the present invention, the molded product must be heated to 400 to 700
After firing at ℃, it is necessary to support the necessary metal elements and the like.

However, as described above, if these are mixed before forming the gel, there is no need to support the metal element again.

The substance to be supported here is one or more of Group I metals of the periodic table, such as nickel, cobalt, and iron.

Furthermore, it is also effective to support one or more of silicon, phosphorus, boron, and fluorine compounds as necessary.

There are no particular limitations on the method of supporting these substances, and simple operations such as sprinkling these substances on the molded article or immersing the molded article in an aqueous solution of these substances may be used.

When using the latter method, ammonia must not be present in the aqueous solution.

This is because ammonia often makes it easier for molybdenum or tungsten to separate from the catalyst.

Molded products immersed in materials such as metals are heated to 250 to 650°C.
It is fired again.

Incidentally, sprinkling or dipping with an aqueous solution of a metal salt or the like may be performed in one step or may be performed in multiple steps.

The catalyst thus obtained is an extremely effective catalyst for the hydrorefining of heavy oil, and has significantly higher activity and extremely long life than conventional catalysts.

In addition, catalysts made by supporting not only Group I metals of the periodic table but also compounds of silicon, phosphorus, boron, or fluorine have remarkable activity in the denitrification reaction of heavy oil hydrogenation reactions. Using this catalyst, the denitrification rate of heavy oil can be significantly increased.

Next, examples of the present invention will be shown.

Comparative Example 1 An aqueous solution of basic aluminum nitrate having a No3-/klcD molar ratio of 0.43 and an A6203 concentration of 5 wt % was hydrothermally treated at 130° C. for 5 hours in an autoclave.

When the resulting slurry was dried, X-ray diffraction showed a broad peak of boehmite.

After adding 0.71 g of 3 mol/l aqueous ammonia to this slurry (5000.9 g) and stirring well, it was filtered, and the filtered cake was filtered and washed three times with 41 g. of distilled water.

The solid content concentration of the final cake was 17 wt%.

An aqueous solution of ammonium paramolybdate was mixed into this cake so that the weight ratio of Mo/Al2O3 was 0.15, and this was dried to form a gel with a solid content concentration of 22%.

This gel was washed with an n-butanol solution of about 10 times the weight and filtered.

Although some molybdenum was eluted into n-butanol, the amount was small.

The solid content concentration of this gel in which water was replaced with n-butanol was 20%.

This gel was molded using a piston-type extruder with a diameter of 1 mm.
An extrusion molded product of 5 dragons was obtained.

This was dried at 80°C and then fired at 550°C for 4 hours.

The fired product was immersed in an ethanol solution of cobalt nitrate so that 4 wt% of CoO was supported on Al2O3, the ethanol was scattered, and the product was fired at 500° C. for 2 hours to produce a catalyst.

This is designated as catalyst R.

Example l An aqueous solution of ammonium paramolybdate was added to an aqueous solution of basic aluminum nitrate with a NO3/A6 molar ratio of 0.4, and a weight ratio of Mo/11120 g was 0.15, Al2O3
A solution with a converted concentration of 5 wt% was prepared, and this was hydrothermally treated at 180° C. for 3 hours.

3 mol/l ammonia water 21 was added to 14,000 g of the resulting slurry and stirred well.

Thereafter, this neutralized slurry was filtered to obtain a hydrogel with a solid content concentration of 15 wt%.

In the filtrate, 0.25~/d of molybdenum and 0.31~/d of aluminum were detected, which corresponds to about 1.5% of the total amount of molybdenum, and 0.5% of the total amount of aluminum. It corresponds to the degree.

This gel was extruded using a piston-type molding machine through a die with a pore diameter of 1.5 mrn.

The extrudate was packed in a packed tower and washed with acetone.

The moisture concentration of acetone at the outlet of the packed tower was measured at regular intervals, and when the value fell below 2%, washing was stopped and the mixture was rapidly dried with hot air.

The melt transfer rate was varied by adjusting the amount of hot air applied to each 200 g of molded product in which water had been replaced with acetone, and four types of xerogels were obtained.

After baking this at 550℃ for 4 hours, sprinkle an aqueous solution of cobalt nitrate as CoO so that it becomes 3wt% relative to Al2O3, and baking it at 500℃ for 2 hours, Co-MO-A
1203 catalysts A, B, C, and D were obtained.

Table 1 shows the physical properties of these four types of catalysts.

Here, the catalyst obtained with a drying time of 250 minutes had a pore volume of 1.
It was less than 0i/g and was not suitable as the intended catalyst.

Further, from Table 1, it can be seen that comparative catalyst R has a lower strength than catalyst B manufactured by the method of the present invention, which has the same pore volume and surface area.

