EP0512652A1 - Hydrodecyclization process - Google Patents

Hydrodecyclization process Download PDF

Info

Publication number
EP0512652A1
EP0512652A1 EP92201302A EP92201302A EP0512652A1 EP 0512652 A1 EP0512652 A1 EP 0512652A1 EP 92201302 A EP92201302 A EP 92201302A EP 92201302 A EP92201302 A EP 92201302A EP 0512652 A1 EP0512652 A1 EP 0512652A1
Authority
EP
European Patent Office
Prior art keywords
gas oil
process according
molar ratio
type zeolite
modified
Prior art date
Legal status (The legal status 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 status listed.)
Granted
Application number
EP92201302A
Other languages
German (de)
French (fr)
Other versions
EP0512652B1 (en
Inventor
Jacques Lucien
Gerardus Leonardus Bosco Thielemans
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
Shell Internationale Research Maatschappij BV
Original Assignee
Shell Internationale Research Maatschappij BV
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 Shell Internationale Research Maatschappij BV filed Critical Shell Internationale Research Maatschappij BV
Publication of EP0512652A1 publication Critical patent/EP0512652A1/en
Application granted granted Critical
Publication of EP0512652B1 publication Critical patent/EP0512652B1/en
Anticipated expiration legal-status Critical
Expired - Lifetime legal-status Critical Current

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
    • C10G45/00—Refining of hydrocarbon oils using hydrogen or hydrogen-generating compounds
    • C10G45/58—Refining of hydrocarbon oils using hydrogen or hydrogen-generating compounds to change the structural skeleton of some of the hydrocarbon content without cracking the other hydrocarbons present, e.g. lowering pour point; Selective hydrocracking of normal paraffins
    • C10G45/60—Refining of hydrocarbon oils using hydrogen or hydrogen-generating compounds to change the structural skeleton of some of the hydrocarbon content without cracking the other hydrocarbons present, e.g. lowering pour point; Selective hydrocracking of normal paraffins characterised by the catalyst used
    • C10G45/64—Refining of hydrocarbon oils using hydrogen or hydrogen-generating compounds to change the structural skeleton of some of the hydrocarbon content without cracking the other hydrocarbons present, e.g. lowering pour point; Selective hydrocracking of normal paraffins characterised by the catalyst used containing crystalline alumino-silicates, e.g. molecular sieves

Definitions

  • the present invention relates to a process for reducing the amount of cyclic structures present in a gas oil.
  • Compounds contributing favourably to the cetane index are paraffins. Naphthenes contribute less favourably to the cetane index, while aromatics are even less desirable from that point of view.
  • Several processes are known for increasing the cetane index of a given gas oil, such as hydrocracking and hydrogenation. Hydrocracking has as a disadvantage that part of the feed is converted into undesired lighter products. Hydrogenation comprises conversion of olefinic compounds, in particular aromatic compounds, into the corresponding saturated compounds. The optimum cetane index which is possible for a given gas oil without substantial cracking of molecules, will not be attained in this way.
  • the present invention relates to a process for reducing the amount of cyclic structures present in a gas oil, which process comprises contacting a gas oil with hydrogen at elevated temperature and pressure using a catalyst comprising one or more Group VIII noble metal(s) on a support wherein the support comprises a modified Y-type zeolite having a unit cell size between 24.20 and 24.40 A and a SiO2/Al2O3 molar ratio of between 10 and 150 and recovering a gas oil comprising a reduced amount of cyclic structures.
  • gas oil is meant a hydrocarbon oil comprising mainly hydrocarbons boiling in the range between 170 and 390 °C and containing at least 25% by weight of hydrocarbons boiling in the range between 250 and 390 °C, which hydrocarbon oil further has a cetane index between 38 and 49.
  • a relatively light gas oil is used, i.e. mainly comprising hydrocarbons boiling in the range between 170 and 320 °C.
  • hydrotreated gas oils are used as these have a relatively low nitrogen and sulphur content which contributes favourably to the life time of the catalyst.
  • Hydrodecyclization is understood to comprise reduction of the amount of cyclic structures present in the gas oil.
  • the amount of cyclic structures present is reduced with at least 10%, based on amount of cyclic structures present in the feed preferably with at least 15%.
  • No substantial cracking takes place, which means that the gas oil recovered from the process according to the present invention comprises at least 5% by weight of hydrocarbons boiling in the range between the 90% by weight boiling point of the feed gas oil and the final boiling point of the feed gas oil.
  • a catalyst comprising one or more Group VIII noble metal(s).
  • Metals which can be suitably present are platinum and/or palladium.
  • the catalyst comprises between 0.05 and 3% by weight of noble metal(s) based on amount of zeolite. More preferably, the catalyst comprises platinum and palladium in a molar ratio of between 0.25 and 0.75.
  • the catalyst further comprises a support comprising a modified Y-type zeolite having a SiO2/Al2O3 molar ratio of between 10 and 150. It has been found that catalysts comprising a relatively low SiO2/Al2O3 molar ratio give surprisingly good results.
  • a molar ratio which is preferred is between 15 and 50, more specifically between 20 and 45.
  • the unit cell size of the Y-type zeolite applied is between 24.20 and 24.40 A, more specifically between 24.22 and 24.35.
  • the hydrodecyclization process can suitably be carried out at a temperature between 150 and 400 °C, preferably at a temperature between 250 and 380 °C.
  • the hydrogen partial pressure applied will usually be between 10 and 150 bar, preferably between 30 and 100 bar.
  • the catalyst temperature and pressure will generally be chosen in such combination that a gas oil is produced having a cetane index of more than 45, preferably more than 50, and comprising less than 25% by weight of aromatic compounds, preferably less than 20. It was found that even gas oils having a cetane index of more than 50 and comprising less than 5% by weight of aromatic compounds, so-called “green gas oils", can be produced in the present process.
  • the cetane index is measured according to ASTM D976.
  • the characteristics of the gas oil produced depend on the feed gas oil and the process conditions.
  • the cetane index and aromatic content which are aimed at in commercial operation, are determined by economic considerations.
  • a hydrotreated straight run gas oil as described in Table 1 was contacted with a catalyst comprising Y-type zeolite having a unit cell size of 24.24 A and a SiO2/Al2O3 molar ratio of 40 and containing 0.3% by weight of platinum and 0.5% by weight of palladium, based on amount of zeolite, at a temperature of 265 °C, a hydrogen partial pressure of 35 bar and a weight hourly space velocity of 1.4 ton/m3.hour.

