JPS6225418B2 - - Google Patents

Description

[Detailed description of the invention]

The present invention relates to a hydrocracking catalyst composition capable of obtaining middle distillates such as kerosene and gas oil in high yield from heavy oil, particularly residual oil. While crude oil is becoming heavier worldwide, the demand for petroleum products is increasing, and as a result, the shortage of middle distillates such as kerosene and diesel oil has become a more serious problem than ever before. In response to these social trends, many hydrocracking techniques for obtaining middle distillates from vacuum gas oil and the like have been proposed, and many oil refineries are actually conducting commercial operations. However, although it is hoped that the hydrocracking technology for producing commercial grade middle distillates from the increasing number of residual oils will be established as soon as possible, large amounts of vanadium and nickel are contained in the hydrocracking technology. Heavy metals such as nitrogen compounds, or even macromolecules such as asphaltene, cause clogging of catalyst pores due to the precipitation of heavy metals, poisoning of decomposition active sites by nitrogen compounds, and further hydrogen decomposition due to the precipitation of carbonaceous substances due to asphaltene. The problem is that the catalyst rapidly deactivates, and no satisfactory technology or catalyst has been developed. Conventional technology uses silica-alumina and alumina-based materials that have a large amount of decomposition activity, that is, highly acidic.
Attempts have been made to improve resolution by using solid acidic carriers such as titania and alumina-zirconia. Some catalysts have been proposed in which zeolite is added in order to further improve the resolution, but the majority of these products are naphtha and gas, and they are not effective for the purpose of obtaining middle distillates. In addition, by making the pore size of the catalyst relatively small, it is possible to prevent asphaltene from entering the pores and suppressing the precipitation of heavy metals and carbonaceous matter, or by making the pore size of the catalyst relatively large, it is possible to prevent asphaltene from entering the pores. A method has been devised to prevent pore clogging caused by heavy metal and carbonaceous precipitation caused by intrusion into the pores.
However, solid acid carriers such as silica-alumina, alumina-titania, and alumina-zirconia
However, it cannot exhibit sufficient cracking activity and shows only low activity for the hydrocracking of heavy oils, especially residual oils. Regarding the pore structure of the catalyst, a catalyst with the above-mentioned characteristics produces better results than a catalyst whose pore diameter is not specially adjusted. Based on the points mentioned above, the present inventors have conducted extensive research and found that alumina-borya has the highest decomposition activity as a solid acid carrier, and that by further controlling the catalyst pore characteristics, a surprising intermediate It was found that it exhibits high distillate yield and long life.
In other words, molecules to be hydrogenated can enter the pores of the catalyst, but by imparting pore characteristics that prevent large molecules such as asphaltene from entering the pores, carbonaceous and They have discovered a catalyst that prevents the precipitation of heavy metals and the accumulation of nitrogen compounds, and maintains high activity and long life. If the pore diameter is made smaller than the limit in order to prevent asphaltene and other substances from entering the pores of the catalyst, not only will the molecules to be hydrogenolyzed not be able to enter the pores, but the pores will gradually become smaller over long-term operation. This undesirably results in a decrease in the decomposition activity of relatively large molecules and an increase in naphtha and gas production. Although there are still many unknowns as to why alumina-borya is particularly superior among solid acid carriers, the solid acid properties of alumina-borya and the support activity of alumina-borya, which contain a large amount of Bresdet acid (B acid), are important. Increased hydrogenation activity due to interaction with metallic components is extremely effective in decomposing heavy oil. Therefore, the present invention provides a hydrocracking catalyst composition for heavy oil in which metals of Groups 6A and 8 of the periodic table are supported on a carrier made of a mixture of alumina and boron oxide. The present invention provides a hydrocracking catalyst composition that satisfies both conditions (A) and (B) below. (A) When measured by nitrogen gas adsorption method, the diameter is 0~
Average diameter of pores in the range of 600Å from 70 to 100Å
, the volume occupied by pores with a diameter of 70-100 Å is at least 70% of the volume occupied by pores with a diameter of 0-600 Å, and the volume occupied by pores with a diameter of 0-60 Å is at least 70% of the volume occupied by pores with a diameter of 0-600 Å. 20% of the volume occupied
Must be below. (B) Diameter between 62 and 600 as measured by mercury porosimetry
The average diameter of pores in the range of Å is 70-100 Å, and the volume occupied by pores with an average diameter ± 10 Å is at least the volume occupied by pores with a diameter of 62-600 Å.
