KR19980702741A - Catalyst composition, and its use in hydrocarbon conversion processes - Google Patents

Abstract

The present invention provides a molecular sieve having substantially the same structure as zeolite Y, a unit cell constant (a ₀ ) of 2.485 nm or less and a mesopore volume of 0.05 ml / g or more contained in mesopores in the range of 2 to 60 nm in diameter, And a binder, wherein the relationship between the unit cell constant (a ₀ ) and the mesopore volume provides a catalyst composition as defined in Table 1 and a hydrocarbon conversion method using the same.

Description

Catalyst composition, and its use in hydrocarbon conversion processes

The present invention relates to a catalyst composition and a hydrocarbon conversion method using the same.

In the petroleum industry many hydrocarbon conversion processes are carried out using Zeolite Y based catalyst compositions. Zeolite Y very often performs certain stabilization and / or dealumination reaction steps during its preparation to have reduced unit cell constant (a ₀ ) and increased silica molar ratio to alumina. The stabilized zeolites, like synthetic zeolites Y, have relatively few pores greater than 2 nm in diameter, so they have a finite mespore volume (the mespores typically have diameters ranging from 2 to 60 nm).

US-A-5 354 452 has a super stable Y zeolite having a molar ratio of silica to alumina of 6 to 20, a molar ratio of silica to alumina of 18 or more, and a unit cell constant (a ₀ ) of 2.420 to 2.448 nm (24.20). Super-stable Y zeolites from 24 to 48.48 kPa) are hydrothermally treated with steam at 1000 to 1200 F ° and then acid treated at 140 to 220 F °. Hydrothermally treated zeolites have a unit cell constant (a ₀ ) typically in the range of 2.427 to 2.439 nm (24.27 to 24.39 mm 3) and in mesopores having a diameter of 10 to 60 nm (100 to 600 mm 3). While the primary pore volume is from 0.09 to 0.13 ml / g and the total pore volume is from 0.16 to 0.20 ml / g, acidified, hydrothermally treated zeolites typically have a unit cell constant (a ₀ ) of 2.405 to 2.418 nm ( Secondary pore volume contained in mesopores having a range of 24.05 to 24.18 mm 3) and having a diameter of 10 to 60 nm (100 to 600 mm 3) from 0.11 to 0.14 ml / g, with a total pore volume of 0.16 to 0.25 ml / g.

Certainly 'Y-type' molecular sieves with larger mesopore volumes, which are now surprisingly useful for the conversion of hydrocarbon oils by catalytic cracking or hydrolysis to produce the desired product in high yield and high selectivity, for example. It has been found that preparation of catalyst compositions having

According to the present invention, a powder having substantially the same structure as zeolite Y, a unit cell constant (a ₀ ) of 2.485 nm or less and a mesopore volume of 0.05 ml / g or more contained in mesopores in the range of 2 to 60 nm in diameter. It provides a catalyst composition comprising itself and a binder, wherein the relationship between the unit cell constant (a ₀ ) and the mesopore volume is as follows.

Unit cell constant (nm) Mesopore volume (ml / g)

2.485 ≥ a ₀ ≥ 2.460 ≥ 0.05

2.460 ≥ a ₀ ≥ 2.450 ≥ 0.18

2.450 ≥ a ₀ ≥ 2.427 ≥ 0.23

2.427 ≥ a ₀ ≥ 0.26

The molecular sieve used in the catalyst composition of the present invention is defined as having substantially the same structure as zeolite Y. The definition is not only the zeolite Y itself, but the replacement of the aluminum ion ratio with other metal ions such as iron, titanium, gallium, tin, chromium or scandium ions-but the structure is determined by X-ray crystallography It is not significantly different from Y-also includes molecular sieves derived from modified zeolite Y. Examples of suitable iron- and / or titanium-modified zeolites Y are disclosed in US Pat. Nos. 5 176 817 and 5 271 761, examples of suitable chromium- and / or tin-modified zeolites Y are EP-A. -321 is published at 177.