Abstract

Process for reducing the amount of cyclic structures present in a gas oil, which process comprises contacting a gas oil with hydrogen at elevated temperature and pressure using a catalyst comprising one or more Group VIII noble metal(s) on a support wherein the support comprises a modified Y-type zeolite.

Description

  • The present invention relates to a process for reducing the amount of cyclic structures present in a gas oil.
  • It is well known that hydrocarbon oil products have to fulfil certain chemical and physical requirements if they are to be commercially applied. One of the requirements a gas oil has to meet is the cetane index.
  • Compounds contributing favourably to the cetane index are paraffins. Naphthenes contribute less favourably to the cetane index, while aromatics are even less desirable from that point of view. Several processes are known for increasing the cetane index of a given gas oil, such as hydrocracking and hydrogenation. Hydrocracking has as a disadvantage that part of the feed is converted into undesired lighter products. Hydrogenation comprises conversion of olefinic compounds, in particular aromatic compounds, into the corresponding saturated compounds. The optimum cetane index which is possible for a given gas oil without substantial cracking of molecules, will not be attained in this way.
  • Further, it is important from an environmental point of view to produce a gas oil comprising a small amount of aromatics.
  • It has now been found that a gas oil of good cetane index and low aromatics content can be obtained in a commercially attractive way by subjecting the gas oil to a specific process for reducing the amount of cyclic structures in a gas oil. In such process, the cetane index of the compounds present are optimized while hydrocracking of the hydrocarbons, whereby undesirable lighter products are produced, is substantially prevented.
  • The present invention relates to a process for reducing the amount of cyclic structures present in a gas oil, which process comprises contacting a gas oil with hydrogen at elevated temperature and pressure using a catalyst comprising one or more Group VIII noble metal(s) on a support wherein the support comprises a modified Y-type zeolite having a unit cell size between 24.20 and 24.40 A and a SiO2/Al2O3 molar ratio of between 10 and 150 and recovering a gas oil comprising a reduced amount of cyclic structures.
  • With gas oil is meant a hydrocarbon oil comprising mainly hydrocarbons boiling in the range between 170 and 390 °C and containing at least 25% by weight of hydrocarbons boiling in the range between 250 and 390 °C, which hydrocarbon oil further has a cetane index between 38 and 49. Suitably a relatively light gas oil is used, i.e. mainly comprising hydrocarbons boiling in the range between 170 and 320 °C. Preferably, hydrotreated gas oils are used as these have a relatively low nitrogen and sulphur content which contributes favourably to the life time of the catalyst.
  • Hydrodecyclization is understood to comprise reduction of the amount of cyclic structures present in the gas oil. Preferably, the amount of cyclic structures present is reduced with at least 10%, based on amount of cyclic structures present in the feed preferably with at least 15%. No substantial cracking takes place, which means that the gas oil recovered from the process according to the present invention comprises at least 5% by weight of hydrocarbons boiling in the range between the 90% by weight boiling point of the feed gas oil and the final boiling point of the feed gas oil.
  • In the process according to the present invention use is made of a catalyst comprising one or more Group VIII noble metal(s). Metals which can be suitably present are platinum and/or palladium. Preferably, the catalyst comprises between 0.05 and 3% by weight of noble metal(s) based on amount of zeolite. More preferably, the catalyst comprises platinum and palladium in a molar ratio of between 0.25 and 0.75.
  • The catalyst further comprises a support comprising a modified Y-type zeolite having a SiO2/Al2O3 molar ratio of between 10 and 150. It has been found that catalysts comprising a relatively low SiO2/Al2O3 molar ratio give surprisingly good results. A molar ratio which is preferred is between 15 and 50, more specifically between 20 and 45. The unit cell size of the Y-type zeolite applied is between 24.20 and 24.40 A, more specifically between 24.22 and 24.35.