The volume occupied by pores with an average diameter of +10 Å or more accounts for 60% of the volume occupied by pores with a diameter of 62 to 600 Å.
Must be 15% or less. The catalyst composition of the present invention is prepared by mixing a boron compound with alumina or its precursor that satisfies both conditions (a) and (b) below, and supporting a group 6A metal and a group 8 metal of the periodic table in this mixture. It is prepared by letting. (a) When measured by nitrogen gas adsorption method, the diameter is 0~
Average pore diameter in the range of 600 Å from 110 to 140
Å, the volume occupied by pores with a diameter of 100 to 150 Å is at least 70% of the volume occupied by pores with a diameter of 0 to 600 Å, and the volume occupied by pores with a diameter of 0 to 60 Å is at least 70% of the volume occupied by pores with a diameter of 0 to 600 Å 10 of the volume occupied by
% or less. (b) Diameter between 62 and 600 when measured by mercury porosimetry
The average diameter of pores in the range of Å is 100-140 Å, and the volume occupied by pores with an average diameter ± 10 Å is at least the volume occupied by pores with a diameter of 62-600 Å.
60%, and the volume occupied by pores with an average diameter + 10 Å or more is the volume occupied by pores with a diameter of 62 to 600 Å.
Must be 10% or less. As mentioned above, the alumina used in the present invention is
The average pore size is approximately 100 to 140 Å, and the pore distribution is in an extremely narrow range. By mixing this alumina and a silicon compound such as boric acid, an alumina-boria support having the characteristic pore distribution of the present invention can be obtained, and furthermore, this support exhibits solid acid properties unique to alumina-boria. It is. Therefore, if alumina does not satisfy both of the above conditions (a) and (b), it is natural that the hydrocracking activity will inevitably decrease. Moreover, if the carrier does not have an alumina-borya composition, the hydrogenolysis activity will naturally be reduced. Alumina that satisfies both conditions (a) and (b) above is obtained by molding amorphous alumina hydrate containing pseudoboehmite with a crystallite size of 40 to 80 Å into particles, etc., and then drying it.
It can be produced by firing at a temperature of ~600°C. Pseudo-boehmite is an aluminate or
It exists in amorphous alumina hydrate obtained by neutralizing aluminum salt with acid or alkali, but its crystal size is generally small, usually around 30 Å. Therefore, the crystallite diameter of pseudo-boehmite was set to 40 to 80.
In order to grow Å, 5wt% as alumina is required.
The amorphous alumina hydrate preferably having a concentration of 8 wt% or more may be stirred under slightly alkaline conditions of pH 8 to 12, preferably PH 9 to 11, and heated to 50°C or higher, preferably 80°C or higher. . The carrier used in the present invention is an alumina-boria to which a boron compound is added so as to contain 5 to 30 wt% of boron oxide. More preferably, a boron compound is added to contain 10 to 20 wt% of boron oxide. The above-mentioned alumina-boria support can be produced by a known method of mechanically mixing alumina hydrate and a boron compound, molding, drying and firing. The carrier obtained in this way contains one or more metals of group 6A of the periodic table and metals of group 8 of the periodic table as hydrogenation metals.
One or more group metals are supported in the form of metal oxides or metal sulfides. In this case, it can be supported by a known method such as an impregnation method. The Group 6A metal may be either chromium molybdenum or tungsten. Similarly, iron as a Group 8 metal,
Both cobalt and nickel can be used. The amount of Group 6A metal supported is preferably 5 to 24 wt% of the final catalyst product in metal terms, preferably 7 to 24 wt%.