However, molecular sieves used in the catalyst compositions of the present invention are published by Robert E. Krieger, Zeolite Molecular Sieves (Structure, Chemistry and Use) (1984) by Donald W. Breck, and U.S. Patent Nos. 3 506 400, 3 671 191 Preference is given to those derived from zeolite Y itself, as described in US Pat. Nos. 3,808,326, 3,929,672 and 5,242,677.

In the molecular sieve used in the composition, the unit cell constant (a ₀ ) is 2.485 nm (24.85 kV) or less (≤), preferably 2.460 nm (24.60 kPa) or less (≤), for example 2.427 to 2.485 nm (24.27). It has a range of VII to 24.85 Hz, preferably 2.427 to 2.460 nm (24.27 Hz to 24.60 Hz). Advantageously, for molecular sieves, the unit cell constant (a ₀ ) is no greater than 2.440 nm (24.40 kPa), such as in the range of 2.427-2.440 nm (24.27 kPa-24.40 kPa), or 2.450-2.460 nm (24.50 kPa-24.60 kPa). ) Has a range of.

The mesopore volume of the molecular sieve when contained in mesopores having a diameter of 2 to 60 nm changes according to the unit cell constant (a ₀ ). The relationship between the unit cell constant (a ₀ ) and the mesopore volume is as follows.

Unit cell constant (nm) Mesopore volume (ml / g)

2.485 ≥ a ₀ ≥ 2.460 ≥ 0.05

2.460 ≥ a ₀ ≥ 2.450 ≥ 0.18

2.450 ≥ a ₀ ≥ 2.427 ≥ 0.23

2.427 ≥ a ₀ ≥ 0.26

The mesopore volume in the molecular sieve is 0.8 ml / g or less, for example 0.05, preferably 0.18, more preferably 0.23, even more preferably 0.26, advantageously 0.3 and especially 0.4 ml / g to 0.6 ml / g, in particular 0.8 ml / g.

Molecular sieves useful in the present invention may be prepared by treating the zeolite Y or modified zeolite Y as described above with a solution at atmospheric pressure for a time sufficient to provide the mesopore volume of mesopore with a diameter in the range of 2 to 60 nm. At a temperature above the boiling point, it is prepared by hydrothermal treatment in which hydrothermal contact is made with an aqueous solution in which at least one salt, acid, base and / or water-soluble organic compound is dissolved. At the end of the hydrothermal treatment, the product is separated, washed (using deionized water or an acid such as nitric acid solution) and recovered. The product obtained by the treatment generally has a unit cell size (unit cell constant), and the silica molar ratio to alumina is similar to the starting material zeolite. However, if desired, the product is subjected to additional stabilization and / or dealumina treatment as known in the art to vary the unit cell size and / or silica molar ratio to alumina.

In the preparation of aqueous hydrothermal treatment solutions, examples of the salts that can be used include aluminum, alkali metals (e.g. sodium and potassium), and alkaline earth metal salts (e.g. nitric acid and hydrochloric acid) of strong, weak, organic and inorganic acids. Examples of possible acids include weak organic acids such as acetic acid and formic acid, as well as strong inorganic acids such as nitric acid and hydrochloric acid, and examples of bases that can be used include organic bases such as quaternary ammonium hydroxide, amine complexes and pyridinium salts. Together are inorganic bases such as ammonium, alkali metal and alkaline earth metal hydroxides, and examples of water-soluble organic compounds that can be used include C ₁ -C ₆ alcohols and ethers. The concentration and amount of the aqueous solution contacted with the starting material zeolite are adjusted to obtain 0.1 parts by weight (pbw) of the solute dissolved per zeolite based on the dry weight.

The pH of the hydrothermal aqueous solution varies from 3 to 10 and depends on the (modified) zeolite Y to be treated, with a high or low pH being preferred. Thus, if the starting material zeolite has a unit cell constant (a ₀ ) of 2.450 to 2.460 nm (2.460 nm ≥ a ₀ ≥ 2.450 nm), the pH of the solution is maintained or adjusted to a value of 4.5 to 8 before contacting the zeolite. Preferably, when the starting material zeolite has a unit cell constant (a ₀ ) (2.450 nm ≧ a ₀ ≧ 2.427 nm) of 2.427 to 2.450 nm, the pH of the solution is preferably maintained or adjusted to 3 to 8 and starting If the material zeolite has a unit cell constant (a ₀ ) of 2.427 nm or less (2.427 nm ≧ a ₀ ), the pH of the solution is preferably maintained or adjusted to 3-7.