  • The hydrodecyclization process can suitably be carried out at a temperature between 150 and 400 °C, preferably at a temperature between 250 and 380 °C. The hydrogen partial pressure applied will usually be between 10 and 150 bar, preferably between 30 and 100 bar.
  • In the present process the catalyst, temperature and pressure will generally be chosen in such combination that a gas oil is produced having a cetane index of more than 45, preferably more than 50, and comprising less than 25% by weight of aromatic compounds, preferably less than 20. It was found that even gas oils having a cetane index of more than 50 and comprising less than 5% by weight of aromatic compounds, so-called "green gas oils", can be produced in the present process. The cetane index is measured according to ASTM D976.
  • The characteristics of the gas oil produced depend on the feed gas oil and the process conditions. The cetane index and aromatic content which are aimed at in commercial operation, are determined by economic considerations.
  • The process of the present invention will be further elucidated by the following example.
    • EXAMPLE
  • A hydrotreated straight run gas oil as described in Table 1, was contacted with a catalyst comprising Y-type zeolite having a unit cell size of 24.24 A and a SiO2/Al2O3 molar ratio of 40 and containing 0.3% by weight of platinum and 0.5% by weight of palladium, based on amount of zeolite, at a temperature of 265 °C, a hydrogen partial pressure of 35 bar and a weight hourly space velocity of 1.4 ton/m³.hour.
  • The results obtained are shown in Table 2.
  • The amount of cyclic structures present in the product obtained was reduced with 18%, based on amount of cyclic structures present in the feed. Table 1
    Boiling point distribution (°C)
    Initial boiling point 179
    10% 205
    30% 218
    50% 233
    70% 249
    90% 272
    Final boiling point 294
    Cetane index 49.3
    Aromatics content (% by volume) 20.1
    Table 2
    Boiling point distribution (°C)
    Initial boiling point 180
    10% 205
    30% 218
    50% 231
    70% 247
    90% 272
    Final boiling point 293
    Cetane index 53.4
    Aromatics content (% by volume) 3.9

Claims (10)

  1. Process for reducing the amount of cyclic structures present in a gas oil, which process comprises contacting a gas oil with hydrogen at elevated temperature and pressure using a catalyst comprising one or more Group VIII noble metal(s) on a support wherein the support comprises a modified Y-type zeolite having a unit cell size between 24.20 and 24.40 A and a SiO2/Al2O3 molar ratio of between 10 and 150 and recovering a gas oil comprising a reduced amount of cyclic structures.
  2. Process according to claim 1, in which the modified Y-type zeolite has a SiO2/Al2O3 molar ratio of between 15 and 50.
  3. Process according to claim 2, in which the modified Y-type zeolite has a SiO2/Al2O3 molar ratio of between 20 and 45.
  4. Process according to any one of the preceding claims, in which the modified Y-type zeolite has a unit cell size of between 24.22 and 24.35 A.
  5. Process according to any one of the preceding claims, in which the process is carried out at a temperature between 150 and 400 °C.
  6. Process according to any one of the preceding claims, in which the process is carried out at a hydrogen partial pressure between 10 and 150 bar.
  7. Process according to any one of the preceding claims, in which the catalyst comprises platinum and palladium in a molar ratio of between 0.25 to 0.75.
  8. Process according to any one of the preceding claims, in which a gas oil is recovered comprising less than 25% by weight of aromatic compounds and having a cetane index of more than 50.
  9. Process according to any one of the preceding claims, in which a gas oil is recovered comprising less than 5% by weight of aromatic compounds and having a cetane index of more than 50.
  10. Hydrocarbons obtained in a process as described in any one of the preceding claims.
EP92201302A 1991-05-09 1992-05-07 Hydrodecyclization process Expired - Lifetime EP0512652B1 (en)