16 wt% Group 8 metal loading is 0.5 to 8 wt% of the final catalyst product in terms of metal, preferably 1.5 to 5 wt%
It is. The catalyst composition of the present invention has an overall specific surface area of 200
It exhibits physical properties of ~400 m ² /g pore volume 0.3-0.8 ml/g. The catalyst composition of the present invention exhibits particularly excellent properties when obtaining middle distillates such as kerosene and gas oil from heavy oil, particularly atmospheric residue oil, in high yield. It can also be used when hydrocracking heavy oils such as vacuum residue oil, visbreaking spill oil, tar sand oil, and black oil. When heavy oil is hydrocracked using the catalyst of the present invention, a wide range of reaction conditions can be employed, including reaction conditions conventionally employed, but the reaction temperature is usually 300 -
500℃ reaction pressure 50~200Kg/ ^cm2 G hydrogen/oil ratio 400~
Conditions of 3000 m ³ /KlLHSV 0.1 to 3.0 hr ⁻¹ are used. If more preferable reaction conditions are shown, the reaction temperature
350-450°C, reaction pressure 100-170 Kg/cm ² G hydrogen/oil ratio 1000-2000 Nm ³ /KlLHSV = 0.2-1.0 ^{hr -1} . Examples and comparative examples are shown below. Example (1) Production of alumina A 50% gluconic acid aqueous solution was added to a sodium aluminate solution with a concentration of 5.0% by weight as alumina, and then an aluminum sulfate solution with a concentration of 2.5% by weight as alumina was added to adjust the pH of the prepared slurry.
I set it to 7.0. This alumina slurry was separated using a table filter and washed with 0.2% by weight ammonia water to produce an alumina hydrate containing pseudo-boehmite. A small amount of ammonia water was added to this alumina hydrate to adjust the slurry pH of the alumina hydrate to 10.60, and the alumina concentration to 8.8% by weight. After stirring under reflux for 20 hours at 95°C, pseudo-boehmite crystals were formed. The particle diameter was grown to 65 angstroms. This alumina hydrate was heated and concentrated using a kneader to obtain a hydrate (X). This =
The compound (X) was molded into granules with a diameter of 0.9 mm using an extrusion molding machine, dried in air at 110°C for 16 hours, and then calcined at 550°C for 3 hours. The average diameter of the pores in the 0-600 angstrom range determined by the nitrogen adsorption method of the obtained alumina was 134 angstroms, and the average diameter of the pores in the 0-600 angstrom range was 84.0 angstroms. %, and the pores in the 0-60 angstrom range were 1.2% of the pores in the 0-600 angstrom range. Also, 62~ determined by mercury intrusion method
The average diameter of pores in the 600 Å range is 128 Å, pores with a diameter in the 128 Å ± 10 Å range account for 90.4% of the pores in the 62-600 Å range, and pores with a diameter of 138 Å or more are 62-600 Å.
It was 6.4% of the pores in the range. (2) Production of catalyst A An aqueous solution prepared by adding 895 g of boric acid to water 4 and dissolving it under heating was mixed with 9 kg of the above hydrate (X), and the mixture was kneaded using a kneader. After drying in a medium temperature at 110°C for 16 hours, the catalyst carrier was calcined at 550°C for 3 hours to obtain a catalyst carrier having a boron oxide content of 15% by weight. An aqueous solution containing 161 g of ammonium paratungstate and 132 g of nickel nitrate in 660 g of this carrier.
ml was added for impregnation, the temperature was gradually raised to 250°C and dried, and then calcined at 550°C for 2 hours to obtain catalyst A. The supported amounts of tungsten and nickel in this catalyst were 13.5 wt% and 3.1 wt% as metals, respectively. (3) Production of Catalyst B Catalyst B with a boron oxide content of 8 wt% based on the carrier was produced in exactly the same manner as in Example (2), except that an aqueous solution in which 428 g of boric acid was added to Water 2 and dissolved under heating was used. . The supported amounts of tungsten and nickel in this catalyst are 13.5wt% and 3.1wt% as metals, respectively.
It was hot. (4) Production of Catalyst C Catalyst C with a boron oxide content of 2.5% by weight was produced in exactly the same manner as in Example (2), except that an aqueous solution prepared by adding 1690g of boric acid to 7.5% water and dissolving it under heating was used. The supported amounts of tungsten and nickel in this catalyst are 13.5wt% and 13.5wt% as metals, respectively.