The hydrothermal treatment temperature should exceed the boiling point of the aqueous solution. Even if a temperature of 400 ° C. or lower is used, a temperature having a range of 110 or 115 to 250 ° C. is usually satisfactory. Good results can be obtained by using a temperature in the range of 140 to 200 ° C.

Treatment time is inversely related to treatment temperature. Thus, at higher temperatures, a shorter time is needed to increase the mesopore volume. The treatment time can vary from 5 minutes to 24 hours, but usually ranges from 2 to 12 hours.

The hydrothermal treatment time and temperature should be able to provide a large mesopore volume in the final product which is at least 5%, preferably at least 10%, of the mesopore volume in the starting material zeolite.

Preferred molecular sieves for use in the catalyst products of the present invention are the (modified) zeolites Y as described previously, after hydrothermal contact with an aqueous solution in which at least one salt, acid, base and / or water-soluble organic compound is dissolved, followed by separation. And washing with an acid solution.

The acid solution is at least one aqueous acid solution selected from inorganic or organic acids, such as nitric acid, hydrochloric acid, acetic acid, formic acid and citric acid. Compared to the (deion) water used, washing with acid solution has the advantage of further improving the intermediate effluent selectivity of the increased mesopore molecular sieve.

As a binder in the catalyst composition of the present invention, it is convenient to use an inorganic oxide or a mixture of two or more thereof. The binder may be amorphous or crystalline. Examples of suitable binders include alumina, silica, magnesia, titania, zirconia, silica-alumina, silica-zirconia, silica-boria, and mixtures thereof. Preferred binders for use are alumina or a combination of alumina with a dispersion of silica-alumina in an alumina matrix, in particular a gamma alumina matrix.

The catalyst composition of the present invention preferably contains 1 to 80% by weight of molecular sieve and 20 to 99% by weight of binder relative to the total dry weight of the molecular sieve and binder. More preferably the catalyst composition comprises from 10 to 70% by weight of the molecular sieve and from 30 to 90% by weight of the binder, in particular from 20 to 50% by weight of the molecular sieve and from 50 to 80% by weight relative to the total dry weight of the molecular sieve and the binder. It contains a binder.

Depending on the application of the present catalyst composition (eg hydrolysis), it may further contain one or more hydrogenation components. Examples of hydrogenation components useful in the present invention include Group 6B (such as molybdenum and tungsten) and Group 8 metals (such as cobalt, nickel, iridium, platinum and palladium), oxides and sulfides thereof. The catalyst composition preferably contains two or more kinds of hydrogenation components, such as the molybdenum and / or tungsten component together with the cobalt and / or nickel component. Particularly preferred combinations are nickel / tungsten and nickel / molybdenum. Very advantageous results are obtained when the metal is used in the form of sulfides.

The catalyst component may contain up to 50 parts by weight of hydrogenation component, calculated as metals relative to 100 parts by weight of the total catalyst composition. By way of example, the catalyst composition may comprise 2-40, more preferably 5-25, particularly 10-20 parts by weight of Group 6 metal (s) and / or 0.05-10, calculated as metals relative to 100 parts by weight of the total catalyst composition. More preferably from 0.5 to 8, advantageously from 2 to 6 parts by weight of group 8 metal (s).

The catalyst composition can be prepared according to the prior art in the art.

A convenient process for the preparation of the catalyst composition used for decomposition involves mixing the binder material and water to form a slurry or sol, adjusting the pH of the slurry or sol appropriately, and then adding the powder molecular sieve as defined above with additional water. Adding together yields a slurry or sol with the desired solid concentration. The slurry or sol is then spray dried. Spray dried particles formed therein can preferably be used or calcined prior to use.

One process for the preparation of catalyst compositions for use in hydrolysis involves mixing the molecular sieve and the binder as defined above well in the presence of water and optionally in the presence of a peptizing agent, extruding the resulting mixture into pellets, and calcining the pellets. It includes. The pellets thus obtained are then deposited with one or more Group 6B and / or Group 8 metal salts and then calcined again.

