WO2004052534A1 - Procede d'hydrotraitement de charge lourde reposant sur l'utilisation d'un melange de catalyseurs - Google Patents

Procede d'hydrotraitement de charge lourde reposant sur l'utilisation d'un melange de catalyseurs Download PDF

Info

Publication number
WO2004052534A1
WO2004052534A1 PCT/EP2003/013791 EP0313791W WO2004052534A1 WO 2004052534 A1 WO2004052534 A1 WO 2004052534A1 EP 0313791 W EP0313791 W EP 0313791W WO 2004052534 A1 WO2004052534 A1 WO 2004052534A1
Authority
WO
WIPO (PCT)
Prior art keywords
catalyst
pore volume
pores
diameter
total pore
Prior art date
Application number
PCT/EP2003/013791
Other languages
English (en)
Inventor
Frans Lodewijk Plantenga
Katsuhisa Fujita
Satoshi Abe
Original Assignee
Albemarle Netherlands B.V.
Nippon Ketjen Co., Ltd.
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Application filed by Albemarle Netherlands B.V., Nippon Ketjen Co., Ltd. filed Critical Albemarle Netherlands B.V.
Priority to ES03782317T priority Critical patent/ES2859557T3/es
Priority to EP03782317.6A priority patent/EP1567262B1/fr
Priority to JP2004558008A priority patent/JP4369871B2/ja
Priority to CA2508605A priority patent/CA2508605C/fr
Priority to AU2003289969A priority patent/AU2003289969A1/en
Publication of WO2004052534A1 publication Critical patent/WO2004052534A1/fr

Links

Classifications

    • 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
    • C10G49/00—Treatment of hydrocarbon oils, in the presence of hydrogen or hydrogen-generating compounds, not provided for in a single one of groups C10G45/02, C10G45/32, C10G45/44, C10G45/58 or C10G47/00
    • C10G49/02—Treatment of hydrocarbon oils, in the presence of hydrogen or hydrogen-generating compounds, not provided for in a single one of groups C10G45/02, C10G45/32, C10G45/44, C10G45/58 or C10G47/00 characterised by the catalyst used
    • C10G49/04—Treatment of hydrocarbon oils, in the presence of hydrogen or hydrogen-generating compounds, not provided for in a single one of groups C10G45/02, C10G45/32, C10G45/44, C10G45/58 or C10G47/00 characterised by the catalyst used containing nickel, cobalt, chromium, molybdenum, or tungsten metals, or compounds thereof

