JPH0117414B2 - - Google Patents

Description

[Detailed description of the invention]

The present invention relates to a catalyst composition used for hydrocracking heavy oil, and more specifically to a catalyst composition for hydrocracking heavy oil, particularly so-called residual oil, under mild reaction conditions to reduce the boiling point range of kerosene and gas oil. The present invention relates to a catalyst composition suitable for obtaining a middle distillate in high yield. While crude oil is becoming heavier worldwide, demand for petroleum products is becoming increasingly lighter. Hydrocracking processes, which convert heavy oil into high-value light fractions, are therefore becoming increasingly important. Many catalysts have been proposed for use in hydrocracking processes, but most of them are effective catalysts for hydrocracking processes targeting relatively high-quality oils such as vacuum gas oil. When hydrocracking so-called residual oil such as residual oil or vacuum residual oil,
Not suitable. This is because heavy oil, especially residual oil, contains large amounts of heavy metals such as vanadium and nickel, organic nitrogen compounds, and even asphaltene, which forms macromolecules. The pores of the catalyst are blocked, organic nitrogen compounds poison the active sites on the catalyst, and asphaltenes form carbonaceous substances on the catalyst.
Even though it is an effective catalyst for hydrocracking high quality oil,
This is because, if this is used for hydrocracking of residual oil, the catalyst will be deactivated. By the way, U.S. Patent No. 3431196 states,
A catalyst has been introduced in which a silica-alumina matrix contains ultra-stable crystalline aluminosilicate zeolite as a carrier, and this carrier supports nickel and/or cobalt. Although it is effective for hydrocracking oil, its hydrocracking activity is extremely low for inferior oils such as residual oil. Regarding hydrocracking catalysts for heavy oils such as residual oil, conventional catalysts include catalysts in which a hydrogenation-active metal is supported on an amorphous carrier such as silica-alumina or silica-titania, and Catalysts can be broadly classified into catalysts in which a crystalline aluminosilicate zeolite is contained in an amorphous carrier, and a hydrogenation-active metal is supported on the amorphous carrier. The former catalyst can produce so-called middle distillates in the boiling point range of kerosene and gas oil from heavy oil in high yield, but because of its low activity, it cannot be used under extremely harsh reaction conditions such as high reaction temperature and low liquid hourly space velocity. There are drawbacks that must be adopted. On the other hand, the latter catalyst has significantly higher activity than the former catalyst, so
Although relatively mild reaction conditions can be employed, the disadvantage is that selectivity to middle distillates is poor and most of the product is comprised of naphtha and gas components. In view of the above-mentioned problems of conventional catalysts, the present invention has been developed by:
The present invention provides a hydrocracking catalyst composition capable of producing a middle distillate in high yield from heavy oil such as residual oil even under relatively mild reaction conditions, and the catalyst composition is ultra-stable. Group metals and group metals of the periodic table are supported on alumina or alumina-boria containing crystalline aluminosilicate (salt) zeolite, and the pore characteristics of the composition measured by mercury porosimetry are as follows. It is characterized by satisfying formulas (a) to (c). The mercury intrusion method was measured under the conditions of a contact angle of 130° and a surface tension of 473 dyn/ ^cm2 .
The average diameter of the pores is the diameter corresponding to 50% of the pore volume determined from the pore distribution curve. (a) Average diameter of pores in the range of 62 to 4,000 Å in diameter = 80 to 150 Å (b) Volume of pores in the range of 62 to 80 Å in diameter / Volume of pores in the range of 62 to 4,000 Å ≦30% (c) Diameter of 150 Å or more volume of pores/volume of pores with a diameter of 62 to 4000 Å≦50% In the catalyst composition of the present invention, alumina or alumina-boria is used as a matrix, and ultra-stable crystalline aluminosilicate zeolite (US - Zeolite is used as a catalyst carrier. Ordinary crystalline aluminosilicate zeolite has too strong solid acidity.
