WO1996027438A1 - Compositions de catalyseur et leur utilisation dans des procedes de conversion d'hydrocarbures - Google Patents

Compositions de catalyseur et leur utilisation dans des procedes de conversion d'hydrocarbures Download PDF

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WO1996027438A1
WO1996027438A1 PCT/EP1996/000915 EP9600915W WO9627438A1 WO 1996027438 A1 WO1996027438 A1 WO 1996027438A1 EP 9600915 W EP9600915 W EP 9600915W WO 9627438 A1 WO9627438 A1 WO 9627438A1
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Prior art keywords
catalyst composition
composition according
molecular sieve
range
zeolite
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PCT/EP1996/000915
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English (en)
Inventor
Theodorus Ludovicus Michael Maesen
Johannes Anthonius Robert Van Veen
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Shell Internationale Research Maatschappij B.V.
Shell Canada Limited
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Priority to NZ303210A priority Critical patent/NZ303210A/en
Priority to JP8526603A priority patent/JPH11500956A/ja
Priority to EP96905859A priority patent/EP0817676A1/fr
Priority to AU49451/96A priority patent/AU4945196A/en
Publication of WO1996027438A1 publication Critical patent/WO1996027438A1/fr
Priority to MXPA/A/1997/006566A priority patent/MXPA97006566A/xx

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    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J35/00—Catalysts, in general, characterised by their form or physical properties
    • B01J35/60—Catalysts, in general, characterised by their form or physical properties characterised by their surface properties or porosity
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J29/00—Catalysts comprising molecular sieves
    • B01J29/04—Catalysts comprising molecular sieves having base-exchange properties, e.g. crystalline zeolites
    • B01J29/06—Crystalline aluminosilicate zeolites; Isomorphous compounds thereof
    • B01J29/08—Crystalline aluminosilicate zeolites; Isomorphous compounds thereof of the faujasite type, e.g. type X or Y
    • B01J29/084—Y-type faujasite
    • C—CHEMISTRY; METALLURGY
    • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10G—CRACKING HYDROCARBON OILS; PRODUCTION OF LIQUID HYDROCARBON MIXTURES, e.g. BY DESTRUCTIVE HYDROGENATION, OLIGOMERISATION, POLYMERISATION; RECOVERY OF HYDROCARBON OILS FROM OIL-SHALE, OIL-SAND, OR GASES; REFINING MIXTURES MAINLY CONSISTING OF HYDROCARBONS; REFORMING OF NAPHTHA; MINERAL WAXES
    • C10G47/00—Cracking of hydrocarbon oils, in the presence of hydrogen or hydrogen- generating compounds, to obtain lower boiling fractions
    • C10G47/02—Cracking of hydrocarbon oils, in the presence of hydrogen or hydrogen- generating compounds, to obtain lower boiling fractions characterised by the catalyst used
    • C10G47/10—Cracking of hydrocarbon oils, in the presence of hydrogen or hydrogen- generating compounds, to obtain lower boiling fractions characterised by the catalyst used with catalysts deposited on a carrier
    • C10G47/12—Inorganic carriers
    • C10G47/16—Crystalline alumino-silicate carriers
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J35/00—Catalysts, in general, characterised by their form or physical properties
    • B01J35/60—Catalysts, in general, characterised by their form or physical properties characterised by their surface properties or porosity
    • B01J35/61—Surface area
    • B01J35/615—100-500 m2/g
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J35/00—Catalysts, in general, characterised by their form or physical properties
    • B01J35/60—Catalysts, in general, characterised by their form or physical properties characterised by their surface properties or porosity
    • B01J35/61—Surface area
    • B01J35/617—500-1000 m2/g
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J35/00—Catalysts, in general, characterised by their form or physical properties
    • B01J35/60—Catalysts, in general, characterised by their form or physical properties characterised by their surface properties or porosity
    • B01J35/63—Pore volume
    • B01J35/635—0.5-1.0 ml/g
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J35/00—Catalysts, in general, characterised by their form or physical properties
    • B01J35/60—Catalysts, in general, characterised by their form or physical properties characterised by their surface properties or porosity
    • B01J35/64—Pore diameter
    • B01J35/647—2-50 nm

