EP0722999A1 - Vorrichtung zum Kühlen von mit Feststoffen beladenen Gasen - Google Patents

Vorrichtung zum Kühlen von mit Feststoffen beladenen Gasen Download PDF

Info

Publication number
EP0722999A1
EP0722999A1 EP96200115A EP96200115A EP0722999A1 EP 0722999 A1 EP0722999 A1 EP 0722999A1 EP 96200115 A EP96200115 A EP 96200115A EP 96200115 A EP96200115 A EP 96200115A EP 0722999 A1 EP0722999 A1 EP 0722999A1
Authority
EP
European Patent Office
Prior art keywords
gas
heat transfer
transfer surfaces
inlet
vessel
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
EP96200115A
Other languages
English (en)
French (fr)
Other versions
EP0722999B1 (de
Inventor
Franciscus G. Van Dongen
Albert Postuma
Pieter L. Zuideveld
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
Priority to EP96200115A priority Critical patent/EP0722999B1/de
Publication of EP0722999A1 publication Critical patent/EP0722999A1/de
Application granted granted Critical
Publication of EP0722999B1 publication Critical patent/EP0722999B1/de
Anticipated expiration legal-status Critical
Expired - Lifetime legal-status Critical Current

Links

Images

Classifications

    • C—CHEMISTRY; METALLURGY
    • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10J—PRODUCTION OF PRODUCER GAS, WATER-GAS, SYNTHESIS GAS FROM SOLID CARBONACEOUS MATERIAL, OR MIXTURES CONTAINING THESE GASES; CARBURETTING AIR OR OTHER GASES
    • C10J3/00—Production of combustible gases containing carbon monoxide from solid carbonaceous fuels
    • C10J3/72—Other features
    • C10J3/86—Other features combined with waste-heat boilers
    • C—CHEMISTRY; METALLURGY
    • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10J—PRODUCTION OF PRODUCER GAS, WATER-GAS, SYNTHESIS GAS FROM SOLID CARBONACEOUS MATERIAL, OR MIXTURES CONTAINING THESE GASES; CARBURETTING AIR OR OTHER GASES
    • C10J3/00—Production of combustible gases containing carbon monoxide from solid carbonaceous fuels
    • C10J3/02—Fixed-bed gasification of lump fuel
    • C—CHEMISTRY; METALLURGY
    • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10K—PURIFYING OR MODIFYING THE CHEMICAL COMPOSITION OF COMBUSTIBLE GASES CONTAINING CARBON MONOXIDE
    • C10K1/00—Purifying combustible gases containing carbon monoxide
    • C10K1/04—Purifying combustible gases containing carbon monoxide by cooling to condense non-gaseous materials
    • C—CHEMISTRY; METALLURGY
    • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10J—PRODUCTION OF PRODUCER GAS, WATER-GAS, SYNTHESIS GAS FROM SOLID CARBONACEOUS MATERIAL, OR MIXTURES CONTAINING THESE GASES; CARBURETTING AIR OR OTHER GASES
    • C10J2300/00—Details of gasification processes
    • C10J2300/18—Details of the gasification process, e.g. loops, autothermal operation
    • C10J2300/1861—Heat exchange between at least two process streams
    • C10J2300/1884—Heat exchange between at least two process streams with one stream being synthesis gas