It was 3.1wt%. Comparative Example (1) An aluminum sulfate solution with a concentration of 1.0 wt% as Al ₂ O ₃ was added to a sodium aluminate solution with a concentration of 2.0 wt % as Al ₂ O ₃ to obtain a slurry with a pH of 7.0. After separating this slurry using a table filter, the filter cake was washed with aqueous ammonia to prepare a pseudo-boehmite-containing alumina hydrate. Divide this alumina hydrate into two parts and add a small amount of ammonia water to one half to reduce the Al ₂ O ₃ concentration.
A slurry of 8.5 wt % and pH 10.5 was refluxed at 95° C. for 2 hours with stirring, and then the remainder of the alumina hydrate that had been divided into two portions was added and spray-dried.
Next, aqueous ammonia was added to the obtained powder and the powder was kneaded to obtain a moldable hydrate (Y).
In addition, the diameter of this Japanese product (Y) is
The pore characteristics of the alumina obtained by molding into 0.9 mm granules, drying in air at 110°C for 16 hours, and then calcining at 550°C for 3 hours are as follows. The average diameter of pores in the range of 0 to 600 angstroms determined by the nitrogen adsorption method is 156 angstroms, and pores with diameters in the range of 100 to 150 angstroms account for 29.8% of the pores in the range of 0 to 600 angstroms. Pores in the 60 angstrom range were 0% of pores in the 0-600 angstrom range. Also, it was determined by mercury intrusion method.
The average diameter of pores in the 62-600 angstrom range is 151 angstroms, and the pores with a diameter of 151 angstroms ± 10 angstroms have a diameter of 62 to 600 angstroms.
59.1% of pores in the 600 angstrom range, and 62 to 600 pores larger than 161 angstrom
It was 22.0% of the pores in the angstrom range. (2) Production of Catalyst D Catalyst D was prepared in exactly the same manner as in Example (2) except for using the above hydrate (Y). The boron oxide content of this catalyst is 15wt as a carrier.
%, the supported amounts of tungsten and nickel are 13.5wt% and 3.1wt in the final catalyst as metals, respectively.
It was %. (3) Production of Catalyst E Aqueous ammonia was added to the alumina hydrate powder obtained by slurrying the pseudoboehmite-containing alumina hydrate obtained in Example 1 and spray-drying it to prepare a hydrate (Z). ) and use an extruder to make the diameter
It was molded into granules of 0.9 mm, dried in air at 110°C for 16 hours, and then calcined at 550°C for 3 hours. The average diameter of pores in the 0-600 angstrom range determined by the nitrogen adsorption method of the obtained alumina was 84 angstroms, and the average diameter of pores in the 100-150 angstrom range was 10.5 of the 0-600 angstrom diameter pores. %, and the pores in the 0-60 angstrom range were 2.7% of the pores in the 0-600 angstrom range. Furthermore, the average diameter of pores in the range of 62 to 600 angstroms determined by mercury intrusion method is 77 angstroms, and the pores in the diameter range of 77 angstroms ± 10 angstroms account for 82.6% of the pores in the range of 62 to 600 angstroms. pores larger than angstroms are in the 62 to 600 angstrom range.
It was 12.0%. Catalyst E was prepared in exactly the same manner as in Example (2) except that the above alumina hydrate (Z) was used. The boron oxide content of this catalyst is 15wt% as a carrier,
The amounts of tungsten and nickel supported as metals in the final catalyst were 13.5 wt% and 3.1 wt%, respectively. (4) Production of Catalyst F An aqueous solution of 2.78 kg of zirconyl nitrate dissolved in water from step 5 and 6 kg of alumina hydrate (X) obtained in Example (1) were mixed, and the mixture was kneaded in a kneader to give a diameter of 0.9 kg. The particles were molded into particles of 1 mm in size, dried in air at 110°C for 16 hours, and then calcined at 550°C for 3 hours to prepare a carrier with a zirconium oxide content of 40 wt%. Other than that, the procedure was exactly the same as in Example (2), and the amount of tungsten and nickel supported was 13.5wt% and 13.5wt% respectively as metals.