Definitions

  • the present invention relates to a process for hydroprocessing a heavy hydrocarbon oil, in particular a process in which a mixture of two catalysts is used to obtain advantageous effects in the hydroprocessing of heavy hydrocarbon oils.
  • the present invention also relates to a mixture of catalysts suitable for use in such a process.
  • the present invention relates to a process suitable for the hydroprocessing of heavy hydrocarbon oils containing a large amount of impurities such as sulfur, metals, and asphaltene to effect hydrodesulfurisation (HDS), hydrodemetallisation (HDM), asphaltene reduction (HDAsp) and/or conversion into lighter products- while limiting the amount of sediment produced.
  • the feed may also contain other contaminants such as Conradson carbon residue (CCR) and nitrogen, and carbon residue reduction (HDCCR) and hydrodenitrification (HDN) may also be desired processes.
  • CCR Conradson carbon residue
  • HDCCR carbon residue reduction
  • HDN hydrodenitrification
  • Hydrocarbon oils containing 50 wt.% or more of components with a boiling point of 538°C or higher are called heavy hydrocarbon oils. These include atmospheric residue (AR) and vacuum residue (VR), which are produced in petroleum refining. It is desired to remove impurities such as sulfur from these heavy hydrocarbon oils by hydroprocessing, and to convert them into lighter oils, which have a higher economic value.
  • AR atmospheric residue
  • VR vacuum residue
  • hydroprocessing of heavy hydrocarbon oils is done in ebullating bed operation or in fixed bed operation.
  • Sediment formed during hydroprocessing operations may settle and deposit in such apparatuses as heat exchangers and reactors, and because it threatens to close off the passage, it can seriously hamper the operation of these apparatuses.
  • sediment formation is an important factor, and there is therefore need for a process for effecting efficient contaminant removal in combination with low sediment formation and high conversion.
  • US 5,100,855 describes a catalyst mixture for effecting hydrodemetallisation, hydrodesulphurisation, hydrodenitrogenation and hydroconversion of an asphaltene-containing feedstock, wherein one catalyst is a relatively small-pore catalyst and the other possesses a relatively large amount of macropore volume.
  • the catalyst mixture is preferably applied in an ebullating bed.
  • the first catalyst has less than 0.10 ml/g of pore volume in pores with a diameter above 200 A, less than 0.02 ml/g in pores with a diameter above 800 A, and a maximum average mesopore diameter of 130 A.
  • the second catalyst has more than 0.07 ml/g of pore volume in pores with a diameter of greater than 800 A.
  • US 6,086,749 describes a process and catalyst system for use in a moving bed, wherein a mixture of two types of catalysts is used, each designed for a different function such as hydrodemetallisation and hydrodenitrogenation, respectively.
  • At least one of the catalysts preferably has at least 75% of its pore volume in pores with a diameter of 100-300 A, and less than 20% of its pore volume in pores with a diameter below 100 A.
  • the object of the present invention is to provide an effective process for the hydroprocessing of a heavy hydrocarbon oil containing a large amount of impurities such as sulfur, Conradson carbon residue, metals, nitrogen, and asphaltene, especially a heavy oil containing 80% or more vacuum residue fractions, for adequately removing the impurities.
  • the process should show low sediment formation, high asphaltene removal, and high conversion. Further, it should possess high flexibility.
  • the first catalyst is specifically designed to decrease the impurities in the heavy hydrocarbon oil. In particular, it achieves demetallisation and efficient asphaltene removal, which is effective in preventing asphaltene precipitation.
  • the second catalyst is tailored to effect advanced desulfurisation and hydrogenation reactions while inhibiting sediment formation due to asphaltene precipitation, to allow stable operation.
  • the process according to the invention is a process for hydroprocessing a heavy hydrocarbon oil, comprising contacting a heavy hydrocarbon oil in the presence of hydrogen with a mixture of hydroprocessing catalyst I and hydroprocessing catalyst II, wherein • catalyst I comprises a Group V1B metal component and optionally a Group VIII metal component on a porous inorganic carrier, said catalyst having a specific surface area of at least 100 m 2 /g, a total pore volume of at least 0.55 ml/g, at least 50% of the total pore volume in pores with a diameter of at least 20 nm (200 A), and 10-30% of the total pore volume in pores with a diameter of at least 200 nm (2000 A) and
  • catalyst II comprises a Group VI B metal component and optionally a Group VIII metal component on a porous inorganic carrier, said catalyst having a specific surface area of at least 100 m 2 /g, a total pore volume of at least 0.55 ml/g, at least 75% of the total pore volume in pores with a diameter of
  • the present invention also pertains to a mixture of catalysts suitable for use in such a process, wherein the catalyst mixture comprises catalysts I and II defined above.
  • the catalysts used in the process according to the invention comprise catalytic materials on a porous carrier.
  • the catalytic materials present on the catalysts used in the process according to the invention comprise a Group VI B metal and optionally a Group VIII metal of the Periodic Table of Elements applied by
  • a Group Vlll metal is present on the catalysts used in the process according to the invention.
  • the Group Vlll metal used in this invention is at least one selected from nickel, cobalt, and iron. In view of performance and economy, cobalt and nickel are preferred. Nickel is especially preferred.
  • As the Group VI B metals which can be used molybdenum, tungsten, and chromium may be mentioned, but in view of performance and economy, molybdenum is preferred.
  • the combination of molybdenum and nickel is particularly preferred for the catalytic materials of the catalyst according to the invention. Based on the weight (100 wt.%) of the final catalyst, the amounts of the respective catalytic materials used in the catalysts used in the process according to the invention are as follows.
  • the catalysts generally comprise 4-30 wt.% of Group VI B metal, calculated as trioxide, preferably 7-20 wt.%, more preferably 8-16 wt.%. If less than 4 wt.% is used, the activity of the catalyst is generally less than optimal. On the other hand, if more than 16 wt.%, in particular more than 20 wt.% is used, the catalytic performance is generally not improved further. Optimum activity is obtained when the Group VI metal content is selected to be within the cited preferred ranges.
  • the catalysts comprise a Group Vlll metal component. If applied, this component is preferably present in an amount of 0.5-6 wt.%, more preferably 1-5 wt.%, of Group Vlll metal, calculated as oxide. If the amount is less than 0.5 wt.%, the activity of the catalysts is less than optimal. If more than 6 wt.% is present, the catalyst performance will not be improved further.
  • the total pore volume of catalyst I and catalyst II is at least 0.55 ml/g, preferably at least 0.6 ml/g. It is preferred for it to be at most 1.0 ml/g, more preferably at most 0.9 ml/g.
  • the determination of the total pore volume and the pore size distribution is effected via mercury penetration at a contact angle of 140° with a surface tension of 480 dynes/cm, using, for example, a mercury porosimeter Autopore II (trade name) produced by Micrometrics.
  • Catalyst I has a specific surface area of at least 100 m 2 /g.
  • the surface area is determined in accordance with the BET method based on N 2 adsorption.
  • Catalyst I has at least 50%o of the total pore volume in pores with a diameter of at least 20 nm (200 A), preferably at least 60%o.
  • the percentage of pore volume in this range is preferably at most 80%). If the percentage of pore volume in this range is below 50%, the catalytic performance, especially the asphaltene
  • the carrier of catalyst I preferably shows at least 43% of pore volume in this range, more preferably at least 47%.
  • the percentage of pore volume in this range for the carrier preferably is at most 75%, more preferably at most 70%.
  • Catalyst I has 10-30% of the total pore volume in pores with a diameter of at least 200 nm (2000 A), preferably 15-25%. If the percentage of pores in this range is too low, the asphaltene removal capacity in the bottom of the reactor will decrease, therewith increasing sediment formation. If the percentage of pores in this range is too high, the mechanical strength of the catalyst will decrease, possibly to a value which may be unacceptable for commercial operation. To improve catalyst strength and activity, Catalyst I preferably has 0-5% of the total pore volume in pores with a diameter above 1000 nm (10000 A), more preferably 0-1%.