Alternatively, the molecular sieve and binder are mixed well in the presence of one or more solutions of group 6B and / or group 8 metal salts, optionally in the presence of peptizing agents, and the mixture formed thereon is extruded into pellets. The pellet can then be calcined.

The invention also provides a process for the conversion of a hydrocarbon feed to a low boiling point material comprising contacting the feed with a catalyst composition according to the invention at elevated temperatures.

Hydrocarbon feeds useful in the process can vary within a wide boiling range. Hydrocarbon feeds include light oil, coker light oil, vacuum light oil, deasphalted oil, short and short chain residues, catalyzed cycle oil, thermal or catalyzed light oil, and synthetic crude oil, optionally tar sand, shale oil. ), Heavy fractions such as residue upgrading processes or biomass, as well as light fractions such as kerosine fractions. Combinations of various hydrocarbon oils may also be used. The feed liquid generally contains a hydrocarbon having a boiling point of at least 330 ° C. In a preferred embodiment of the invention, at least 50% by weight of the feed liquid has a boiling point above 370 ° C. The feed may have a nitrogen content of up to 5000 ppmw (parts by weight in weight) and a sulfur content of up to 6 weight percent. Typically, the nitrogen content is in the range of 250 to 2000 ppmw and the sulfur content is in the range of 0.2 to 5% by weight. Some or all of the feed may be pre-treated, such as hydrodenitrogen reactions, hydrodesulfurization reactions, or hydrodemetallization reactions known in the art, and such treatment may often be preferred.

When the method is carried out under catalytic cracking conditions (i.e., in the absence of added hydrogen), a vertically moving catalyst bed, such as conventional Thermofor Catalytic Cracking (TCC) or Fluidized Catalytic Cracking ( According to the FCC)) method, the method is conveniently performed. As the method conditions, the reaction temperature is preferably in the range of 400 to 900 ° C, more preferably 450 to 800 ° C, particularly 500 to 650 ° C, and the total pressure is 1 × 10 ⁵ to 1 × 10 ⁶ Pa (1 To 10 bar), in particular 1 x 10 ⁵ to 7.5 x 10 ⁵ Pa (1 to 7.5 bar), and the weight ratio (kg / kg) of the catalyst composition / feed liquid has a range of 5 to 150, in particular 20 to 100 The contact time between the catalyst composition and the feed liquid is 0.1 to 10 seconds, advantageously 1 to 6 seconds.

However, the process according to the invention is preferably carried out under hydrogenation conditions, ie catalytic hydrolysis conditions such as residue hydrolysis conditions.

Therefore, the reaction temperature preferably has a range of 250 to 500 ° C, more preferably 300 to 450 ° C, particularly 350 to 450 ° C.

The total pressure is preferably 5 x 10 ⁶ to 3 x 10 ⁷ Pa (50 to 300 bar), more preferably 7.5 x 10 ⁶ to 2.5 x 10 ⁷ Pa (75 to 250 bar), more preferably 1 x 10 ⁷ To 2 x 10 ⁷ Pa (100 to 200 bar).

The hydrogen partial pressure is preferably 2.5 x 10 ⁶ to 2.5 x 10 ⁷ Pa (25 to 250 bar), more preferably 5 x 10 ⁶ to 2 x 10 ⁷ Pa (50 to 200 bar), more preferably 6 x 10 ⁶ to 1.8 x 10 ⁷ Pa (60 to 180 bar).

A space velocity having a range of 0.05 to 10 kg feed liquid / catalyst composition (L) · hour (h) (kg · l ⁻¹ · h ⁻¹ ) is conveniently used. Preferably the space velocity is from 0.1 to 8, in particular from 0.1 to 5 kg · l ⁻¹ · h ⁻¹ . It also uses a total gas velocity (gas / injection ratio) of 100 to 5000 Nl / kg. Preferably the total gas velocity used is in the range of 250 to 2500 Nl / kg.