Definitions

  • the present invention relates to catalytic compo ⁇ sitions and hydrocarbon conversion processes using them.
  • zeolite Y has very often been subjected to certain stabilising and/or dealumination process steps during its preparation which result in its having a reduced unit cell constant (a 0 ) and an increased silica to alumina molar ratio.
  • These stabilised zeolites, as well as the as-synthesised zeolite Y possess relatively few pores that are larger than 2 nanometres (nm) in diameter and therefore have a limited mesopore volume (a mesopore has a diameter typically in the range from 2 to 60 nm) .
  • US-A-5 354 452 discloses a process in which ultra- stable Y zeolites having a silica to alumina molar ratio of 6 to 20, and superultrastable Y zeolites having a silica to alumina molar ratio of at least 18 and a unit cell constant (a 0 ) of 2.420 to 2.448 nm (24.20 to 24.48 A) are subjected to a hydrother al treatment with steam at 1000 to 1200 °F followed by an acid treatment at 140 to 220 °F.
  • the hydrothermally-treated zeolite is characterised by a unit cell constant (a 0 ) typically in the range from 2.427 to 2.439 nm (24.27 to 24.39 A), a secondary pore volume contained in mesopores having a diameter in the range from 10 to 60 nm (100 to 600 A) of 0.09 to 0.13 ml/g, and a total pore volume of 0.16 to 0.20 ml/g, whereas the acidified, hydrothermally-treated zeolite is characterised by a unit cell constant (a 0 ) typically in the range from 2.405 to 2.418 nm (24.05 to 24.18 A), a secondary pore volume contained in mesopores having a diameter in the range from 10 to 60 nm (100 to 600 A) of 0.11 to 0.14 ml/g, and a total pore volume of 0.16 to 0.25 ml/g.
  • a unit cell constant a 0
  • a 0 typically in the range
  • catalyst compositions containing certain 'Y-type' molecular sieves with even higher mesopore volumes which may advantageously be used in the conversion of hydro ⁇ carbon oils, e.g. by catalytic cracking or hydrocracking. to produce desirable products in greater yield and selectivity.
  • a catalyst composition comprising a molecular sieve having a structure substantially the same as zeolite Y, a unit cell constant (a 0 ) less than or equal to 2.485 nm and a mesopore volume, contained in mesopores having a diameter in the range from 2 to 60 nm, of at least 0.05 ml/g, and a binder, wherein the relationship between the unit cell constant (a 0 ) and the mesopore volume is defined as follows:
  • Unit Cell Cons an (nm) Mesopore Volume (ml/gj 2.485 > a 0 > 2.460 > 0.05
  • the molecular sieve used in the catalyst compositions of the invention is defined as having a structure substantially the same as zeolite Y. This definition is intended to embrace molecular sieves derived not only from zeolite Y per ⁇ e_ but also from modified zeolites Y in which a proportion of the aluminium ions have been replaced by other metal ions such as iron, titanium, gallium, tin, chromium or scandium ions but whose structures are not significantly different from that of zeolite Y, as may be determined by X-ray crystallography.
  • suitable iron- and/or titanium-modified zeolites Y are those disclosed in US Patents Nos. 5 176 817 and 5 271 761, and examples of suitable chromium- and/or tin-modified zeolites Y are those disclosed in EP-A-321 177.
  • the molecular sieve used in the catalyst compositions of the invention is preferably derived from a zeolite Y per ⁇ £, e.g. as described in Zeolite Molecular Sieves (Structure, Chemistry and Use) by Donald W. Breck published by Robert E. Krieger Publishing Company Inc., 1984; and US Patents Nos. 3 506 400, 3 671 191, 3 808 326, 3 929 672 and 5 242 677.
  • the molecular sieve used in the present compositions has a unit cell constant (a 0 ) less than or equal to ( ⁇ ) 2.485 nm (24.85 A) , preferably less than or equal to ( ⁇ ) 2.460 nm (24.60 A) , e.g. in the range from 2.427 to 2.485 nm (24.27 to 24.85 A) , preferably in the range from 2.427 to 2.460 nm (24.27 to 24.60 A) .
  • the molecular sieve has a unit cell constant (a 0 ) up to 2.440 nm (24.40 A), e.g. in the range from 2.427 to
  • the mesopore volume of the molecular sieve as contained in mesopores having a diameter in the range " from 2 to 60 nm, will vary depending on 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 Vnlums (ml/ ⁇ ) 2.485 > a 0 > 2.460 > 0.05 2.460 > a 0 > 2.450 > 0.18