  • Catalyst I when the feedstock contains a large amount of vacuum residue, that is, if the percentage of the feed boiling above 538°C is at least 70%, more preferably at least 80%>, it is preferred for Catalyst I to have a %PV(10-120 nm) (%PV(100-1200 A)) of less than 85%, preferably less than 82%, still more preferably less than 80%. If the percentage of pore volume present in this range becomes too high, the percentage of pore volume in pores with a diameter above 200 nm (2000 A) will decrease, and the residue cracking rate may be insufficient.
  • Catalyst I it is preferred for Catalyst I to have less than 0.2 ml/g of pore volume in pores with a diameter of 50-150 nm (500 to 1,500 A). If more than 0.2 ml/g of pore volume is present in this range, the relative percentage of pore volume present in pores with a diameter below 30 nm (300 A) will decrease, and the catalytic performance may decline. Additionally, since pores with a diameter below 30 nm (300 A) are liable to closing by very heavy feedstock components, it is feared that the life of the catalyst may be shortened if the amount of pore volume present in this range is relatively too small.
  • Catalyst I it is preferred for Catalyst I to have less than 25% of its pore volume in pores with a diameter of 10 nm (100 A) or less, more preferably less than 17%), still more preferably less than 10%. If the percentage of pore volume present in this range is above this value, sediment formation may increase due to increased hydrogenation of the non-asphaltenic feed constituents.
  • Catalyst I is based on a porous inorganic oxide carrier which generally comprises the conventional oxides, e.g., alumina, silica, silica-alumina, alumina with silica-alumina dispersed therein, silica-coated alumina, magnesia, zirconia, boria, and titania, as well as mixtures of these oxides. It is preferred for the carrier to consist for at least 80%> of alumina, more preferably at least 90%, still more preferably at least 95%.
  • a carrier consisting essentially of alumina is preferred, the wording "consisting essentially of being intended to mean that minor amounts of other components may be present, as long as they do not detrimentally affect the catalytic activity of the catalyst.
  • An example of a suitable catalyst I is the catalyst described in WO 01/100541.
  • Catalyst II has a specific surface area of at least 100 m 2 /g, preferably at least 130 m 2 /g. If the surface area is below 100 m 2 /g, the catalytic activity will be insufficient.
  • Catalyst II will have at least 75% of the total pore volume in pores with a diameter of 10-120 nm (100-1200 A), preferably at least 78%. If the percentage of pore volume in this range is insufficient, the hydrocracking and hydrodesulfurisation activity of the catalyst will be insufficient. Catalyst II has 0- 2% of the total pore volume in pores with a diameter of at least 400 nm (4000 A), and 0-1% of the total pore volume in pores with a diameter of at least 1000 nm (10000 A). If these requirements are not met, the stability of the hydrodesulfurisation and hydrocracking activity of Catalyst II cannot be guaranteed.
  • Catalyst II has a %PV(>2000 A) which is less than that of catalyst I. Preferably, it is less than 10%, more preferably it is less than 5 %, still more preferably it is less than 3%.
  • Catalyst II it is preferred for Catalyst II to have less than 25% of its pore volume in pores with a diameter of 10 nm (100 A) or less, more preferably less than 17%), still more preferably less than 10%. If the percentage of pore volume present in this range is above this value, sediment formation may increase due to increased hydrogenation of the non-asphaltenic feed constituents.
  • Catalyst II is also based on a porous inorganic oxide carrier which generally comprises the conventional oxides, e.g., alumina, silica, silica-alumina, alumina with silica-alumina dispersed therein, silica-coated alumina, magnesia, zirconia, boria, and titania, as well as mixtures of these oxides. It is preferred for the carrier to consist for at least 70 wt.% of alumina, more preferably at least 88 wt.%), with the balance being made up of silica.
  • the first specific embodiment further indicated as Catalyst lla, has a surface area of at least 100 m 2 /g. It is preferably between 100 and 180 m 2 /g, more preferably between 150 and 170 m 2 /g. It has at least 75% of the total pore volume in pores with a diameter of 10-120 nm (100-1200 A), preferably at least 85%, more preferably at least 87%o.
  • Catalyst lla preferably has a %PV(>200 A of at least 50%, preferably 60-80%, a %PV(>1000 A) of at least 5%, preferably 5-30%, more preferably 8-25%.
  • Catalyst lla preferably is based on an alumina carrier.
  • alumina carrier in this embodiment, a carrier consisting essentially of alumina is preferred, the wording "consisting essentially of being intended to mean that minor amounts of other components may be present, as long as they do not detrimentally affect the catalytic activity of the catalyst.
  • the carrier can contain at least one material selected, for example, from oxides of silicon, titanium, zirconium, boron, zinc, phosphorus, alkali metals and alkaline earth metals, zeolite, and clay minerals. These material are preferably present in an amount of less than 5 wt.%, based on the weight of the completed catalyst, preferably less than 2.5 wt.%), more preferably less than 1.5 ' wt.%, still more preferably less than 0.5 wt.%.
  • Suitable catalysts meeting the requirements of catalyst lla are described in WO 02/053286.
  • the second specific embodiment further indicated as Catalyst lib, has a surface area of at least 150 m 2 /g, preferably 185-250 m 2 /g. It has at least 75% of the total pore volume in pores with a diameter of 10-120 nm (100-1200 A), preferably at least 78%. It may be preferred for catalyst Mb to have less than 50% of its pore volume present in pores with a diameter of above 20.0 A, more preferably less than 40%.
  • Catalyst lib is preferably based on a carrier comprising at least 3.5 wt.%> of silica, calculated on the weight of the final catalyst, more preferably 3.5-30 wt.%, still more preferably 4-12 wt.%, even more preferably 4.5-10 wt.%).
  • the presence of at least 3.5 wt.% of silica has been found to increase the performance of Catalyst lib.
  • the balance of the carrier of. catalyst lib is generally made up of alumina, optionally containing other refractory oxides, such as titania, zirconia, etc. It is preferred that the balance of the carrier of catalyst lib is made up of at least 90%> of alumina, more preferably at least 95%).
  • the carrier of the catalyst of the invention may consist essentially of silica and alumina, the wording "consists essentially of being intended to mean that minor amounts of other components may be present,. as long as they do not detrimentally affect the catalytic activity of the catalyst. It may also be preferred for Catalyst lib to comprise a Group IA metal component. Sodium and potassium may be mentioned as suitable materials. Sodium is preferred for reasons of performance and economy.
  • the amount of Group IA metal is 0.1-2 wt.%, preferably 0.2-1 wt.%>, more preferably 0.1-0.5 wt.%, calculated as oxide.
  • catalyst lib may additionally be preferred for catalyst lib to comprise a compound of Group VA, more in particular one or more compounds selected from phosphorus, arsenic, antimony, and bismuth. Phosphorus is preferred.
  • the compound in this case preferably is present in an amount of 0.05-3 wt.%, more preferably 0.1-2 wt.%., still more preferably 0.1-1 wt.%, calculated as P 2 Os.
  • a particularly preferred embodiment of catalyst lib comprises the combination of silica and a Group IA metal component, in particular sodium, as described above.
  • catalyst lib comprises the combination of silica and phosphorus as described above.
  • Still another particularly preferred embodiment of catalyst lib comprises the combination of silica, Group IA metal component, in particular sodium, and phosphorus as described above.
  • catalyst II of the present invention comprises a mixture of catalysts lla and lib. If a mixture of catalyst lla and catalyst lib is used, it is preferred for catalyst lla to have at least 50%o of its pore volume in pores with a diameter above 200 A, more preferably 60-80%), while for catalyst lib it is preferred to have less than 50%o of its pore volume present in pores with a diameter of above 200 A, more preferably less than 40%.