The unit cell constant (a ₀ ) is obtained according to the standard test method ASTM D 3942-80, and the relative crystallinity (%) is the X-ray crystallographic data of the increased mesoporous zeolite Y and the X of the corresponding standard zeolite Y in the prior art. Obtained by comparing the line crystallographic data, the following practice of obtaining surface properties (ie surface area (m ² / g) and mesopore volume (ml / g)) using nitrogen adsorption at 77 ° K (-196 ° C.) The present invention is further illustrated by way of example.

Example 1

(i) Preparation of molecular sieves with increased mesopore volume

Very ultrastable zeolite Y having a molar ratio of silica to alumina of 7.4, unit cell constant (a ₀ ) of 2.433 nm (24.33 kPa), surface area of 691 m ² / g and mesopore volume of 0.177 ml / g VUSY) is added to an aqueous solution of 4N ammonium nitrate (NH ₄ NO ₃ ) in an amount such that the ratio of the number of g of ammonium nitrate to the number of g of zeolite Y to the number of g of zeolite Y on a dry weight basis is 1.5. The resulting slurry is placed in a 2 liter capacity autoclave and the slurry is stirred at 150 ° C. for 12 hours. After cooling, the contents of the autoclave were filtered and washed twice with nitric acid solution (2 milli-equivalents; meq) of hydrogen ions (H ⁺ ) / zeolite for 3 hours at 93 ° C., A molecular sieve having a structure substantially the same as a zeolite dried at 110 ° C. is obtained, which has a ratio of silica to alumina of 13.2, a unit cell constant (a ₀ ) of 2.429 nm (24.29 μs), a relative crystallinity of 87%, It was found to have a surface area of 756 m ² / g and a mesopore volume of 0.322 ml / g.

(ii) Preparation of Catalyst Composition

To a mixture consisting of molecular sieve (5 g), amorphous 55/45 silica-alumina (104 g) and high microporous precipitated alumina (50 g) prepared as described in (i) above, water (145 g) and acetic acid (96%, 4 g) is added. The mixture is mixed well first and then extruded to add the extrusion aid to the cylindrical pellets. The pellet is heated at 120 ° C. for 2 hours and then calcined at 530 ° C. for 2 hours. The pellet thus obtained has a circular terminal area of 1.6 mm and a water pore volume of 0.72 ml / g. The pellet contains 4 wt% molecular sieve and 96 wt% binder (66 wt% silica-alumina and 30 wt% alumina) on a dry weight basis.

10.07 g of nickel nitrate aqueous solution (14 wt% nickel) and 16.83 g of ammonium metatungstate aqueous solution (39.8 wt% tungsten) are combined, and the obtained nickel / tungsten solution is diluted with water (18 g) and homogenized. . 25.0 g of pellets are immersed in a homogenized nickel / tungsten solution, dried at 120 ° C. for 1 hour and then calcined at 500 ° C. for 2 hours. The pellet contains 3.9 wt% nickel and 18.9 wt% tungsten based on the total composition.

Example 2

(i) Preparation of molecular sieves with increased mesopore volume

Very ultra stable zeolite Y having a molar ratio of silica to alumina of 8.4, unit cell constant (a ₀ ) of 2.434 nm (24.34 kPa), surface area of 727 m ² / g, and mesopore volume of 0.180 ml / g VUSY) is added to an aqueous solution of 4N ammonium nitrate (NH ₄ NO ₃ ) in an amount such that the ratio of the number of g of ammonium nitrate to the number of g of zeolite Y to the number of g of zeolite Y on a dry weight basis is 1.5. The resulting slurry is placed in a 2 liter capacity autoclave and the slurry is stirred at 200 ° C. for 6 hours. After cooling, the contents of the autoclave were filtered and washed twice with nitric acid solution (2 milli-equivalents; meq) of hydrogen ions (H ⁺ ) / zeolite for 3 hours at 93 ° C., Obtained having a structure substantially the same as that of zeolite dried at 110 ° C., which has a ratio of silica to alumina of 10.0, unit cell constant (a ₀ ) of 2.427 nm (24.27 μs), relative crystallinity of 71%, 605 m ² It was found to have a surface area of / g and a mesopore volume of 0.423 ml / g.