  • the molecular sieve may have a mesopore volume of up to 0.8 ml/g, e.g. in the range from 0.05, preferably from 0.18, more preferably from 0.23, still more preferably from 0.26, advantageously from 0.3 and particularly from 0.4 ml/g, up to 0.6 ml/g, especially up to 0.8 ml/g.
  • the molecular sieves useful in the present invention may conveniently be prepared by a hydrothermal treatment in which a zeolite Y or modified zeolite Y as described above is contacted hydrothermally with an aqueous solution having dissolved therein one or more salts, acids, bases and/or water-soluble organic compounds at a temperature above the boiling point of the solution at atmospheric pressure for a period of time sufficient to provide the zeolite with an increased mesopore volume in mesopores having a diameter in the range from 2 to 60 nm.
  • the product is separated, washed (using deionized water or an acid, e.g. nitric acid, solution) and recovered.
  • the product obtained by this treatment will generally have a unit cell size (unit cell constant) and a silica to alumina molar ratio similar to those of the starting zeolite.
  • the product may be subjected to additional stabilisation and/or dealumination treatments as are well known in the art in order to change the unit cell size and/or the silica to alumina molar ratio.
  • examples of salts which may be used include ammonium, alkali metal (e.g. sodium and potassium) and alkaline earth metal salts of strong and weak, organic and inorganic acids, (e.g nitric and hydrochloric acids) ; examples of acids which may be used include strong inorganic acids such as nitric acid and hydrochloric acid as well as weak organic acids such as acetic acid and formic acid; examples of bases which may be used include inorganic bases such as ammonium, alkali metal and alkaline earth metal hydroxides together with organic bases such as quaternary ammonium hydroxides, amine complexes and pyridinium salts; and examples of water-soluble organic compounds which may be used include Ci-Cg alcohols and ethers.
  • concentration and amount of the aqueous solution contacted with the starting zeolite is adjusted to provide at least 0.1 part by weight (pbw) of dissolved solute per part by weight of ze
  • the pH of the aqueous hydrothermal treatment solution may vary between 3 and 10 and depending on the (modified) zeolite Y to be treated, a high or a low pH may be preferred.
  • a unit cell constant (a 0 ) of from 2.450 to 2.460 nm (2.460 nm > a 0 > 2.450 nm)
  • the starting zeolite has a unit cell constant (a 0 ) of from greater than 2.427 to less than 2.450 nm (2.450 nm > a 0 > 2.427 nm)
  • the pH of the solution should desirably be maintained or adjusted to a value of 3 to 8; and if the starting zeolite has a unit cell constant (a 0 ) less than or equal to 2.427 nm (2.427 nm > a 0
  • the temperature of the hydrothermal treatment should be above the atmospheric boiling point of the aqueous solution. Although temperatures up to 400 °C can be used, a temperature in the range from 110 or 115 to 250 °C is usually satisfactory. Good results can be obtained using a temperature in the range from 140 to 2-00 °C.
  • the treatment time is inversely related to the treatment temperature. Thus, at a higher temperature, a shorter time will be required to effect a given increase in mesopore volume.
  • the treatment time may vary between 5 minutes and 24 hours but is usually in the range from 2 to 12 hours.
  • the duration of the hydrothermal treatment and the temperature at which it is applied should be such as to provide a mesopore volume in the final product which is at least 5%, preferably at least 10%, larger than the mesopore volume in the starting zeolite.
  • a preferred molecular sieve to use in the catalyst composition of the present invention is one prepared by a process comprising contacting a (modified) zeolite Y as hereinbefore defined hydrothermally with an aqueous solution having dissolved therein one or more salts, acids, bases and/or water-soluble organic compounds at a temperature above the atmospheric boiling point of the solution, followed by separation and washing with an acid solution.
  • the acid solution may be an aqueous solution of one or more acids selected from inorganic and organic acids, e.g. nitric acid, hydrochloric acid, acetic acid, formic acid and citric acid.