  • catalyst lla will show good asphaltene cracking properties and low sediment formation and catalyst lib will show good hydrodesulfurisation activity and good hydrogenation activity, and the combination will lead to very good results.
  • the mixture has to comprise at least 1 wt.%) of catalyst lib, calculated on the total amount of catalysts lla and lib, preferably at least 10 wt.%>.
  • the mixture preferably comprises up to 50 wt.% of catalyst lib, preferably up to 30 wt.%.
  • catalyst II comprises a mixture of catalysts lla and lib
  • catalyst lib it is particularly preferred for catalyst lib to comprise a compound of Group VA, more in particular one or more compounds selected from phosphorus, arsenic, antimony, and bismuth, more in part phosphorus, as described above.
  • the present invention is directed to a mixture of catalyst I and catalyst II and its use in the hydroprocessing of heavy hydrocarbon feeds.
  • mixture is intended to refer to a catalyst system wherein, when the catalyst has been brought into the unit, both the top half of the catalyst volume and the bottom half of the catalyst volume contain at least 1% of both types of catalyst.
  • mixture is not intended to refer to a catalyst system wherein the feed is first contacted with one type of catalyst and then with the other type of catalyst.
  • catalyst volume is intended to refer to the volume of catalyst comprising both catalyst I and catalyst II. Optional following layers or units comprising other catalyst types are not included therein.
  • each part contains at least 1% of both types of catalyst. It is even more preferred for the mixture in the context of the present invention to be such that if the catalyst volume is horizontally divided into ten parts of equal volume, each part contains at least 1 % of both types of catalyst.
  • At least 1%> of both types of catalyst should be present in the indicated section, preferably at least 5%, more preferably at least 10%.
  • both the right-hand side and the left hand side of the catalyst volume contain at least 1% of both types of catalyst.
  • each part contains at least 1 %> of both types of catalyst. More preferably, if the catalyst volume is vertically divided into ten parts of equal volume, each part contains at least 1%) of both types of catalyst.
  • at least 1% of both types of catalyst should be present in the indicated section, preferably at least 5%>, more preferably at least 10%.
  • the first one which is inherent to ebullating bed operation and preferred for fixed bed operation, is a random mixture of the two types of catalyst particles.
  • ebullating bed operation it should be noted that the word random includes natural segregation taking place in the unit due to differences in density between the catalyst particles.
  • a further method applicable to fixed bed units would be to apply the two types of catalysts in (thin) alternating layers.
  • An additional method would be to sock-load the unit with socks of the two types of catalysts, wherein each sock contains one type of catalyst, but wherein the combination of socks results in a mixture of catalysts as defined above.
  • the mixture of catalysts I and II generally comprises 2-98 wt.%> of catalyst I and 2-98 wt.% of catalyst II.
  • the mixture comprises 10-90 wt.% of catalyst I, more preferably 20-80 wt.% of catalyst I, still more preferably 30-70 wt.%) of catalyst I.
  • the mixture preferably comprises 10-90 wt.%> of catalyst II, more preferably 20-80 wt.% of catalyst II, still more preferably 30-70 wt.% of catalyst II.
  • the catalyst particles can have the shapes and dimensions common to the art.
  • the particles may be spherical, cylindrical, or polylobal and their diameter may range from 0.5 to 10 mm. Particles with a diameter of 0.5-3 mm, preferably 0.7-1.2 mm, for example 0.9-1 mm, and a length of 2-10 mm, for example 2.5- 4.5 mm, are preferred.
  • polylobal particles are preferred, because they lead to a reduced pressure drop in hydrodemetallisation operations. Cylindrical particles are preferred for use in ebullating bed operations.
  • the carrier to be used in the catalysts to be used in the process according to the invention can be prepared by processes known in the art.
  • a typical production process for a carrier comprising alumina is coprecipitation of sodium aluminate and aluminium sulfate.
  • the resulting gel is dried, extruded, and calcined, to obtain an alumina-containing carrier.
  • other components such as silica may be added before, during, or after precipitation.
  • a process for preparing an alumina gel will be described below.
  • a tank containing tap water or warm water is charged with an alkali solution of sodium aluminate, aluminium hydroxide or sodium hydroxide, etc., and an acidic aluminium solution of aluminium sulfate or aluminium nitrate, etc. is added for mixing.
  • the hydrogen ion concentration (pH) of the mixed solution changes with the progression of the reaction. It is preferable that when the addition of the acidic aluminium solution is completed, the pH is 7 to 9, and that during mixing, the temperature is 60 to 75°C. The mixture is then kept at that temperature for, in general, 0.5-1.5 hours, preferably for 40-80 minutes.
  • an alkali solution such as sodium aluminate, ammonium hydroxide or sodium hydroxide is fed into a tank containing tap water or hot water, an acid solution of an aluminium source, e.g., aluminium sulfate or aluminium nitrate, is added, and the resulting mixture is mixed.
  • an aluminium source e.g., aluminium sulfate or aluminium nitrate
  • the pH of the mixture changes as the reaction progresses.
  • the pH is 7 to 9.
  • an alkali metal silicate such as a water glass or an organic silica solution is added as silica source.
  • silica source it can be fed into the tank together with the acid aluminium compound solution or after the aluminium hydrogel has been produced.
  • the silica-containing alumina carrier can, for another example, be produced by combining a silica source such as sodium silicate with an alumina source such as sodium aluminate or aluminium sulfate, or by mixing an alumina gel with a silica gel, followed by moulding, drying, and calcining.
  • the carrier can also be produced by causing alumina to precipitate in the presence of silica in order to form an aggregate mixture of silica and alumina. Examples of such processes are adding a sodium aluminate solution to a silica hydrogel and increasing the pH by the addition of, e.g., sodium hydroxide to precipitate alumina, and coprecipitating sodium silicate with aluminium sulfate.
  • a further possibility is to immerse the alumina carrier, before or after calcination, in an impregnation solution comprising a silicon source dissolved therein.
  • an impregnation solution comprising a silicon source dissolved therein.
  • the gel is separated from the solution and a commercially used washing treatment, for example a washing treatment using tap water or hot water, is carried out to remove impurities, mainly salts, from the gel.
  • a commercially used washing treatment for example a washing treatment using tap water or hot water, is carried out to remove impurities, mainly salts, from the gel.
  • the gel is shaped into particles in a manner known in the art, e.g., by way of extrusion, beading or pelletising.
  • the shaped particles are dried and calcined.
  • the drying is generally carried out at a temperature from room temperature up to 200°C, generally in the presence of air.
  • the calcining is generally carried out at a temperature of 300 to 950°C, preferably 600 to 900°C, generally in the presence of air, for a period of 30 minutes to six hours. If so desired, the calcination may be carried out in the presence of steam to influence the crystal growth in the oxide.
  • a carrier having properties which will give a catalyst with the surface area, pore volume, and pore size distribution characteristics specified above.
  • the surface area, pore volume, and pore size distribution characteristics can be adjusted in a manner known to the skilled person, for example by the addition during the mixing or shaping stage of an acid, such as nitric acid, acetic acid or formic acid, or other compounds as moulding auxiliary, or by regulating the water content of the gel by adding or removing water.
  • the carriers of the catalysts to be used in the process according to the invention have a specific surface area, pore volume, and pore size distribution of the same order as those of the catalysts themselves.
  • the carrier of catalyst I preferably has a surface area of 100-200m 2 /g, more preferably 130-170 m 2 /g.
  • the total pore volume is preferably 0.5-1.2 ml/g, more preferably 0.7-1.1 ml/g.