3.1 wt% catalyst F was produced. (5) Production of Catalyst G The same procedure as in Comparative Example (4) was used except that an aqueous solution of 463 g of zirconyl nitrate dissolved in 830 ml of water was used. The content of zirconium oxide in the carrier was 10 wt%, and the amount of tungsten and nickel supported in the catalyst was Catalyst G was prepared with 13.5 wt% and 3.1 wt% as metal, respectively. (6) Production of Catalyst H A solution of 1.2 kg of zinc nitrate dissolved in 1 part of water and 9 kg of alumina hydrate (X) obtained in Example (1) were mixed and mixed in a kneader, and the mixture was mixed with a diameter of 0.9 mm. After molding into granules and drying in air at 110℃ for 16 hours,
A carrier having a zinc oxide content of 10 wt% was prepared by calcining at ℃ for 3 hours. Other than that, Catalyst H was produced in exactly the same manner as in Example (2), with the amount of tungsten and nickel supported as metals being 13.5 wt% and 3.1 wt%, respectively. (7) Production of Catalyst I The hydrate (X) described in Example (1) was formed into granules with a diameter of 0.9 mm, and after drying in air at 110°C for 16 hours, the
161 g of ammonium paratungstate and 132 g of nickel nitrate are added to 660 g of carrier obtained by firing at ℃ for 3 hours.
After adding 412ml of an aqueous solution containing 250
The mixture was dried while gradually increasing the temperature to 550°C, and then calcined at 550°C for 2 hours to obtain catalyst I. The tungsten and nickel loadings of this catalyst comprised 13.5 wt% and 3.1 wt% of the metal in the final catalyst, respectively. Table 1 shows the pore characteristics of catalysts A to I prepared as described above.

[Table] Example of catalyst usage Hydrocracking of atmospheric residual oil was carried out under the following conditions using catalysts A to C of the present invention and comparative catalysts D to H. The reactor has an inner diameter of 19 mm and is filled with 200 g of catalyst.
A fixed bed reactor with a length of 3 m was used. Raw material oil properties Specific gravity 0.890 (15/4℃) Viscosity 79.6cst (at 50℃) Sulfur 0.15wt% Residual carbon 3.5wt% Nitrogen 2100ppm Vanadium 5.4ppm Nickel 1.1ppm Reaction conditions Reaction pressure 150Kg/cm ^2Reaction temperature 430°C Hydrogen/oil ratio 2000nM ³ /Kl LHSV 0.3Hr ^-1 Hydrogen concentration 90mol% Table 2 shows the data 200 hours after the start of the reaction. Here, the 343° ^C. conversion rate refers to the rate at which the heavy components of the feedstock oil are converted to components having a boiling point of 343° C. or lower through a hydrocracking reaction.

【table】

[Table] As is clear from the table, the catalyst of the present invention exhibits superior hydrocracking activity and superior middle distillate (171 to 343° C.) yield compared to catalysts D to I.

Claims (1)

[Scope of Claims] 1. In a heavy oil hydrocracking catalyst composition comprising metals of Groups 6A and 8 of the Periodic Table supported on a carrier made of alumina boria exhibiting solid acidity, A hydrocracking catalyst composition characterized in that the catalyst composition satisfies both conditions (A) and (B) below. (A) When measured by nitrogen gas adsorption method, the diameter is 0~
Average diameter of pores in the range of 600Å from 70 to 100Å
, the volume occupied by pores with a diameter of 70-100 Å is at least 70% of the volume occupied by pores with a diameter of 0-600 Å, and the volume occupied by pores with a diameter of 0-60 Å is at least 70% of the volume occupied by pores with a diameter of 0-600 Å. 20% of the volume occupied
(B) have a diameter between 62 and 600 as measured by mercury porosimetry;
The average diameter of pores in the range of Å is 70-100 Å, and the volume occupied by pores with an average diameter ± 10 Å is at least the volume occupied by pores with a diameter of 62-600 Å.
The volume occupied by pores with an average diameter of +10 Å or more accounts for 60% of the volume occupied by pores with a diameter of 62 to 600 Å.
_2. The catalyst composition according to claim 1, wherein the boria content in the alumina-boria is 5 to 30 wt% as _B2O3 . 3. The catalyst composition according to claim 1, wherein the Group 6A metal is tungsten and the Group 8 metal is nickel. 4. Claim 1, wherein the supported amount of the Group 6A metal is 5 to 24 wt% of the catalyst composition as a metal, and the supported amount of the Group 8 metal is 0.5 to 8 wt% of the catalyst composition as a metal. catalyst composition.