  • washing with an acid solution has the advantage of further enhancing the middle distillate selectivity of the increased mesopore molecular sieve.
  • binder in the catalyst compositions of the invention it is convenient to use an inorganic oxide or a mixture of two or more such oxides.
  • the binder may be amorphous or crystalline.
  • suitable binders include alumina, silica, magnesia, titania, zirconia, silica-alumina, silica-zirconia, silica-boria and mixtures thereof.
  • a preferred binder to use is alumina, or alumina in combination with a dispersion of silica- alumina in an alumina matrix, particularly a matrix of gamma alumina.
  • the catalyst composition of the present invention preferably contains from 1 to 80 %w (per cent by weight) of the molecular sieve and from 20 to 99 %w binder, based on the total dry weight of molecular sieve and binder. More preferably, the catalyst composition contains from 10 to 70 %w of the molecular sieve and from 30 to 90 %w binder, in particular from 20 to 50 %w of the molecular sieve and from 50 to 80 %w binder, based on the total dry weight of molecular sieve and binder.
  • the present catalyst compositions may further comprise at least one hydrogenation component.
  • hydrogenation components useful in the present invention include Group 6B (e.g. molybdenum and tungsten) and Group 8 metals (e.g. cobalt, nickel, iridium, platinum and palladium) , their oxides and sulphides.
  • the catalyst composition preferably contains at least two hydrogenation components, e.g. a molybdenum and/or tungsten component in combination with a cobalt and/or nickel component. Particularly preferred combinations are nickel/tungsten and nickel/molybdenum. Very advantageous results are obtained when the metals are used in the sulphide form.
  • the catalyst composition may contain up to 50 parts by weight of hydrogenation component, calculated as metal per 100 parts by weight of total catalyst composition.
  • the catalyst composition may contain from 2 to 40, more preferably from 5 to 25 and especially from 10 to 20, parts by weight of Group 6 metal (s) and/or fror. 0.05 to 10, more preferably from 0.5 to 8 and advantage ⁇ ously from 2 to 6, parts by weight of Group 8 metal (s) , calculated as metal per 100 parts by weight of total catalyst composition.
  • the present catalyst compositions may be prepared in accordance with techniques conventional in the art .
  • a convenient method for preparing a catalyst composition for use in cracking comprises mixing binder material with water to form a slurry or sol, adjusting the pH of the slurry or sol as appropriate and then adding a powdered molecular sieve as defined above together with additional water to obtain a slurry or sol with a desired solids concentration.
  • the slurry or sol is then spray-dried.
  • the spray-dried particles thus formed may be used directly or may be calcined prior to use.
  • One method for preparing a catalyst composition for use in hydrocracking comprises mulling a molecular sieve as defined above and binder in the presence of water and optionally a peptising agent, extruding the resulting mixture into pellets and calcining the pellets.
  • the pellets thus obtained are then impregnated with one or more solutions of Group 6B and/or Group 8 metal salts and again calcined.
  • the molecular sieve and binder may be co-mulled in the presence of one or more solutions of Group 6B and/or Group 8 metal salts and optionally a peptising agent, and the mixture so formed extruded into pellets.
  • the pellets may then be calcined.
  • the present invention further provides a process for converting a hydrocarbonaceous feedstock into lower boiling materials which comprises contacting the feedstock at elevated temperature with a catalyst composition according to the invention.
  • the hydrocarbonaceous feedstocks useful in the present process can vary within a wide boiling range. They include lighter fractions such as kerosine fractions as well as heavier fractions such as gas oils, coker gas oils, vacuum gas oils, deasphalted oils, long and short residues, catalytically cracked cycle oils, thermally or catalytically cracked gas oils, and syncrudes, optionally originating from tar sands, shale oils, residue upgrading processes or bio ass. Combinations of various hydro ⁇ carbon oils may also be employed.