  • the carrier of catalyst II preferably has a surface area of 180-300 m 2 /g, more preferably 185-250 m 2 /g, and a pore volume of 0.5-1.0 ml/g, more preferably 0.6-0.9 ml/g.
  • the Group VI B metal components, Group Vlll metal components, and, where appropriate, Group IA metal components and compounds of Group V such as phosphorus, can be incorporated into the catalyst carrier in a conventional manner, e.g., by impregnation and/or by incorporation into the support material before it is shaped into particles.
  • the metal components can be incorporated into the catalyst composition in the form of suitable precursors, preferably by impregnating the catalyst with an acidic or basic impregnation solution comprising suitable metal precursors.
  • suitable precursors ammonium heptamolybdate, ammonium dimolybdate, and ammonium tungstenate may be mentioned as suitable precursors.
  • Other compounds, such as oxides, hydroxides, carbonates, nitrates, chlorides, and organic acid salts, may also be used.
  • suitable precursors include oxides, hydroxides, carbonates, nitrates, chlorides, and organic acid salts. Carbonates and nitrates are particularly suitable. Suitable Group IA metal precursors include nitrates and carbonates. For phosphorus, phosphoric acid may be used. The impregnation solution, if applied, may contain other compounds the use of which is known in the art, such as organic acids, e.g., citric acid, ammonia water, hydrogen peroxide water, gluconic acid, tartaric acid, malic acid or EDTA (ethylenediamine tetraacetic acid). It will be clear to the skilled person that there is a wide range of variations on this process.
  • organic acids e.g., citric acid, ammonia water, hydrogen peroxide water, gluconic acid, tartaric acid, malic acid or EDTA (ethylenediamine tetraacetic acid).
  • the impregnating solutions to be used containing one or more of the component precursors that are to be deposited, or a portion thereof.
  • impregnating techniques instead of impregnating techniques, dipping processes, spraying processes, etc. can be used. In the case of multiple impregnation, dipping, etc., drying and/or calcining may be carried out in between.
  • the metals After the metals have been incorporated into the catalyst composition, it is optionally dried, e.g., in air flow for about 0.5 to 16 hours at a temperature between room temperature and 200°C, and subsequently calcined, generally in air, for about 1 to 6 hours, preferably 1-3 hours at 200-800°C, preferably 450- 600°C.
  • the drying is done to physically remove the deposited water.
  • the calcining is done to bring at least part, preferably all, of the metal component precursors to the oxide form.
  • the catalyst i.e., the Group VIB and Group Vlll metal components present therein
  • This can be done in an otherwise conventional manner, e.g., by contacting the catalyst in the reactor at increasing temperature with hydrogen and a sulfur-containing feedstock, or with a mixture of hydrogen and hydrogen sulfide. Ex situ presulfiding is also possible.
  • the process of the present invention is particularly suitable for the hydroprocessing of heavy hydrocarbon feeds. It is particularly suitable for hydroprocessing heavy feedstocks of which at least 50 wt.%, preferably at least 80 wt.%., boils above 538°C (1000°F) and which comprise at least 2 wt.% of sulfur and at least 5 wt.%> of Conradson carbon.
  • the sulfur content of the feedstock may be above 3 wt.%>.
  • Conradson carbon content may be above 8 wt.%), preferably above 10 wt.%>.
  • the feedstock may contain contaminant metals, such as nickel and vanadium.
  • these metals are present in an amount of at least 20 wtppm, calculated on the total of Ni and V, more particularly in an amount of at least 30 wtppm.
  • the asphaltene content of the feedstock is preferably between 3 and 15 wt.%>, more preferably between 5 and 10 wt.%..
  • Suitable feedstocks include atmospheric residue, vacuum residue, residues blended with gas oils, particularly vacuum gas oils, crudes, shale oils, tar sand oils, solvent deasphalted oil, coal liquefied oil, etc. Typically they are atmospheric residue (AR), vacuum residue (VR), and mixtures thereof.
  • gas oils particularly vacuum gas oils, crudes, shale oils, tar sand oils, solvent deasphalted oil, coal liquefied oil, etc.
  • gas oils particularly vacuum gas oils, crudes, shale oils, tar sand oils, solvent deasphalted oil, coal liquefied oil, etc.
  • gas oils particularly vacuum gas oils, crudes, shale oils, tar sand oils, solvent deasphalted oil, coal liquefied oil, etc.
  • AR atmospheric residue
  • VR vacuum residue
  • the process according to the invention can be carried out in a fixed bed, in a moving bed, or in an ebullated bed. Carrying out the process in an e
  • the process according to the invention can be carried out in a single reactor or in multiple reactors. If multiple reactors are used, the catalyst mixture used in the two reactors may be the same or different. If two reactors are used, one may or may not one perform or more of intermediate phase separation, stripping, H 2 quenching, etc. between the two stages.
  • the process conditions for the process according to the invention may be as follows.
  • the temperature generally is 350-450°C, preferably 400-440°C.
  • the pressure generally is 5-25 MPA, preferably 14-19 MPA.
  • the liquid hourly space velocity generally is 0.1-3 h-1, preferably 0.3-2 h-1.
  • the hydrogen to feed ratio generally is 300-1,500 Nl/I, preferably 600-1000 Nl/I.
  • the process is carried out in the liquid phase.
  • a sodium aluminate solution and an aluminium sulfate solution were simultaneously added dropwise to a tank containing tap water, mixed at pH 8.5 at 77°C, and held for 70 minutes.
  • the thus produced alumina hydrate gel was separated from the solution and washed with warm water, to remove the impurities in the gel. Then, the gel was kneaded for about 20 minutes and extruded as cylindrical particles having a diameter of 0.9 to 1 mm and a length of 3.5 mm.
  • the extruded alumina particles were calcined at 800°C for 2 hours, to obtain an alumina carrier.
  • Catalyst A meets the requirements of Catalyst I of the present invention.
  • Catalyst B The preparation of Catalyst A was repeated, except for the following modifications: In the carrier preparation, the temperature during the alumina gel formation was 65°C. The carrier calcination temperature was 900°C. In the catalyst preparation the impregnation solution contained 16.4 g of ammonium molybdate tetrahydrate, and the catalyst calcination temperature was 600°C. The composition and properties of Catalyst B are given in Table 1. Catalyst B meets the requirements of Catalyst II of the present invention.
  • a sodium aluminate solution was supplied to a tank containing tap water, and an aluminium sulfate solution and a sodium silicate solution were added and mixed.
  • the mixture had a pH of 8.5.
  • the mixture was kept at 64°C for 1.5 hours.
  • the sodium silicate concentration was set at 1.6 wt.%o of the alumina gel solution.
  • the silica-alumina gel was isolated by filtration and washed with hot water to remove impurities from the gel. It was then extruded into cylindrical grains with a diameter of 0.9-1 mm and a length of 3.5 mm. The resulting particles were dried in air at a temperature of 120°C for 16 hours and subsequently calcined in the presence of air for two hours at 800°C to obtain a silica-alumina carrier. The silica-content of the obtained carrier was 7 wt.%.
  • Catalysts A through C were tested in various combinations in the hydroprocessing of a heavy hydrocarbon feedstock.
  • the feedstock used in these examples was a Middle East petroleum consisting of 90 wt.% of vacuum residue (VR) and 10 wt.% of atmospheric residue (AR).
  • the composition and properties of the feed are given in Table 2.
  • the feedstock was introduced into the unit in the liquid phase at a liquid hourly space velocity of 1.5 h-1, a pressure of 16.0 MPa, an average temperature of 427°C, with the ratio of supplied hydrogen to feedstock (H 2 /oil) being kept at 800 Nl/I.
  • the oil product produced by this process was collected and analysed to calculate the amounts of sulfur (S), metals (vanadium + nickel) (M), and asphaltene (Asp) removed by the process, as well as the 538°C+fraction.
  • S sulfur
  • M metals
  • Asp asphaltene
  • RVA 100 * k (tested catalyst combination)/ k (comparative catalyst combination 2)
  • x being the content of S, M, or Asp in the feedstock
  • y being the content of S, M, or Asp in the product.
  • the catalyst combinations according to the invention show high activities in HDS, HDM, and asphaltene removal in combination with a high residue cracking rate and low sediment formation.