(ii) Preparation of Catalyst Composition

In the method described in Example 1 (ii), the molecular sieve (5 g) prepared according to the method described in (i) above was subjected to amorphous 55/45 silica-alumina (82 g) and high microporous precipitated alumina (40 g). To form a cylindrical pellet, which after drying and calcining, has a circular end surface diameter of 1.2 mm and a water pore volume of 0.717 ml / g. The pellet contains 5% by weight molecular sieve and 95% by weight binder (65% by weight silica-alumina and 30% by weight alumina) on a dry weight basis.

Combine 8.34 g of nickel nitrate aqueous solution (14.1 wt% nickel) and 8.29 g of ammonium metatungstate aqueous solution (67.3 wt% tungsten), and the obtained nickel / tungsten solution is diluted with water (7.2 g) and homogenized. . 25.0 g of pellets are immersed in a homogenized nickel / tungsten solution, dried at 120 ° C. for 1 hour and then calcined at 500 ° C. for 2 hours. The pellet contains 3.9 wt% nickel and 18.9 wt% tungsten based on the total composition.

Example 3

(i) Preparation of molecular sieves with increased mesopore volume

Very ultra stable zeolite Y having a molar ratio of silica to alumina of 7.4, unit cell constant (a ₀ ) of 2.433 nm (24.33 μs), surface area of 691 m ² / g, and mesopore volume of 0.177 ml / g. VUSY) is added to an aqueous solution of 4N ammonium nitrate (NH ₄ NO ₃ ) in an amount such that the ratio of the number of g of ammonium nitrate to the number of g of zeolite Y to the number of g of zeolite Y on a dry weight basis is 1.5. The resulting slurry is placed in a 2-liter stirred autoclave and the slurry is stirred at 180 ° C. for 12 hours. After cooling, the contents of the autoclave were filtered and washed twice with nitric acid solution (2 milli-equivalents; meq) of hydrogen ions (H ⁺ ) / zeolite for 3 hours at 93 ° C., Obtained having a structure substantially the same as that of zeolite dried at 110 ° C., which has a ratio of silica to alumina of 10.2, unit cell constant (a ₀ ) of 2.428 nm (24.28 kPa), relative crystallinity of 57%, 519 m ² It was found to have a surface area of / g and a mesopore volume of 0.458 ml / g.

(ii) Preparation of Catalyst Composition

In the method described in Example 1 (ii), the molecular sieve (7 g) prepared according to the method described in (i) above was subjected to amorphous 55/45 silica-alumina (125 g) and high microporous precipitated alumina (60 g). To form a cylindrical pellet, which after drying and calcining, has a circular end surface diameter of 1.6 mm and a water pore volume of 0.792 ml / g. The pellet contains 4% by weight molecular sieve and 96% by weight binder (66% by weight silica-alumina and 30% by weight alumina) on a dry weight basis.

13.12 g of nickel nitrate aqueous solution (14.1 wt% nickel) and 12.94 g of ammonium metatungstate aqueous solution (67.3 wt% tungsten) are combined, and the obtained nickel / tungsten solution is diluted with water (13.69 g) and homogenized. . 32.53 g of pellets are immersed in a homogenized nickel / tungsten solution, dried at 120 ° C. for 1 hour, and finally calcined at 500 ° C. for 2 hours. The pellet contains 3.9 wt% nickel and 18.9 wt% tungsten based on the total composition.

Example 4

Hydrolysis experiment

Each catalyst composition of Examples 1 to 3 is subjected to hydrodegradability testing to assess intermediate effluent selectivity. This test involves contacting a hydrocarbon feed (via hydrotreated heavy vacuum) and a catalyst composition (conventionally sulphide):

Space velocity: Diesel oil (1.5 kg) / catalyst composition (l) · hour (hour) (kg · l ⁻¹ · h ⁻¹ ), hydrogen sulfide partial pressure: 5.5 x 10 ⁵ Pa (5.5 bar), ammonia partial pressure: 7.5 x 10 ³ Pa (0.075 bar), Gross pressure: 14 x 10 ⁶ Pa (140 bar) and gas / feed ratio: 1500 Nl / kg.