If this is used, there is a risk that hydrogen cracking will proceed excessively and the amount of naphtha and gas produced will increase. In contrast, US-zeolite retains the solid acid strength necessary to crack heavy oil into middle distillates, but has a lower solid acid density than regular crystalline aluminosilicate zeolites, so it Excessive decomposition of the fraction into naphtha or gas components is suppressed. The US-zeolite used in the present invention is expressed by the following oxide molar ratio, has a crystal lattice constant of 24.48 Å or less, and has a specific surface area of 200 m ² / g or more. M _2/o O: Al ₂ O ₃ : 6-200 SiO ₂ : 0-9 H ₂ O [However, M represents at least one type of cation, and n represents the charge of M] The catalyst carrier of the present invention is made of alumina. Or alumina
It is composed of a matrix made of boria and US-zeolite dispersed therein, and the amount of US-zeolite in the carrier is 20 to 80wt of the carrier.
%, preferably 40 to 60 wt%. If it is less than 20wt%, the expected effects of US-zeolite will not be fully expressed, and if it is more than 80wt%, not only will the expected effects of the matrix not be sufficiently expressed, but the amount of matrix will be insufficient.
The shape-retaining strength of the carrier and therefore of the catalyst composition cannot be ensured. Alumina can be used alone as a matrix, but boria can be used as a matrix with B ₂ O ₃ .
Even better catalytic activity can be obtained by using alumina-boria containing 30 wt% or less, preferably 10 to 20 wt%. This is thought to be because the amount of solid acid in alumina-boria is maximum in the range of B ₂ O ₃ content of 10 to 20 wt%. As the alumina or alumina-boria matrix, an amorphous alumina hydrate containing pseudoboehmite having a crystallite diameter of 40 to 80 Å can be used. This type of alumina hydrate is produced by neutralizing aluminate or aluminum salt with acid or alkali, and preferably has a concentration of 5wt% or more as alumina.
Amorphous alumina hydrate having a concentration of 8wt% or more is prepared, and this hydrate is heated to a pH of 8 to 12, preferably PH
9 to 11 under mildly alkaline conditions with stirring.
It can be produced by heating to 80°C or higher, preferably 80°C or higher. The above-mentioned catalyst carrier is loaded with a group metal and a group B metal of the periodic table as a hydrogenation active component by a known method. It is preferable to use nickel and/or cobalt as the group metal, and tungsten or molybdenum as the group B metal, and the supported amount thereof is preferably 1 to 8 wt% of the catalyst composition as metal for the group metal. For group B metals, the metal is selected to be in the range of 5 to 24 wt%, preferably 7 to 16 wt% of the catalyst composition. The hydrocracking catalyst composition according to the present invention is unique in that its carrier is composed of a matrix of alumina or alumina-boria and US-zeolite dispersed therein. is characterized by the pore characteristics of the catalyst composition.
In general, in the case of hydrocracking catalysts, the metal active component participates in the hydrogenation and the carrier participates in the decomposition reaction. The raw material hydrocarbon undergoes slight lightening in the amorphous matrix, and then the lightened molecules diffuse inside the pores,
It is thought that this process proceeds through a mechanism in which it is further decomposed by the US-zeolite dispersed within the pores. Therefore, if the pore diameter of the amorphous matrix is small, it becomes difficult for long molecules to be decomposed to enter the pores, and the decomposition activity inevitably decreases. In addition, molecules that penetrate into the pores and undergo slight decomposition in the amorphous matrix have slow molecular diffusion within the pores due to the small pore diameter, and therefore
Since the contact time with US-zeolite is longer,
Over-decomposition occurs and the yield of the middle distillate decreases. On the other hand, when the pore diameter of an amorphous matrix becomes larger than a certain level, macromolecules such as asphaltene not only invade the pores and poison the decomposition active sites, but also cause the molecules to be decomposed to interact with the decomposition active sites. Collision frequency is reduced due to the large pore size, thus reducing decomposition activity. In other words, even in the case of a hydrocracking catalyst in which US-zeolite is dispersed in an amorphous matrix made of alumina or alumina-boria, and a metal active component is supported on this carrier, its pore characteristics are Unless these conditions are met, middle distillates cannot be obtained from heavy oil in high yield. Therefore, the hydrocracking catalyst composition of the present invention is
The pore characteristics of the composition when measured by mercury intrusion porosimetry are required to satisfy the three formulas (a) to (c) described above. The hydrocracking catalyst composition of the present invention comprises atmospheric residual oil,
It is particularly suitable for hydrocracking treatment of heavy oil, of which vacuum residual oil is a typical example, but it can also be used for hydrocracking treatment of vacuum light oil, visbreaking oil, tar sand oil, and the like. By using the catalyst of the present invention, middle distillates in the boiling point range of kerosene and gas oil can be produced from heavy oil in high yield under a wide range of reaction conditions ranging from relatively mild to severe reaction conditions. . The reaction conditions are: reaction temperature 300~500℃, reaction pressure 80~200Kg/ ^cm2 , hydrogen/oil ratio 500~3000N.