Landscapes

  • Chemical & Material Sciences (AREA)
  • Oil, Petroleum & Natural Gas (AREA)
  • Engineering & Computer Science (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • General Chemical & Material Sciences (AREA)
  • Organic Chemistry (AREA)
  • Catalysts (AREA)
  • Production Of Liquid Hydrocarbon Mixture For Refining Petroleum (AREA)

Abstract

L'invention concerne un procédé d'hydrotraitement de charges d'hydrocarbures lourds, de préférence en réacteur à combustible en suspension, par contact entre la charge et un mélange de deux catalyseurs d'hydrotraitement qui satisfont des conditions spécifiées relatives à la distribution de la taille des pores. Plus précisément, le catalyseur I comporte au moins 50 % du volume total de pores en pores ayant un diamètre d'au moins 20 nm (200 Å), et de 10 à 30 % du volume total de pores en pores ayant un diamètre d'au moins 200 nm (2000 Å), tandis que le catalyseur II comporte au moins 75 % du volume total de pores en pores ayant un diamètre compris entre 10 et 120 nm (100-1200 Å), de 0 à 2 % du volume total de pores en pores ayant un diamètre d'au moins 400 nm (4000 Å), et de 0 à 1 % du volume total de pores en pores ayant un diamètre d'au moins 1000 nm (10000 Å). Le procédé décrit combine un degré élevé d'élimination des contaminants, un degré de conversion élevé, un faible degré de formation de sédiments, et un degré élevé de flexibilité de traitement.
PCT/EP2003/013791 2002-12-06 2003-12-04 Procede d'hydrotraitement de charge lourde reposant sur l'utilisation d'un melange de catalyseurs WO2004052534A1 (fr)

Priority Applications (5)

Application Number Priority Date Filing Date Title
ES03782317T ES2859557T3 (es) 2002-12-06 2003-12-04 Hidroprocesamiento de alimentación pesada usando una mezcla de catalizadores
EP03782317.6A EP1567262B1 (fr) 2002-12-06 2003-12-04 Procede d'hydrotraitement de charge lourde reposant sur l'utilisation d'un melange de catalyseurs
JP2004558008A JP4369871B2 (ja) 2002-12-06 2003-12-04 触媒の混合物を使用する重質原料のｈｐｃ法
CA2508605A CA2508605C (fr) 2002-12-06 2003-12-04 Procede d'hydrotraitement de charge lourde reposant sur l'utilisation d'un melange de catalyseurs
AU2003289969A AU2003289969A1 (en) 2002-12-06 2003-12-04 Heavy feed hpc process using a mixture of catalysts

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
EP02080141.1 2002-12-06
EP02080141 2002-12-06

Publications (1)

Publication Number Publication Date
WO2004052534A1 true WO2004052534A1 (fr) 2004-06-24

Family

ID=32479753

Family Applications (1)

Application Number Title Priority Date Filing Date
PCT/EP2003/013791 WO2004052534A1 (fr) 2002-12-06 2003-12-04 Procede d'hydrotraitement de charge lourde reposant sur l'utilisation d'un melange de catalyseurs

Country Status (8)

Country Link
EP (1) EP1567262B1 (fr)
JP (1) JP4369871B2 (fr)
CN (1) CN100444956C (fr)
AU (1) AU2003289969A1 (fr)
CA (1) CA2508605C (fr)
ES (1) ES2859557T3 (fr)
PL (1) PL213492B1 (fr)
WO (1) WO2004052534A1 (fr)