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
GB9110012 1991-05-09
GB919110012A GB9110012D0 (en) 1991-05-09 1991-05-09 Hydrodecyclization process

Publications (2)

Publication Number Publication Date
EP0512652A1 true EP0512652A1 (en) 1992-11-11
EP0512652B1 EP0512652B1 (en) 1995-08-23

Family

ID=10694685

Family Applications (1)

Application Number Title Priority Date Filing Date
EP92201302A Expired - Lifetime EP0512652B1 (en) 1991-05-09 1992-05-07 Hydrodecyclization process

Country Status (9)

Country Link
EP (1) EP0512652B1 (en)
JP (1) JP3210729B2 (en)
CA (1) CA2068174C (en)
DE (1) DE69204206T2 (en)
DK (1) DK0512652T3 (en)
ES (1) ES2077338T3 (en)
FI (1) FI114317B (en)
GB (1) GB9110012D0 (en)
NO (1) NO304029B1 (en)

Cited By (7)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO2001027223A1 (en) * 1999-10-13 2001-04-19 Veba Oil Refining & Petrochemicals Gmbh Method for production of n-alkanes from mineral oil fractions and catalyst for carrying out said method
US6399845B1 (en) 1997-05-29 2002-06-04 Fortum Oil & Gas Oy Process for producing high grade diesel fuel
US6444865B1 (en) 1997-12-01 2002-09-03 Shell Oil Company Process wherein a hydrocarbon feedstock is contacted with a catalyst
US7709408B2 (en) * 2002-07-16 2010-05-04 Consejo Superior De Investigaciones Cientificas Catalyst based on a solid microporous crystalline material and method of improving diesel fraction quality using said catalyst
CN105713657A (en) * 2014-12-01 2016-06-29 中国石油化工股份有限公司 Hydrocracking method
WO2017148735A1 (en) 2016-03-01 2017-09-08 Sabic Global Technologies B.V. Process for producing monoaromatic hydrocarbons from a hydrocarbon feed comprising polyaromatics
US11001765B2 (en) 2016-02-25 2021-05-11 Sabic Global Technologies B.V. Process for combined hydrodesulfurization and hydrocracking of heavy hydrocarbons

Families Citing this family (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
KR100438816B1 (en) * 1998-03-09 2004-07-16 삼성전자주식회사 Personal solid image head mount display device, especially including two dimensional image display
KR100419288B1 (en) * 2001-06-22 2004-02-19 인천정유 주식회사 Method for preparing catalysts for dearomatization in distillate

Citations (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
EP0247678A2 (en) * 1986-05-30 1987-12-02 Shell Internationale Researchmaatschappij B.V. Hydrocarbon conversion process and catalysts

Patent Citations (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
EP0247678A2 (en) * 1986-05-30 1987-12-02 Shell Internationale Researchmaatschappij B.V. Hydrocarbon conversion process and catalysts