^m3 /Kl, LHSV0.1~3.0hr ^-1 , hydrogen concentration 75 mol%
The above is usually adopted, but the preferred reaction conditions are reaction temperature 350-450°C, reaction pressure 100-170Kg/cm ² , hydrogen/oil ratio 700-2000Nm ³ /Kl, LHSV 0.2-
1.0hr ^-1 , hydrogen concentration is 85 mol% or more. The present invention will now be described in more detail with reference to Examples. Example 1 A 50% aqueous glyconic acid solution was added to a sodium aluminate solution with a concentration of 5.0 wt% as Al ₂ O ₃ , and then
An aluminum sulfate solution with a concentration of 2.5 wt% as Al ₂ O ₃ was added to obtain a slurry with a pH of 7.0. After filtering this slurry using a table filter, the filter cake was washed with 0.2% by weight ammonia water to prepare a pseudo-boehmite-containing alumina hydrate. Add a small amount of ammonia water to this alumina hydrate
As a slurry with Al ₂ O ₃ concentration 8.8wt% and pH 10.60,
This was refluxed at 95° C. for 20 hours with stirring, and then heated and concentrated using a kneader to obtain a hydrate (X). In addition, the molar ratio of SiO ₂ /Al ₂ O ₃ is 8.2,
Contains 1.5wt% or less of alkali metal as Na ₂ O, has a crystal lattice constant of 24.37Å, and is heated at 740℃
The specific surface area when fired for 2 hours at a temperature of 602
m ² /g US-Y zeolite was prepared. Next, 219 g of US-Y zeolite was mixed with 1.5 kg of the above hydrate (X), heated and concentrated in a kneader, formed into pellets with a diameter of 0.9 mm, dried in air at 110°C for 16 hours, and then heated at 550°C. After firing for 3 hours, a catalyst carrier having a US-Y zeolite content of 30 wt% was obtained. Add ammonium paratungstate to 660g of this carrier.
After adding 396 ml of an aqueous solution containing 161 g of tungsten and 132 g of nickel nitrate for impregnation, it was dried while gradually increasing the temperature to 250°C, and then calcined at 550°C for 2 hours to achieve a supported amount of tungsten and nickel of 13.5 as metals, respectively. Catalyst A was prepared with wt% and 3.1 wt%. Example 2 A catalyst carrier with a US-Y zeolite content of 50 wt% was prepared using the same recipe as in Example 1, except that the amount of US-Y zeolite used was 510 g, and tungsten and nickel were added to this carrier in the same manner as in Example 1. Catalyst B was supported by the following procedure, and 13.5 wt% and 3.1 wt% of tungsten and nickel were supported as metals, respectively.
was manufactured. Example 3 A catalyst carrier with a US-Y zeolite content of 70 wt% was prepared using the same recipe as in Example 1, except that the amount of US-Y zeolite used was 1190 g, and the metal active component was added to this carrier in the same manner as in Example 1. It is supported by the procedure of
Catalyst C in which the amount of tungsten supported and the amount of nickel supported are respectively 13.5 wt% and 3.1 wt% as metal
was manufactured. Example 4 An aqueous solution prepared by adding 85 g of boric acid to 120 c.c. of water and dissolving it by heating, and US-Y Zeolite 344 used in Example 1.
g and the alumina hydrate (X) prepared in Example 1
Mix 858g, heat and concentrate with a kneader, and make a diameter of 0.9
It was molded into pellets of mm. this pellet in the air
After drying at 110°C for 16 hours, the mixture was calcined at 550°C for 3 hours to obtain a catalyst carrier. This carrier uses US-Y zeolite.