Cited By (11)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO2013095856A1 (fr) 2011-12-22 2013-06-27 Advanced Refining Technologies Llc Supports d'alumine contenant de la silice, catalyseurs obtenus à partir de ce support et procédé d'utilisation de ces derniers
WO2015189196A1 (fr) 2014-06-13 2015-12-17 IFP Energies Nouvelles Catalyseur a porosite bimodal, son procede de preparation par comalaxage de la phase active et son utilisation en hydrotraitement de residus d'hydrocarbures
WO2015189194A1 (fr) 2014-06-13 2015-12-17 IFP Energies Nouvelles Catalyseur mesoporeux et macroporeux d'hydroconversion de résidus et méthode de préparation
WO2015189198A1 (fr) 2014-06-13 2015-12-17 IFP Energies Nouvelles Alumine mesoporeuse et macroporeuse amorphe a distribution poreuse optimisee et son procede de preparation
WO2016192894A1 (fr) 2015-06-05 2016-12-08 IFP Energies Nouvelles Procede de preparation d'une boehmite presentant des cristallites particulieres
US10533141B2 (en) 2017-02-12 2020-01-14 Mag{tilde over (e)}mã Technology LLC Process and device for treating high sulfur heavy marine fuel oil for use as feedstock in a subsequent refinery unit
US10604709B2 (en) 2017-02-12 2020-03-31 Magēmā Technology LLC Multi-stage device and process for production of a low sulfur heavy marine fuel oil from distressed heavy fuel oil materials
WO2021105253A1 (fr) * 2019-11-29 2021-06-03 Rhodia Operations Alumine présentant un profil poreux particulier
WO2021105252A1 (fr) * 2019-11-29 2021-06-03 Rhodia Operations Alumine présentant un profil poreux particulier
US11344865B2 (en) 2013-11-25 2022-05-31 Shell Usa, Inc. Process for the catalytic conversion of micro carbon residue content of heavy hydrocarbon feedstocks and a low surface area catalyst composition for use therein
US11788017B2 (en) 2017-02-12 2023-10-17 Magëmã Technology LLC Multi-stage process and device for reducing environmental contaminants in heavy marine fuel oil

Families Citing this family (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP4822705B2 (ja) * 2004-12-24 2011-11-24 日揮触媒化成株式会社 重質炭化水素油の水素化処理触媒組成物およびその製造方法
CN101942317B (zh) * 2009-07-09 2013-08-28 中国石油化工股份有限公司 一种沸腾床催化剂的级配方法
CN102443414B (zh) * 2010-10-13 2014-05-21 中国石油化工股份有限公司 重质原料油沸腾床加氢处理方法
CN102465010B (zh) * 2010-11-04 2014-05-21 中国石油化工股份有限公司 一种重质、劣质原料加氢处理方法
CN104560138B (zh) * 2013-10-22 2016-10-26 中国石油化工股份有限公司 一种沸腾床重油加氢处理方法

Citations (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US4499203A (en) * 1982-06-17 1985-02-12 Societe Francaise Des Produits Pour Catalyse Pro-Catalyse Supported catalyst of increased resistance to poisons, useful for hydrotreating metal-containing oil fractions
US5100855A (en) * 1990-03-30 1992-03-31 Amoco Corporation Mixed catalyst system for hyproconversion system
US6086749A (en) * 1996-12-23 2000-07-11 Chevron U.S.A. Inc. Catalyst and method for hydroprocessing a hydrocarbon feed stream in a reactor containing two or more catalysts
WO2002100541A1 (fr) * 2001-06-08 2002-12-19 Nippon Ketjen Co., Ltd. Catalyseur d'hydrocraquage presentant un nombre eleve de macropores, et procede d'utilisation d'un tel catalyseur

Family Cites Families (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US4534852A (en) * 1984-11-30 1985-08-13 Shell Oil Company Single-stage hydrotreating process for converting pitch to conversion process feedstock
CN1030328C (zh) * 1991-09-05 1995-11-22 中国石油化工总公司石油化工科学研究院 加氢催化剂的制备方法

Patent Citations (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US4499203A (en) * 1982-06-17 1985-02-12 Societe Francaise Des Produits Pour Catalyse Pro-Catalyse Supported catalyst of increased resistance to poisons, useful for hydrotreating metal-containing oil fractions
US5100855A (en) * 1990-03-30 1992-03-31 Amoco Corporation Mixed catalyst system for hyproconversion system
US6086749A (en) * 1996-12-23 2000-07-11 Chevron U.S.A. Inc. Catalyst and method for hydroprocessing a hydrocarbon feed stream in a reactor containing two or more catalysts
WO2002100541A1 (fr) * 2001-06-08 2002-12-19 Nippon Ketjen Co., Ltd. Catalyseur d'hydrocraquage presentant un nombre eleve de macropores, et procede d'utilisation d'un tel catalyseur