Example 2 An aqueous solution of ammonium paratungstate was added to an aqueous solution of basic aluminum nitrate with a NO3-/A6 (molar ratio) of 0.4, and a weight ratio of W/Al2O3 of 0.167 and Al
Prepare a solution with a 2O3 concentration of 5wt% and heat it at 170°C for 5%.
Hydrothermally treated for hours.

3 mol/l ammonia water 2e was added to the produced slurry 14000.9 and stirred well.

When this neutralized slurry was filtered, a hydrogel with a solid content concentration of 18% was obtained.

Almost no molybdenum or aluminum was present in the P liquid at this time.

This gel was extruded using a piston-type molding machine through a die having a hole diameter of 1.5 mm.

The extruded product was replaced with methanol in the same manner as in Example 1, rapidly dried, and then calcined at 550° C. for 4 hours.

A nickel nitrate aqueous solution was added to this xerogel as NiO.
500 immersed in 8wt% of l2O3
C. for 2 hours to obtain a Nt-W-A6203 catalyst.

Its physical properties are shown in Table-1. Example 3 Catalysts A, B, C, D, E, and R were tested for activity using Gatsuchisaran atmospheric distillation residue oil having the properties shown in Table 2.

The reaction conditions are shown in Table-3. The results were as shown in Figure 1.

From this result, when the pore volume is less than 1 d, the activity decreases and the life becomes significantly shortened, and the catalyst initially has high activity, but the activity decreases significantly (G).

Furthermore, it can be seen that the activity of Comparative Catalyst R is clearly lower than that of Catalyst B according to the present invention, which has approximately the same surface area and pore volume.

Example 4 A molybdenum-containing boehmite gel prepared in the same manner as in Example 1 was filtered to obtain a hydrogel with a solid content concentration of 16%.

In addition, aluminum ions are present in the P solution at 3.81n9/i.
exists, but molybdenum ion is 0.03■/cr
IL, or did not exist.

Silica sol was added to this hydrogel so that the weight ratio of sio 2 /A 1203 was 0.10, and Cod/
An aqueous cobalt nitrate solution was added so that the weight ratio of λ1203 was 0.04, and finally aqueous ammonia was added and stirred well.

The final pH of this slurry was 8.2.

This slurry was dried to obtain a mixed gel with a solid content concentration of 18%, which was molded, washed and dried in exactly the same manner as in Example 1, and finally baked at 500° C. for 4 hours.

This was designated as Catalyst F and its physical properties are shown in Table 4.

Example 5 A solution of 5 wt% as Al2O3 of basic aluminum chloride with C1/kl (mol) 0.5 10000. ! Molybdic acid (H2MOO4) powder in 9 126.6.9
were mixed and hydrothermally treated at 180°C for 5 hours while stirring well.

To the resulting gel, 3 mol/l of ammonia water 21 was added and stirred well to precipitate free aluminum chloride, and washing and filtration were repeated until the presence of C1- ions was no longer recognized in the P solution.

The filtered cake had a solids concentration of 19%.

This cake was molded and washed with acetone in exactly the same manner as in Example 1, rapidly dried, and then baked.

Calcined alumina molybdena has a pore volume of 1, s 2
cyyt/&, showed a surface area of 366 ml 9.

Cobalt nitrate was added to this as CoO to make it 4.0 wt% based on Al2O3, and Al2O3 was added as B2O3.
An aqueous solution to which boric acid was added at a concentration of 8 wt % based on O3 was sprayed onto the surface and baked at 500° C. for 2 hours.

This was designated as Catalyst G and its physical properties are shown in Table 4. Example
6 A reaction test was carried out on Catalysts B, E, F, and G in the same manner as in Example 3 using the same feedstock oil, and changes in denitrification rates were investigated.

This change is shown in FIG.

It can be seen that Catalysts F and G clearly have higher denitrification properties than Catalysts B and E.

However, the analytical values for asphaltenes and Conradson carbon after 300 hours were as shown in Table 5 below, indicating that catalyst E had the highest activity in removing asphaltenes.

[Brief explanation of the drawing]

Figure 1 shows Table 1 using the feedstock oil in Table 2 in Example 3.
The desulfurization performance of six types of catalysts was investigated under the operating conditions of No. 3. FIG. 2 shows the results of examining the denitrification performance of four types of catalysts under the operating conditions shown in Table 3 using the feedstock oil shown in Table 2.