Cited By (12)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US6399845B1 (en) 1997-05-29 2002-06-04 Fortum Oil & Gas Oy Process for producing high grade diesel fuel
US6444865B1 (en) 1997-12-01 2002-09-03 Shell Oil Company Process wherein a hydrocarbon feedstock is contacted with a catalyst
WO2001027223A1 (en) * 1999-10-13 2001-04-19 Veba Oil Refining & Petrochemicals Gmbh Method for production of n-alkanes from mineral oil fractions and catalyst for carrying out said method
US7067448B1 (en) 1999-10-13 2006-06-27 Veba Oil Refining And Petrochemicals Gmbh Method for production of n-alkanes from mineral oil fractions and catalyst for carrying out said method
CZ297150B6 (en) * 1999-10-13 2006-09-13 Veba Oil Refining & Petrochemicals Gmbh Process for preparing n-alkanes, catalyst for making the process and use of such a catalyst
US7709408B2 (en) * 2002-07-16 2010-05-04 Consejo Superior De Investigaciones Cientificas Catalyst based on a solid microporous crystalline material and method of improving diesel fraction quality using said catalyst
CN105713657A (en) * 2014-12-01 2016-06-29 中国石油化工股份有限公司 Hydrocracking method
CN105713657B (en) * 2014-12-01 2017-05-17 中国石油化工股份有限公司 Hydrocracking method
US11001765B2 (en) 2016-02-25 2021-05-11 Sabic Global Technologies B.V. Process for combined hydrodesulfurization and hydrocracking of heavy hydrocarbons
WO2017148735A1 (en) 2016-03-01 2017-09-08 Sabic Global Technologies B.V. Process for producing monoaromatic hydrocarbons from a hydrocarbon feed comprising polyaromatics
CN108699449A (en) * 2016-03-01 2018-10-23 沙特基础工业全球技术有限公司 Method for producing mononuclear aromatics by the hydrocarbon charging comprising polycyclic aromatic hydrocarbon
US10822552B2 (en) 2016-03-01 2020-11-03 Sabic Global Technologies B.V. Process for producing monoaromatic hydrocarbons from a hydrocarbon feed comprising polyaromatics

Also Published As

Publication number Publication date
NO921806L (en) 1992-11-10
DK0512652T3 (en) 1995-09-25
GB9110012D0 (en) 1991-07-03
NO304029B1 (en) 1998-10-12
CA2068174A1 (en) 1992-11-10
ES2077338T3 (en) 1995-11-16
FI922069A (en) 1992-11-10
DE69204206T2 (en) 1996-02-01
NO921806D0 (en) 1992-05-07
FI114317B (en) 2004-09-30
JP3210729B2 (en) 2001-09-17
FI922069A0 (en) 1992-05-07
EP0512652B1 (en) 1995-08-23
DE69204206D1 (en) 1995-09-28
JPH05179260A (en) 1993-07-20
CA2068174C (en) 2003-12-02

Similar Documents

Publication Publication Date Title
US5525209A (en) Process for the improved production of middle distillates jointly with the production of high viscosity oils with high viscosity indices from heavy petroleum cuts
US5350504A (en) Shape selective hydrogenation of aromatics over modified non-acidic platinum/ZSM-5 catalysts
US6210561B1 (en) Steam cracking of hydrotreated and hydrogenated hydrocarbon feeds
CA1196879A (en) Hydrocracking process
US6623623B2 (en) Simultaneous hydroprocessing of two feedstocks
EP0303332B1 (en) Process for the hydrogenation of hydrocarbon oils
US5152883A (en) Process for the production of improved octane numbers gasolines
US3699036A (en) Hydrocracking nitrogen containing feedstocks
US5609752A (en) Process for Cetane improvement of distillate fractions
EP0512652B1 (en) Hydrodecyclization process
US6328879B1 (en) Simultaneous hydroprocesssing of two feedstocks
US5198099A (en) Three-stage process for producing ultra-clean distillate products
US3173853A (en) Catalytic hydrocracking process employing water as a promoter
US3700586A (en) Production of high octane gasoline from coal liquids
US3420768A (en) Middle distillate hydrogen treating processes
JP4248142B2 (en) Low pressure naphtha hydrocracking process
US5552033A (en) Integrated process for increasing C6 to C8 aromatics content in reformate prepared from C9+ aromatics-containing feed
US3481996A (en) Process for hydrodesulfurization of cracked gas oils and the production of dimethyldecalins and fuel oil blending components
US3172833A (en) Catalytic conversion process for the production of low luminosity fuels
US3575844A (en) Hydrocracking process
EP0226289B1 (en) Processing of aromatic vacuum gas oil for jet fuel production
US2944089A (en) Process for producing xylenes
US3110662A (en) Catalytic conversion process for the production of low freezing point fuels
US3520798A (en) Hydrocracking process with controlled addition of sulfur
WO1996002612A1 (en) Shape selective hydrogenation of aromatics

Legal Events

Date Code Title Description
PUAI Public reference made under article 153(3) epc to a published international application that has entered the european phase

Free format text: ORIGINAL CODE: 0009012

AK Designated contracting states

Kind code of ref document: A1

Designated state(s): BE DE DK ES FR GB IT NL SE

17P Request for examination filed

Effective date: 19930322

17Q First examination report despatched

Effective date: 19931007

GRAA (expected) grant

Free format text: ORIGINAL CODE: 0009210

AK Designated contracting states

Kind code of ref document: B1

Designated state(s): BE DE DK ES FR GB IT NL SE

REG Reference to a national code

Ref country code: DK

Ref legal event code: T3

REF Corresponds to:

Ref document number: 69204206

Country of ref document: DE

Date of ref document: 19950928

ITF It: translation for a ep patent filed

Owner name: ING. C. GREGORJ S.P.A.