Cited By (29)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US11090638B2 (en) 2011-12-22 2021-08-17 Advanced Refining Technologies Llc Silica containing alumina supports, catalysts made therefrom and processes using the same
EP2794088A4 (fr) * 2011-12-22 2015-09-09 Advanced Refining Technologies Llc Supports d'alumine contenant de la silice, catalyseurs obtenus à partir de ce support et procédé d'utilisation de ces derniers
US11642664B2 (en) 2011-12-22 2023-05-09 Advanced Refining Technologies Llc Silica containing alumina supports, catalysts made therefrom and processes using the same
WO2013095856A1 (fr) 2011-12-22 2013-06-27 Advanced Refining Technologies Llc Supports d'alumine contenant de la silice, catalyseurs obtenus à partir de ce support et procédé d'utilisation de ces derniers
US11344865B2 (en) 2013-11-25 2022-05-31 Shell Usa, Inc. Process for the catalytic conversion of micro carbon residue content of heavy hydrocarbon feedstocks and a low surface area catalyst composition for use therein
WO2015189196A1 (fr) 2014-06-13 2015-12-17 IFP Energies Nouvelles Catalyseur a porosite bimodal, son procede de preparation par comalaxage de la phase active et son utilisation en hydrotraitement de residus d'hydrocarbures
WO2015189194A1 (fr) 2014-06-13 2015-12-17 IFP Energies Nouvelles Catalyseur mesoporeux et macroporeux d'hydroconversion de résidus et méthode de préparation
WO2015189198A1 (fr) 2014-06-13 2015-12-17 IFP Energies Nouvelles Alumine mesoporeuse et macroporeuse amorphe a distribution poreuse optimisee et son procede de preparation
WO2016192894A1 (fr) 2015-06-05 2016-12-08 IFP Energies Nouvelles Procede de preparation d'une boehmite presentant des cristallites particulieres
US11447706B2 (en) 2017-02-12 2022-09-20 Magēmā Technology LLC Heavy marine fuel compositions
US11492559B2 (en) 2017-02-12 2022-11-08 Magema Technology, Llc Process and device for reducing environmental contaminates in heavy marine fuel oil
US10655074B2 (en) 2017-02-12 2020-05-19 Mag{hacek over (e)}m{hacek over (a)} Technology LLC Multi-stage process and device for reducing environmental contaminates in heavy marine fuel oil
US10836966B2 (en) 2017-02-12 2020-11-17 Magēmā Technology LLC Multi-stage process and device utilizing structured catalyst beds and reactive distillation for the production of a low sulfur heavy marine fuel oil
US11912945B2 (en) 2017-02-12 2024-02-27 Magēmā Technology LLC Process and device for treating high sulfur heavy marine fuel oil for use as feedstock in a subsequent refinery unit
US11884883B2 (en) 2017-02-12 2024-01-30 MagêmãTechnology LLC Multi-stage device and process for production of a low sulfur heavy marine fuel oil
US10584287B2 (en) 2017-02-12 2020-03-10 Magēmā Technology LLC Heavy marine fuel oil composition
US11136513B2 (en) 2017-02-12 2021-10-05 Magëmä Technology LLC Multi-stage device and process for production of a low sulfur heavy marine fuel oil from distressed heavy fuel oil materials
US11203722B2 (en) 2017-02-12 2021-12-21 Magëmä Technology LLC Multi-stage process and device for treatment heavy marine fuel oil and resultant composition including ultrasound promoted desulfurization
US11345863B2 (en) 2017-02-12 2022-05-31 Magema Technology, Llc Heavy marine fuel oil composition
US10563133B2 (en) 2017-02-12 2020-02-18 Magëmä Technology LLC Multi-stage device and process for production of a low sulfur heavy marine fuel oil
US11441084B2 (en) 2017-02-12 2022-09-13 Magēmā Technology LLC Multi-stage device and process for production of a low sulfur heavy marine fuel oil
US10563132B2 (en) 2017-02-12 2020-02-18 Magēmā Technology, LLC Multi-stage process and device for treatment heavy marine fuel oil and resultant composition including ultrasound promoted desulfurization
US10604709B2 (en) 2017-02-12 2020-03-31 Magēmā Technology LLC Multi-stage device and process for production of a low sulfur heavy marine fuel oil from distressed heavy fuel oil materials
US11530360B2 (en) 2017-02-12 2022-12-20 Magēmā Technology LLC Process and device for treating high sulfur heavy marine fuel oil for use as feedstock in a subsequent refinery unit
US10533141B2 (en) 2017-02-12 2020-01-14 Mag{tilde over (e)}mã Technology LLC Process and device for treating high sulfur heavy marine fuel oil for use as feedstock in a subsequent refinery unit
US11788017B2 (en) 2017-02-12 2023-10-17 Magëmã Technology LLC Multi-stage process and device for reducing environmental contaminants in heavy marine fuel oil
US11795406B2 (en) 2017-02-12 2023-10-24 Magemä Technology LLC Multi-stage device and process for production of a low sulfur heavy marine fuel oil from distressed heavy fuel oil materials
WO2021105252A1 (fr) * 2019-11-29 2021-06-03 Rhodia Operations Alumine présentant un profil poreux particulier
WO2021105253A1 (fr) * 2019-11-29 2021-06-03 Rhodia Operations Alumine présentant un profil poreux particulier

Also Published As

Publication number Publication date
EP1567262B1 (fr) 2021-02-03
JP2006509084A (ja) 2006-03-16
AU2003289969A8 (en) 2004-06-30
PL213492B1 (pl) 2013-03-29
CN1735456A (zh) 2006-02-15
CA2508605A1 (fr) 2004-06-24
JP4369871B2 (ja) 2009-11-25
EP1567262A1 (fr) 2005-08-31
CA2508605C (fr) 2011-11-29
ES2859557T3 (es) 2021-10-04
CN100444956C (zh) 2008-12-24
PL377092A1 (pl) 2006-01-23
AU2003289969A1 (en) 2004-06-30

Similar Documents

Publication Publication Date Title
US7922894B2 (en) HPC process using a mixture of catalysts
EP1347832B1 (fr) Catalyseur d'hydrotraitement et son utilisation
CA2508630C (fr) Hydrotraitement d'hydrocarbones au moyen d'un melange de catalyseurs
CA2360121C (fr) Catalyseur d'hydrocraquage et utilisation de ce dernier
CA2508605C (fr) Procede d'hydrotraitement de charge lourde reposant sur l'utilisation d'un melange de catalyseurs
US7476309B2 (en) Two-stage heavy feed hpc process
US7186329B2 (en) High-macropore hydroprocessing catalyst and its use
EP1392798B1 (fr) Procédé d'hydrocraquage en deux étapes
US8012343B2 (en) Heavy feed HPC process using a mixture of catalysts

Legal Events

Date Code Title Description
AK Designated states

Kind code of ref document: A1

Designated state(s): AE AG AL AM AT AU AZ BA BB BG BR BW BY BZ CA CH CN CO CR CU CZ DE DK DM DZ EC EE EG ES FI GB GD GE GH GM HR HU ID IL IN IS JP KE KG KP KR KZ LC LK LR LS LT LU LV MA MD MG MK MN MW MX MZ NI NO NZ OM PG PH PL PT RO RU SC SD SE SG SK SL SY TJ TM TN TR TT TZ UA UG UZ VC VN YU ZA ZM ZW

AL Designated countries for regional patents

Kind code of ref document: A1

Designated state(s): BW GH GM KE LS MW MZ SD SL SZ TZ UG ZM ZW AM AZ BY KG KZ MD RU TJ TM AT BE BG CH CY CZ DE DK EE ES FI FR GB GR HU IE IT LU MC NL PT RO SE SI SK TR BF BJ CF CG CI CM GA GN GQ GW ML MR NE SN TD TG

121 Ep: the epo has been informed by wipo that ep was designated in this application
REEP Request for entry into the european phase

Ref document number: 2003782317

Country of ref document: EP

WWE Wipo information: entry into national phase

Ref document number: 2003782317

Country of ref document: EP

WWE Wipo information: entry into national phase

Ref document number: 2508605

Country of ref document: CA

WWE Wipo information: entry into national phase

Ref document number: 377092

Country of ref document: PL

Ref document number: 2004558008

Country of ref document: JP

WWE Wipo information: entry into national phase

Ref document number: 20038A83088

Country of ref document: CN

WWP Wipo information: published in national office

Ref document number: 2003782317

Country of ref document: EP