The boria content in the alumina-boria, which contains 50 wt% and occupies the remaining 50 wt%, was 15 wt%. A metal active component was supported on the above carrier in the same manner as in Example 1 to prepare catalyst D in which the supported amounts of tungsten and nickel were 13.5 wt% and 3.1 wt% as metals, respectively. The pore characteristics of catalysts A to D prepared in Examples 1 to 4 measured by mercury porosimetry are shown in Table 1.

[Table] Comparative example 1 Mixed rare earth chloride (main components: CeCl ₃ , LaCl ₃ ,
Y-type zeolite was placed in a 0.5% solution of NdCl ₃ ),
72.4% by adjusting the pH to 5 with ammonia water, stirring at 80℃ for 30 minutes, then dehydrating and washing.
After performing rare earth metal ion exchange, 5%
A rare earth metal-ammonium exchanged Y-type zeolite was produced by performing ammonium ion exchange with an ammonium nitrate solution. The rare earth metal exchange rate of this Y-type zeolite is 65.2%, and the ammonium exchange rate is
25.4%, and the Na ₂ O content was 1.04%. 1.5 kg of the alumina hydrate (X) obtained in Example 1 was added to 510 g of the above Y-type zeolite, heated and concentrated in a kneader, formed into pellets with a diameter of 0.9 mm, and dried in air at 110°C for 16 hours. C. for 3 hours to obtain a catalyst carrier having a Y-type zeolite content of 50 wt%. A metal active component was supported on this catalyst carrier in the same manner as in Example 1, and the supported amounts of tungsten and nickel were 13.5wt% and 3.1wt% as metals, respectively.
A catalyst R was obtained. Comparative Example 2 Alumina hydrate (X) prepared in Example 1 1.01
16 kg of silica hydrogel with a concentration of 3 wt% as SiO ₂ was added to the kg, and after heating and concentrating with a kneader, the diameter
Formed into 0.9 mm pellets, dried in air at 110°C for 16 hours, and then calcined at 550°C for 3 hours to determine the silica content.
A 60wt% catalyst support was obtained. A metal active component was supported on this carrier in the same manner as in Example 1 to obtain a catalyst S in which the supported amounts of tungsten and nickel were 13.5 wt% and 3.1 wt% as metals, respectively. Comparative Example 3 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 filtering this slurry using a table filter, the filter cake was washed with aqueous ammonia to prepare a pseudo-boehmite-containing alumina hydrate. This alumina hydrate was divided into two parts, and a small amount of aqueous ammonia was added to one half to form a slurry with an Al ₂ O ₃ concentration of 8.5 wt% and a pH of 10.5. After refluxing this at 95 °C for 20 hours with stirring, first The remainder of the bisected alumina hydrate was added and spray dried. Next, aqueous ammonia was added to the obtained powder, and the mixture was heated and concentrated in a kneader to obtain a moldable hydrate (Y). 1.5 kg of the above hydrate (Y) was mixed with 515 g of US-Y zeolite used in Example 1, heated and concentrated in a kneader, and then the US-Y zeolite was mixed in the same manner as in Example 1.