ET Fr: translation filed
REG Reference to a national code

Ref country code: ES

Ref legal event code: FG2A

Ref document number: 2077338

Country of ref document: ES

Kind code of ref document: T3

PLBE No opposition filed within time limit

Free format text: ORIGINAL CODE: 0009261

STAA Information on the status of an ep patent application or granted ep patent

Free format text: STATUS: NO OPPOSITION FILED WITHIN TIME LIMIT

26N No opposition filed
REG Reference to a national code

Ref country code: GB

Ref legal event code: IF02

PGFP Annual fee paid to national office [announced via postgrant information from national office to epo]

Ref country code: DK

Payment date: 20080602

Year of fee payment: 17

Ref country code: DE

Payment date: 20080528

Year of fee payment: 17

Ref country code: ES

Payment date: 20080529

Year of fee payment: 17

PGFP Annual fee paid to national office [announced via postgrant information from national office to epo]

Ref country code: BE

Payment date: 20080509

Year of fee payment: 17

Ref country code: IT

Payment date: 20080526

Year of fee payment: 17

PGFP Annual fee paid to national office [announced via postgrant information from national office to epo]

Ref country code: NL

Payment date: 20080526

Year of fee payment: 17

Ref country code: SE

Payment date: 20080404

Year of fee payment: 17

PGFP Annual fee paid to national office [announced via postgrant information from national office to epo]

Ref country code: FR

Payment date: 20080331

Year of fee payment: 17

PGFP Annual fee paid to national office [announced via postgrant information from national office to epo]

Ref country code: GB

Payment date: 20080421

Year of fee payment: 17

BERE Be: lapsed

Owner name: *SHELL INTERNATIONALE RESEARCH MAATSCHAPPIJ B.V.

Effective date: 20090531

REG Reference to a national code

Ref country code: DK

Ref legal event code: EBP

GBPC Gb: european patent ceased through non-payment of renewal fee

Effective date: 20090507

NLV4 Nl: lapsed or anulled due to non-payment of the annual fee

Effective date: 20091201

PG25 Lapsed in a contracting state [announced via postgrant information from national office to epo]

Ref country code: NL

Free format text: LAPSE BECAUSE OF NON-PAYMENT OF DUE FEES

Effective date: 20091201

REG Reference to a national code

Ref country code: FR

Ref legal event code: ST

Effective date: 20100129

PG25 Lapsed in a contracting state [announced via postgrant information from national office to epo]

Ref country code: FR

Free format text: LAPSE BECAUSE OF NON-PAYMENT OF DUE FEES

Effective date: 20090602

Ref country code: DK

Free format text: LAPSE BECAUSE OF NON-PAYMENT OF DUE FEES

Effective date: 20090531

PG25 Lapsed in a contracting state [announced via postgrant information from national office to epo]

Ref country code: GB

Free format text: LAPSE BECAUSE OF NON-PAYMENT OF DUE FEES

Effective date: 20090507

PG25 Lapsed in a contracting state [announced via postgrant information from national office to epo]

Ref country code: BE

Free format text: LAPSE BECAUSE OF NON-PAYMENT OF DUE FEES

Effective date: 20090531

Ref country code: DE

Free format text: LAPSE BECAUSE OF NON-PAYMENT OF DUE FEES

Effective date: 20091201

REG Reference to a national code

Ref country code: ES

Ref legal event code: FD2A

Effective date: 20090508

PG25 Lapsed in a contracting state [announced via postgrant information from national office to epo]

Ref country code: ES

Free format text: LAPSE BECAUSE OF NON-PAYMENT OF DUE FEES

Effective date: 20090508

PG25 Lapsed in a contracting state [announced via postgrant information from national office to epo]

Ref country code: IT

Free format text: LAPSE BECAUSE OF NON-PAYMENT OF DUE FEES

Effective date: 20090507

PG25 Lapsed in a contracting state [announced via postgrant information from national office to epo]

Ref country code: SE

Free format text: LAPSE BECAUSE OF NON-PAYMENT OF DUE FEES

Effective date: 20090508