Definitions

  • the present invention to an apparatus for cooling solids laden hot gases.
  • a solids laden gas is, for example, synthesis gas obtainable from a coal gasification process.
  • the coal gasification process is a well-known process for partial oxidation of finely divided solid carbonaceous fuel wherein an oxygen-containing gas, which is applied as an oxidiser, and a finely divided solid carbonaceous fuel are supplied to a gasification zone wherein substantially autothermically under appropriate conditions of temperature and pressure a gaseous stream containing synthesis gas (which is substantially a gaseous mixture of hydrogen and carbon monoxide) is produced.
  • solid impurities such as fly ash particles are usually present in the synthesis gas. Such particles may be sticky.
  • the oxygen-containing gas, which is applied as an oxidiser is usually air or (pure) oxygen or steam or a mixture thereof.
  • the above partial oxidation reaction usually takes place in a gasification reactor.
  • a moderator gas e.g. steam, water or carbon dioxide or a combination thereof
  • a moderator gas e.g. steam, water or carbon dioxide or a combination thereof
  • the said carbonaceous fuel (optionally with a moderator gas) and the said oxygen-containing gas, applied as oxidiser (optionally with a moderator gas) are supplied to the reactor via at least a burner.
  • the hot raw effluent gas stream leaving the reactor, usually at or near its top, is optionally quenched and is usually cooled in an indirect heat exchanger such as a convection cooler.
  • the raw gas stream is cooled off by means of convective heat transfer surfaces arranged in a gascooler located next to the gasification reactor and connected through a duct to the said reactor.
  • the gases are solids laden and therefore problems may arise with respect to erosion of the heat transfer surfaces (when the gas velocity is too high) or with respect to fouling/blocking the gas passages between the heat transfer surfaces (when the gas velocity is too low).
  • the gas velocity will decrease when operating at a constant throughput and pressure, to such an extent that fouling/blocking of the equipment may occur (e.g. by sticky particles) and expensive rapping devices are required to avoid fouling/blocking.
  • the invention therefore provides a self-cleaning apparatus for cooling a solids laden hot gas, said apparatus comprising a vessel with a gas inlet and a gas outlet and heat transfer structure comprising a plurality of heat transfer surfaces extending in the vessel between said inlet and said outlet in a longitudinal direction and forming a plurality of gas passages in the said structure, wherein the said plurality of heat transfer surfaces is arranged in such a way that the overall cross-sectional inlet area of the said gas passages in the said structure is larger than the overall cross-sectional outlet area between said gas passages and that the said gas passages are arranged in such a manner that, in operation, the velocity of the gas flowing through the said gas passages, is kept substantially constant between the cross-sectional inlet area of the said gas passages and the cross-sectional outlet area of the said gas passages.
  • a vessel 1, made of any material suitable for the purpose, is shown.
  • the vessel 1 has a vessel wall 1a and is provided at its upstream side with an inlet 2 for solids laden gas A from a reactor (not shown for reasons of clarity) and at its downstream side with an outlet 3 for cooled gas B which is supplied in any suitable manner to any suitable further gas treating and processing equipment (not shown for reasons of clarity).
  • the inlet 2 is located at or near the top of vessel 1 and the outlet 3 is located at or near the bottom of vessel 1.
  • the gascooler is substantially cylindrical and arranged substantially vertically, but it will be appreciated by those skilled in the art that any arrangement suitable for the purpose can be applied.
  • the cooler 1 is internally provided in any suitable manner with a heat transfer structure comprising a plurality of panels 4 of (convective) heat transfer surfaces arranged in such a manner, that a plurality of gas passages 13 from said inlet to said outlet extending in downstream direction is provided (i.e. in the direction of decreasing process temperature).
  • the arrangement of the heat transfer surfaces is such that the overall cross-sectional inlet area of the gas passages 13 is larger than the overall cross-sectional outlet area of the gas passages 13.
  • the height of the heat transfer structure is M, whereas the distances between the outer heat transfer surfaces of said structure are W1 (inlet) and W2 (outlet) respectively.
  • each panel 4 of heat transfer surfaces arranged in the gas cooler comprises a plurality of cooling tubes (not shown in fig. 1 for reasons of clarity) in mutual mechanical connection by any suitable means such as a webbing, through which tubes any suitable cooling fluid flows (e.g. water or steam, advantageously in counter current flow with the gas) and these panels are designed such that the cross-sectional areas of the passages between the heat transfer surfaces are in tapering arrangement aiming at keeping the gas velocity substantially constant, advantageously in the velocity region of 6-12 m/s.
  • the tubes are provided with fins.