Claims (1)

[Claims] 1. An aqueous solution containing 100 parts by weight of a basic aluminum salt in terms of aluminum oxide and 1 to 30 parts by weight of a molybdenum compound or tungsten compound in terms of molybdenum or tungsten.
A gel is formed by hydrothermal treatment at ℃ for 1 hour or more, then the resulting gel is molded, and the water in the molded product is replaced with a water-soluble organic solvent that has a lower surface tension than water. 1. A method for producing a catalyst for hydrorefining heavy oil, which comprises drying, then calcining at 400 to 700°C, and then supporting one or more metals from Group 1 of the periodic table. 2 The amount of the molybdenum compound or tungsten compound contained in the aqueous solution is 10 to 20 parts by weight (converted to molybdenum or tungsten) per 100 parts by weight of the basic aluminum salt (converted to aluminum oxide). The method described in Section 1. 3. The method according to claim 1, wherein the temperature of the hydrothermal treatment is 130 to 200°C. 4 A water-soluble organic solvent with a lower surface tension than water has a carbon number of 1.
The method according to claim 1, wherein the compound is one or more compounds selected from the group consisting of -6 alcohols, acetone, and acetic acid. 5. The method according to claim 1, wherein the drying time is 60 minutes or less. 6. The method according to claim 5, wherein the drying time is 20 minutes or less. 7. An aqueous solution containing 100 parts by weight of a basic aluminum salt in terms of aluminum oxide and 1 to 30 parts by weight of a molybdenum compound or tungsten compound in terms of molybdenum or tungsten.
A gel is formed by hydrothermal treatment at °C for 1 hour or more, and then one or more metals from group Ⅰ of the periodic table are mixed with the resulting gel, which is then molded, and the water in the molded product is further removed. A method for producing a catalyst for hydrorefining heavy oil, which comprises replacing the catalyst with a water-soluble organic solvent having a surface tension lower than that of water, drying in a short period of time, and then calcining at 400 to 700°C. 8. Claim No. 8, wherein the amount of the molybdenum compound or tungsten compound contained in the aqueous solution is 10 to 20 parts by weight (converted to molybdenum or tungsten) per 100 parts by weight of the basic aluminum salt (converted to aluminum oxide). The method described in Section 7. 9. The method according to claim 7, wherein the temperature of the hydrothermal treatment is 130 to 200°C. 10 A water-soluble organic solvent with a lower surface tension than water has a carbon number of 1.
8. The method according to claim 7, wherein the compound is one or more compounds selected from the group consisting of alcohols, acetone, and acetic acid. 11 Claim 7 where the drying time is 60 minutes or less
The method described in section. 12 Claim 11: Drying time is 20 minutes or less
The method described in section. 13 An aqueous solution containing 100 parts by weight of a basic aluminum salt in terms of aluminum oxide and 1 to 30 parts by weight of a molybdenum compound or tungsten compound in terms of molybdenum or tungsten,
A gel is formed by hydrothermal treatment at ℃ for 1 hour or more, then the resulting gel is molded, and the water in the molded product is replaced with a water-soluble organic solvent that has a lower surface tension than water. A heavy material characterized by being dried, then calcined at 400 to 700°C, and then supporting one or more metals of Group I of the periodic table and one or more compounds of silicon, phosphorus, boron, and fluorine. A method for producing a catalyst for oil hydrorefining. 14 The amount of the molybdenum compound or tungsten compound contained in the aqueous solution is 10 to 20 parts by weight (converted to molybdenum or tungsten) per 100 parts by weight of the basic aluminum salt (converted to aluminum oxide). The method described in item 13. 15. The method according to claim 13, wherein the temperature of the hydrothermal treatment is 130 to 200°C. 16 Water-soluble organic solvents with a surface tension higher than water have a carbon number of 1
14. The method according to claim 13, wherein the compound is one or more compounds selected from the group consisting of -6 alcohols, acetone, and acetic acid. 17 Claim 13, wherein the drying time is 60 minutes or less
The method described in section. 18 Claim 17: Drying time is 20 minutes or less
The method described in section. 19 An aqueous solution containing 100 parts by weight of a basic aluminum salt in terms of aluminum oxide and 1 to 30 parts by weight of a molybdenum compound or tungsten compound in terms of molybdenum or tungsten,
A gel is formed by hydrothermal treatment at ℃ for 1 hour or more, and then one or more metals from group Ⅰ of the periodic table, silicon,
After mixing with one or more of phosphorus, boron, and fluorine compounds, it is molded, and the water in the molded product is replaced with a water-soluble organic solvent that has a lower surface tension than water, and then dried for a short time. A method for producing a catalyst for hydrorefining heavy oil, which comprises firing at a temperature of 400 to 700°C. The content of the molybdenum compound or tungsten compound contained in the aqueous solution is 10 to 20 parts by weight (converted to molybdenum or tungsten) per 100 parts by weight of the basic aluminum salt (converted to aluminum oxide). The method according to item 19. 21. The method according to claim 19, wherein the temperature of the hydrothermal treatment is 130 to 200°C. ηA water-soluble organic solvent with a lower surface tension than water has 1 or more carbon atoms.
20. The method according to claim 19, wherein the compound is one or more compounds selected from the group consisting of No. 6 alcohol, acetone, and acetic acid. 23 Claim No. 19 in which the drying time is 60 minutes or less
The method described in section. 24. Claim 23, wherein the drying time is 20 minutes or less
The method described in section.