  • the feedstock will generally comprise hydrocarbons having a boiling point of at least 330 °C. In a preferred embodiment of the invention, at least 50 %w of the feedstock has a boiling point above 370 °C.
  • the feedstock may have a nitrogen content of up to 5000 ppmw (parts per million by weight) and a sulphur content of up to 6 %w. Typically, nitrogen contents are in the range from 250 to 2000 ppmw and sulphur contents are in the range from 0.2 to 5 %w. It is possible and may sometimes be desirable to subject part or all of the feedstock to a pre-treatment, for example, hydrodenitrogenation, hydrodesulphurisation or hydrodemetallisation, methods for which are known in the art.
  • the process is carried out under catalytic cracking conditions (i.e. in the absence of added hydrogen) , the process is conveniently carried out in an upwardly or downwardly moving catalyst bed, e.g. in the manner of conventional Thermofor Catalytic Cracking (TCC) or Fluidised Catalytic Cracking (FCC) processes.
  • TCC Thermofor Catalytic Cracking
  • FCC Fluidised Catalytic Cracking
  • the process conditions are preferably a reaction temperature in the range from 400 to 900 °C, more preferably from 450 to 800 °C and especially from 500 to 650 °C; a total pressure of from 1 x 10 5 to 1 x 10 6 Pa (1 to 10 bar) , in particular from 1 x 10 5 to 7.5 x 10 5 Pa (1 to 7.5 bar) ; a catalyst composition/feedstock weight ratio (kg/kg) in the range from 5 to 150, especially 20 to 100; and a contact time between catalyst composition and feedstock of from 0.1 to 10 seconds, advantageously from 1 to 6 seconds.
  • the process according to the present invention is preferably carried out under hydrogenating conditions, i.e. under catalytic hydrocracking conditions, e.g. residue hydrocracking conditions.
  • the reaction temperature is preferably in the range from 250 to 500 °C, more preferably from 300 to 450 °C and especially from 350 to 450 °C.
  • the total pressure is preferably in the range from 5 x 10 6 to 3 x 10 7 Pa (50 to 300 bar), more preferably from 7.5 x 10 6 to 2.5 x 10 7 Pa (75 to 250 bar) and even more preferably from 1 x 10 7 to 2 x 10 7 Pa (100 to 200 bar) .
  • the hydrogen partial pressure is preferably in the range from 2.5 x 10 6 to 2.5 x 10 7 Pa (25 to 250 bar), more preferably from 5 x 10 6 to 2 x 10 7 Pa (50 to 200 bar) and still more preferably from 6 x 10 6 to 1.8 x 10 7 Pa (60 to 180 bar).
  • a space velocity in the range from 0.05 to 10 kg feedstock per litre catalyst composition per hour (kg.l-i.h "1 ) is conveniently used.
  • the space velocity is in the range from 0.1 to 8, particularly from 0.1 to 5, kg.l -1 .h _1 .
  • gas/feed ratios in the range from 100 to 5000 Nl/kg are conveniently employed.
  • the total gas rate employed is in the range from 250 to 2500 Nl/kg.
  • VUSY very ultrastable zeolite Y having a silica to alumina molar ratio of 7.4, a unit cell constant (a 0 ) of 2.433 nm (24.33 A), a surface area of 691 m 2 /g and a mesopore volume of 0.177 ml/g was added to an aqueous 4N solution of ammonium nitrate (NH4NO3) in an amount such that, on a dry weight basis, the ratio of the number of grams of ammonium nitrate to the number of grams of zeolite Y was 1.5.
  • NH4NO3 ammonium nitrate
  • the pellets comprised 4 %w of the molecular sieve and 96 %w binder (66 %w silica-alumina and 30 %w alumina), on a dry weight basis. 10.07 g of an aqueous solution of nickel nitrate
  • VUSY very ultrastable zeolite Y having a silica to alumina molar ratio of 8.4, a unit cell constant (a 0 ) of 2.434 nm (24.34 A), a surface area of 727 m 2 /g and a mesopore volume of 0.180 ml/g was added to an aqueous 4N solution of ammonium nitrate (NH4NO3) in an amount such that, on a dry weight basis, the ratio of the number of grams of ammonium nitrate to the number of grams of zeolite Y was 1.5.
  • NH4NO3 ammonium nitrate
  • a molecular sieve having a structure substantially the same as zeolite Y which, after 2 three-hour washes at 93 °C with a nitric acid solution (2 milli-equivalents (meq) hydrogen ions (H + ) per gram of zeolite) and drying at 110 °C, was found to have a silica to alumina molar ratio of 10.0, a unit cell constant (a 0 ) of 2.427 nm (24.27 A), a relative crystallinity of 71%, a surface area of 605 m 2 /g and a mesopore volume of 0.423 ml/g.