The hydrotreated heavy vacuum diesel has the following properties:

Carbon content: 86.5 wt%

Hydrogen content: 13.4 wt%

Sulfur content: 0.007 weight%

Nitrogen content: 16.1 ppmw

Density (70/4): 0.8493 g / ml

Dynamic viscosity at 100 ° C: 8.81 mm ² / s (cs)

Initial boiling point: 345 ℃

10 weight% boiling point: 402 ℃

20 weight% boiling point: 423 ℃

30% by weight boiling point: 441 ℃

40 wt% boiling point: 456 ℃

50% by weight boiling point: 472 ℃

60% by weight boiling point: 490 ℃

70 weight% boiling point: 508 ℃

80% by weight boiling point: 532 ℃

90 weight% boiling point: 564 ℃

Final boiling point: 741 ℃

The performance of each catalyst composition is evaluated at a net conversion of 65% by weight of the injection component having a boiling point at temperatures above 370 ° C. The intermediate effluents (ie the fractions having boiling points in the range of 150 to 370 ° C.) indicated by the catalyst compositions of Examples 1 to 3 are shown in Table 1 below.

Example Catalyst Compositions Selectivity of middle distillate at net conversion of 65% by weight (% w / w) One 70.5 2 72.5 3 72.5

As can be seen from Table 1 above, the catalyst compositions of Examples 1 to 3 according to the present invention exhibit high intermediate effluent selectivity.

Example 5

(i) Preparation of molecular sieves with increased mesopore volume

Very ultra stable zeolite Y having a molar ratio of silica to alumina of 7.9, unit cell constant (a ₀ ) of 2.431 nm (24.31 kPa), surface area of 550 m ² / g and mesopore volume of 0.141 ml / g VUSY) is added to an aqueous solution of 4N ammonium nitrate (NH ₄ NO ₃ ) in an amount such that the ratio of the number of g of ammonium nitrate to the number of g of zeolite Y to the number of g of zeolite Y on a dry weight basis is 1.5. The resulting slurry is placed in a 2 liter capacity autoclave and the slurry is stirred at 200 ° C. for 6 hours. After cooling, the contents of the autoclave were filtered and washed twice with nitric acid solution (2 milli-equivalents; meq) of hydrogen ions (H ⁺ ) / zeolite for 3 hours at 93 ° C., Obtained having a structure substantially the same as that of zeolite dried at 110 ° C., which has a ratio of silica to alumina of 8.5, unit cell constant (a ₀ ) of 2.432 nm (24.32 kPa), relative crystallinity of 69%, 481 m ² It has been found to have a surface area of / g and a mesopore volume of 0.41 ml / g.

(ii) Preparation of Catalyst Composition

In the method described in Example 1 (ii), the molecular sieve (22.3 g) prepared according to the method described in (i) above is combined with high microporous precipitated alumina (110.0 g) to form a cylindrical pellet, thereby The pellet has a circular end surface diameter of 1.6 mm and a water pore volume of 0.642 ml / g after drying and calcining. The pellet contains 20% by weight molecular sieve and 80% by weight binder on a dry weight basis.

8.92 g of nickel nitrate aqueous solution (13.9 wt% nickel) and 7.85 g of ammonium metatungstate aqueous solution (67.3 wt% tungsten) are combined, and the obtained nickel / tungsten solution is diluted with water (6.6 g) and homogenized. . 22.76 g of pellets are immersed in a homogenized nickel / tungsten solution, dried at 120 ° C. for 1 hour and then calcined at 500 ° C. for 2 hours. The pellet contains 4.0 wt% nickel and 17.0 wt% tungsten based on the total composition.

Example 6

Hydrolysis experiment

The catalyst composition of Example 5, which is the catalyst composition according to the present invention, is subjected to a hydrolysis test to evaluate the intermediate effluent selectivity. This test included contacting a hydrocarbon feed (via hydrotreated heavy vacuum) with the catalyst composition of Example 5 (pre-sulfurized by conventional methods):

Space velocity: Diesel oil (1.5 kg) / catalyst composition (l) · hour (hour) (kg · l ⁻¹ · h ⁻¹ ), hydrogen sulfide partial pressure: 5.5 x 10 ⁵ Pa (5.5 bar), ammonia partial pressure: 1.65 x 10 ⁴ Pa (0.165 bar), Gross pressure: 14 x 10 ⁶ Pa (140 bar) and gas / feed ratio: 1500 Nl / kg.