A catalyst carrier having a Y zeolite content of 50 wt% was obtained. A metal active component was supported on this carrier in the same manner as in Example 1 to prepare a catalyst T in which the supported amounts of tungsten and nickel were 13.5 wt% and 3.1 wt% as metals, respectively. Comparative Example 4 The pseudoboehmite-containing alumina hydrate, which is a precursor of the alumina hydrate (X) prepared in Example 1, was made into a slurry and spray-dried, and ammonia water was added to the obtained alumina hydrate powder. In addition = Japanese food (Z)
I got it. 1.5 kg of the above hydrate (Z) was mixed with 515 kg of US-Y zeolite used in Example 1, and the same procedure as in Example 1 was followed to obtain a catalyst carrier having a US-Y zeolite content of 50 wt%. A metal active component was supported on this carrier in the same manner as in Example 1, and the amounts of tungsten and nickel supported as metals were 13.5 wt% and 3.1 wt%, respectively. Catalyst U was prepared. Table 2 shows the pore characteristics of catalysts R to U prepared in Comparative Examples 1 to 4, measured by mercury intrusion method.

[Table] Example of using catalyst In order to confirm the effect of the present invention, hydrogenolysis of atmospheric residual oil was carried out under the following conditions using catalysts A to D and comparative catalysts R to U. Catalyst 200 in reactor
A fixed bed reactor with an inner diameter of 19 mm and a length of 3 m was used. Raw material residual oil properties Specific gravity 0.896 (15/4℃) 343℃ ⁺ 95vol% Viscosity 194cst (at 50℃) Sulfur 0.17wt% Residual carbon 4.5wt% Nitrogen 2380ppm Vanadium >0.1ppm Nickel 5.6ppm Reaction conditions Reaction pressure 150Kg/cm ² Reaction temperature 410°C Hydrogen/oil ratio 2000Nm ³ /Kl LHSV 0.6hr ^-1 Hydrogen concentration 90mol% Table 3 shows the data 400 hours after the start of the reaction.
Here, 343℃ ^- conversion rate refers to the heavy content of the residual oil (343℃).
℃ ⁺ ) is converted to components with a boiling point of 343℃ or less by hydrogenolysis reaction.

[Table] As is clear from the upper chamber, this is a catalyst in which a metal active component is supported on a carrier consisting of a matrix of alumina or alumina-boria and US-zeolite dispersed therein. The hydrocracking catalyst of the present invention, which has pore characteristics, exhibits excellent cracking activity (conversion rate at 343 ^° C) and middle distillate selectivity (middle distillate yield) for heavy oils such as residual oil. .

Claims (1)

[Scope of Claims] 1. A catalyst composition in which a group metal and a group metal of the periodic table are supported on alumina or alumina-boria containing ultra-stable crystalline aluminosilicate zeolite, which The pore characteristics of the catalyst composition measured by mercury porosimetry are as shown in (a) to (c) below.
A hydrocracking catalyst composition characterized by satisfying the formula: (a) Average diameter of pores with a diameter in the range of 62 to 4000 Å = 80 to 150 Å (b) Volume of pores with a diameter of 62 to 80 Å / Volume of pores with a diameter of 62 to 4000 Å ≦ 30% (c) Diameter Volume of pores of 150 Å or more / Volume of pores of 62 to 4000 Å in diameter ≦50% 2. The ultrastable crystalline aluminosilicate zeolite is expressed in the following oxide molar ratio, and 24.48
The catalyst composition according to claim 1, which has a crystal lattice constant of Å or less and maintains a specific surface area of 200 m ² /g or more when calcined at a temperature of 740° C. for 2 hours. . M _2/o O: Al ₂ O ₃ : 6-200 SiO ₂ : 0-9 H ₂ O [However, M represents at least one type of cation, and n
represents the charge of M] 3. Catalyst composition according to claim 1, characterized in that the amount of ultrastable crystalline aluminosilicate zeolite in the carrier is 20 to 80 wt% of the carrier. 4. The catalyst composition according to claim 1, wherein the alumina-boria weight ratio of the alumina-boria used in the carrier is 7:3 or less. 5. A patent claim characterized in that the supported amount of the Group metal of the Periodic Table is 1 to 8 wt% of the catalyst composition as a metal, and the supported amount of the Group metal is 5 to 24 wt% of the catalyst composition as a metal. The catalyst composition according to item 1. 6. The catalyst composition according to claim 1, wherein the group metal is nickel and the group metal is tungsten.