  • Example l-(ii) a molecular sieve prepared as described in (i) above (5 g) was combined with amorphous 55/45 silica-alumina (82 g) and high microporosity precipitated alumina (40 g) to form cylindrically-shaped pellets which, after drying and calcination, had a circular end surface diameter of 1.2 mm and a water pore volume of 0.717 ml/g.
  • the pellets comprised 5 %w of the molecular sieve and 95 %w binder (65 %w silica-alumina and 30 %w alumina), on a dry weight basis.
  • VUSY very ultrastable zeolite Y having a silica to alumina molar ratio of 7.4, a unit cell constant (a 0 ) of 2.433 nm (24.33 A), a surface area of 691 m 2 /g and a mesopore volume of 0.177 ml/g was added to an aqueous 4N solution of ammonium nitrate (NH4NO3) in an amount such that, on a dry weight basis, the ratio of the number of grams of ammonium nitrate to the number of grams of zeolite Y was 1.5.
  • NH4NO3 ammonium nitrate
  • Example 1 a molecular sieve prepared as described in (i) above (7 g) was combined with amorphous 55/45 silica-alumina (125 g) and high microporosity precipitated alumina (60 g) to form cylindrically-shaped pellets which, after drying and calcination, had a circular end surface diameter of 1.6 mm and a water pore volume of 0.792 ml/g.
  • the pellets comprised 4 %w of the molecular sieve and 96 %w binder (66 %w silica-alumina and 30 %w alumina), on a dry weight basis.
  • Each of the catalyst compositions of Examples 1 to 3 was assessed for middle distillates selectivity in a hydrocracking performance test.
  • the test involved contacting a hydrocarbonaceous feedstock, (a hydrotreated heavy vacuum gas oil) with the catalyst compositions (pre-sulphided in conventional manner) in a once-through operation under the following operating conditions: a space velocity of 1.5 kg gas oil per litre catalyst composition per hour (kg.1 ⁇ * .h ⁇ l) , a hydrogen sulphide partial pressure of 5.5 x 10 ⁇ Pa (5.5 bar), an ammonia partial pressure of 7.5 x 10 ⁇ Pa (0.075 bar), a total pressure of 14 x 10 6 Pa (140 bar) and a gas/feed ratio of 1500 Nl/kg.
  • the hydrotreated heavy vacuum gas oil had the following properties: Carbon content 86.5 %w Hydrogen content 13.4 %w Sulphur content 0.007 %w Nitrogen content 16.1 ppmw Density (70/4) 0.8493 g/ml
  • Example 5 As can be seen from Table I above, the catalyst compositions of Examples 1 to 3 according to the invention show high middle distillate selectivity. Example 5
  • VUSY very ultrastable zeolite Y having a silica to alumina molar ratio of 7.9, a unit cell constant (a 0 ) of 2.431 nm (24.31 A), a surface area of 550 m 2 /g and a mesopore volume of 0.141 ml/g was added to an aqueous 4N solution of ammonium nitrate (NH4NO3) in an amount such that, on a dry weight basis, the ratio of the number of grams of ammonium nitrate to the number of grams of zeolite Y was 1.5.
  • NH4NO3 ammonium nitrate
  • Example l(ii) a molecular sieve prepared as described in (i) above (22.3 g) was combined with high microporosity precipitated alumina (110.0 g) to form cylindrically-shaped pellets which, after drying and calcination, had a circular end surface diameter of 1.6 mm and a water pore volume of 0.642 ml/g.
  • the pellets comprised 20 %w of the molecular sieve and 80 %w alumina binder, on a dry weight basis. 8.92 g of an aqueous solution of nickel nitrate
  • Example 5 which is a catalyst composition according to the present invention, was assessed for middle distillates selectivity in a hydrocracking performance test.
  • the test involved contacting a hydrocarbonaceous feedstock (a hydrotreated heavy vacuum gas oil) with the catalyst .composition of Example 5 (pre-sulphided in conventional manner) in a once-through operation under the following operating conditions: a space velocity of 1.5 kg gas oil per litre catalyst composition per hour (kg.l ⁇ l .h ⁇ ) , a hydrogen sulphide partial pressure of 5.5 x 10 ⁇ Pa (5.5 bar), an ammonia partial pressure of 1.65 x 10 4 Pa (0.165 bar), a total pressure of 14 x 10 ⁇ Pa (140 bar) and a gas/feed ratio of 1500 Nl/kg.
  • the hydrotreated heavy vacuum gas oil had the following properties:
  • the performance of the catalyst composition was assessed at 65 %w net conversion of feed components boiling above 370 °C.
  • the selectivity for middle distillates (i.e. the fraction boiling in the temperature range from 150 to 370 °C) shown by the catalyst composition of Example 5 was found to be high at 69.0 %w/w.