The hydrotreated heavy vacuum diesel has the following properties:

Carbon content: 86.7 wt%

Hydrogen content: 13.3 weight%

Sulfur content: 0.007 weight%

Nitrogen content: 19.0 ppmw

Density (70/4): 0.8447 g / ml

Initial boiling point: 349 ℃

10 weight% boiling point: 390 ℃

20 weight% boiling point: 410 ℃

30% by weight boiling point: 427 ℃

40 wt% boiling point: 444 ℃

50% by weight boiling point: 461 ℃

60% by weight boiling point: 478 ℃

70 weight% boiling point: 498 ℃

80% by weight boiling point: 523 ℃

90 weight% boiling point: 554 ℃

Final boiling point: 620 ℃

The performance of each catalyst composition is evaluated at a net conversion of 65% by weight of the injection component having a boiling point at temperatures above 370 ° C. The selectivity of the intermediate effluent (ie, the fraction having a boiling point in the range from 150 to 370 ° C.) indicated by the catalyst composition of Example 5 is 69.0% w / w.

Claims (16)

A molecular sieve having a structure substantially the same as zeolite Y, a unit cell constant (a ₀ ) of 2.485 nm or less and a mesopore volume of 0.05 ml / g or more contained in mesopores ranging from 2 to 60 nm in diameter, and a binder A catalyst composition comprising, wherein the relationship between unit cell constant (a ₀ ) and mesopore volume is as follows: Unit cell constant (nm) Mesopore Volume (ml / g) 2.485 ≥ a ₀ ≥ 2.460 ≥ 0.05 2.460 ≥ a ₀ ≥ 2.450 ≥ 0.18 2.450 ≥ a ₀ ≥ 2.427 ≥ 0.23 2.427 ≥ a ₀ ≥ 0.26 The catalyst composition of claim 1, wherein the molecular sieve is derived from zeolite Y. The catalyst composition of claim 1 or 2, wherein the molecular sieve has a unit cell constant (a ₀ ) of 2.460 nm or less. The catalyst composition according to any one of claims 1 to 3, wherein the molecular sieve has a mesopore volume of 0.8 ml / g or less. The catalyst composition of claim 1, wherein the molecular sieve has a mesopore volume in the range of 0.3 to 0.8 ml / g. 6. The catalyst composition of claim 1, wherein the molecular sieve has a mesopore volume having a range of 0.4 to 0.6 ml / g. 7. The aqueous solution and hot water according to any one of claims 1 to 6, wherein (modified) zeolite Y is dissolved in at least one salt, acid, base and / or water-soluble organic compound at a temperature above the boiling point of the solution at atmospheric pressure. A catalyst composition for preparing a molecular sieve by a method comprising contacting. 8. The catalyst composition of any one of claims 1 to 7, wherein the binder is an inorganic oxide. The catalyst composition of claim 1, wherein the binder is selected from alumina, silica, magnesia, titania, zirconia, silica-alumina, silica-zirconia, silica-boria, and mixtures thereof. 10. The catalyst composition according to claim 1, further comprising one or more hydrogenation components. The catalyst composition of claim 10, wherein the at least one hydrogenation component is selected from Group 6B and Group 8 metals, oxides and sulfides thereof. 12. The catalyst composition of claim 10 or 11, wherein the at least one hydrogenation component is selected from molybdenum, tungsten, cobalt, nickel, platinum and palladium, oxides and sulfides thereof. 13. A process for converting a hydrocarbon feed into a low boiling point material comprising contacting the feed at an elevated temperature with the catalyst composition as defined in any of claims 1-12. The method of claim 13, wherein the feed liquid is contacted under hydrogenation conditions with the catalyst composition as defined in claim 10. The process of claim 14, wherein the process is carried out at a temperature in the range of 250 to 500 ° C. and at a total pressure in the range of 5 × 10 ⁶ to 3 × 10 ⁷ Pa. The method according to claim 14 or 15, wherein a space velocity of 0.05 to 10 kg feed liquid / catalyst (L) time (h) (kg · l ⁻¹ · h ⁻¹ ) is used.