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Abstract

La présente invention concerne une composition de catalyseur et un procédé de conversion d'hydrocarbures utilisant cette composition. Ce catalyseur est constitué d'un tamis moléculaire et d'un liant. Le tamis moléculaire a sensiblement la même structure que la zéolithe Y, une constante de cellule unitaire (ao) égale ou inférieure à 2,458 nm et un volume des mésopores, correspondant aux mésopores ayant un diamètre compris entre 2 et 60 nm, d'au moins 0,05 ml/g. La relation entre la constante de cellule unitaire (ao) et le volume des mésopores est donnée dans le tableau (I).
PCT/EP1996/000915 1995-03-03 1996-03-01 Compositions de catalyseur et leur utilisation dans des procedes de conversion d'hydrocarbures WO1996027438A1 (fr)

Priority Applications (5)

Application Number Priority Date Filing Date Title
NZ303210A NZ303210A (en) 1995-03-03 1996-03-01 Zeolite catalyst compositions and their use in hydrocarbon conversion processes
JP8526603A JPH11500956A (ja) 1995-03-03 1996-03-01 触媒組成物および炭化水素変換法におけるその使用
EP96905859A EP0817676A1 (fr) 1995-03-03 1996-03-01 Compositions de catalyseur et leur utilisation dans des procedes de conversion d'hydrocarbures
AU49451/96A AU4945196A (en) 1995-03-03 1996-03-01 Catalyst compositions and their use in hydrocarbon conversion processes
MXPA/A/1997/006566A MXPA97006566A (en) 1995-03-03 1997-08-28 Catalytic compositions and their use in hydrocarbon conversion processes

Applications Claiming Priority (2)

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US39884795A 1995-03-03 1995-03-03
US398,847 1995-03-03

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EP (1) EP0817676A1 (fr)
JP (1) JPH11500956A (fr)
KR (1) KR19980702741A (fr)
AU (1) AU4945196A (fr)
CA (1) CA2214331A1 (fr)
CZ (1) CZ274697A3 (fr)
NZ (1) NZ303210A (fr)
WO (1) WO1996027438A1 (fr)

Cited By (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN1068528C (zh) * 1997-08-27 2001-07-18 中国石油化工总公司 具有丰富次级孔的y沸石及其制备方法
WO2005084799A1 (fr) * 2004-03-03 2005-09-15 Shell Internationale Research Maatschappij B.V. Support catalytique et composition catalytique, procedes de preparation et d'utilisation associes
WO2007043731A1 (fr) * 2005-10-14 2007-04-19 Korea Advanced Institute Of Science And Technology Procede de preparation d'un tamis moleculaire cristallin microporeux comprenant des structures mesoporeuses
FR2940265A1 (fr) * 2008-12-22 2010-06-25 Total Raffinage Marketing Zeolites y modifiees, leur procede de fabrication et leur utilisation
JP2014510614A (ja) * 2010-12-23 2014-05-01 トータル・マーケティング・サービシーズ 産業用の水素化転換触媒、例えば、水素化分解触媒の製造方法、それによって得られた触媒、及び、水素化転換におけるその触媒の使用

Citations (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US4668649A (en) * 1982-08-02 1987-05-26 Catalysts & Chemicals Industries Co., Ltd. Modified zeolite
US5354452A (en) * 1990-01-11 1994-10-11 Texaco Inc. Synthesis of zeolites

Patent Citations (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US4668649A (en) * 1982-08-02 1987-05-26 Catalysts & Chemicals Industries Co., Ltd. Modified zeolite
US5354452A (en) * 1990-01-11 1994-10-11 Texaco Inc. Synthesis of zeolites

Cited By (9)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN1068528C (zh) * 1997-08-27 2001-07-18 中国石油化工总公司 具有丰富次级孔的y沸石及其制备方法
WO2005084799A1 (fr) * 2004-03-03 2005-09-15 Shell Internationale Research Maatschappij B.V. Support catalytique et composition catalytique, procedes de preparation et d'utilisation associes
CN100428995C (zh) * 2004-03-03 2008-10-29 国际壳牌研究有限公司 催化剂载体和催化剂组合物、其制备方法和用途
WO2007043731A1 (fr) * 2005-10-14 2007-04-19 Korea Advanced Institute Of Science And Technology Procede de preparation d'un tamis moleculaire cristallin microporeux comprenant des structures mesoporeuses
KR100727288B1 (ko) 2005-10-14 2007-06-13 한국과학기술원 메조다공성 골격을 갖는 미세다공성 결정성 분자체의제조방법
US7785563B2 (en) 2005-10-14 2010-08-31 Korea Advanced Institute Of Science And Technology Method of the preparation of microporous crystalline molecular sieve possessing mesoporous frameworks
EP1937592A4 (fr) * 2005-10-14 2015-07-15 Korea Advanced Inst Sci & Tech Procede de preparation d'un tamis moleculaire cristallin microporeux comprenant des structures mesoporeuses
FR2940265A1 (fr) * 2008-12-22 2010-06-25 Total Raffinage Marketing Zeolites y modifiees, leur procede de fabrication et leur utilisation
JP2014510614A (ja) * 2010-12-23 2014-05-01 トータル・マーケティング・サービシーズ 産業用の水素化転換触媒、例えば、水素化分解触媒の製造方法、それによって得られた触媒、及び、水素化転換におけるその触媒の使用

Also Published As

Publication number Publication date
AU4945196A (en) 1996-09-23
CA2214331A1 (fr) 1996-09-12
NZ303210A (en) 1997-12-19
CZ274697A3 (cs) 1998-07-15
EP0817676A1 (fr) 1998-01-14
JPH11500956A (ja) 1999-01-26
KR19980702741A (ko) 1998-08-05
MX9706566A (es) 1997-11-29

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