  • the overall cross-sectional area decrease of the gas passages between the said heat transfer surfaces is such that the gas flow A is smoothly directed to the said surfaces and the gas flow impingement represented by the arrow C on the heat transfer surfaces is at small angles ⁇ such that the gas flow substantially parallel to the said surfaces from erosion point of view.
  • An advantageous impact angle ⁇ of the gas flow is 2.5 degrees.
  • the gascooler is provided at its one end with a plurality of inlet headers feeding the panels of cooling tubes with any suitable cooling medium.
  • the gascooler is provided at its other end with a plurality of outlet headers.
  • outlet headers For reasons of clarity the inlet headers, outlet headers and the mechanical connections of the tubes with said headers have not been shown in fig. 1.
  • Each end of a cooling tube of a panel is connected to an outlet header 6 and inlet header 5 respectively as will be explained in more detail below referring to figs. 2a and 2b.
  • the arrangement of the panels and tubes is such that a so-called membrane pipe wall is formed, the (ring-shaped) inlet of which and the (ring-shaped) outlet of which have been represented schematically in fig. 1 by reference numerals 8 and 9 respectively.
  • the membrane pipe wall forms within the vessel 1a a "cage" surrounding the said panels and will be shown in more detail below by reference to figs. 3a and 3b.
  • Fig. 2a represents a partial side view of the inlet header arrangement applied in the gascooler of the invention as shown in fig. 1. Fur reasons of clarity only 7 tubes have been shown.
  • the inlet header 5 is in any suitable manner connected to each cooling tube 10 of a panel 4.
  • Reference numeral 1a represents the vessel wall.
  • the tubes 10 of the panel 4 are mechanically connected via webbings 10a (e.g. by welding).
  • end or outer tube 10' of a panel 4 is part of the "cage" formed by the membrane pipe wall and is in fluid-connection to the inlet 8 (Fig. 1).
  • the membrane pipe wall tube is not connected to the inlet header 5. It will be appreciated that where appropriate the tubes of the membrane pipe wall are suitably bent to provide space for the connecting tubes between the panel 4 and the inlet header 5.
  • Fig. 2b represents a partial side view of a similar arrangement for an outlet header 6 applied in the gascooler of the invention as shown in fig. 1. For reasons of clarity only 7 tubes have been shown. The same reference numerals as in fig. 2a have been used and where appropriate the tubes of the membrane pipe wall are suitably bent. The end or outer tube 10' is part of the "cage" and is in fluid-connection to the outlet 9 (fig. 1).
  • Fig. 3a represents a cross-sectional view of the arrangement of heat transfer surfaces along the line I-I of fig. 1.
  • thirteen panels 4 have been shown, each panel 4 comprising a plurality of cooling tubes 10 and end or outer tubes 10'.
  • the tubes 10 of each panel are connected via webbings 10a.
  • the end or outer tubes 10' of each panel 4 are connected to the end or outer tubes 10' of the adjacent panel 4 via tubes 7.
  • the outer tubes 7 and 10' form the "cage" 11.
  • the tubes 7 (except two which are arranged in a symmetry-plane of the arrangement) are diminishing in diameter from top to bottom so that a tapering arrangement and a sloping position of the panels 4 at both sides of a symmetry-plane are obtained. For reasons of clarity, only a limited number of tubes 10 of each panel 4 is represented.
  • Reference numeral 13 represents the gas passages between the heat transfer surfaces.
  • the panel distance C 1 at the inlet side of the panels is larger than the panel distance at the outlet side (C 2 ) due to the arrangement of tapering tubes 7 arranged between the outer tubes 10' of each panel 4.
  • the cage overall dimensions are V x W1 (inlet) and V x W2 (outlet) wherein W1 > W2 and V remaining constant.
  • Fig. 3b represents a top view of the outlet header arrangement of fig. 1.
  • the same reference numerals have been used as in previous figures.
  • Fig. 4 represents an advantageous embodiment (partially represented) of a tapering tube 7 of the "cage", arranged between the outer tubes 10' of each panel 4 (vide figs. 3a and 3b).
  • Z represents a tapered webbing.
  • the diameter of the tube 7 decreases gradually from inlet end to outlet end with a suitable tapering angle ⁇ (e.g. 2.5°) for the plurality of tapered parts of the said tube.
  • ⁇ e.g. 2.5°
  • the diameter of the tube is gradually decreasing in downflow direction from 60 to 30 mm and the length M is 25-35 m.
  • headers suitable for the purpose can be applied.
  • E.g. two headers per panel of tubes can be used.
  • the webbings between the tubes are provided with openings. More advantageously, the webbings are 25-90% open.

Landscapes

  • Chemical & Material Sciences (AREA)
  • Engineering & Computer Science (AREA)
  • Combustion & Propulsion (AREA)
  • Oil, Petroleum & Natural Gas (AREA)
  • Organic Chemistry (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • General Chemical & Material Sciences (AREA)
  • Heat-Exchange Devices With Radiators And Conduit Assemblies (AREA)
EP96200115A 1995-01-20 1996-01-18 Vorrichtung zum Kühlen von mit Feststoffen beladenen Gasen Expired - Lifetime EP0722999B1 (de)

Priority Applications (1)

Application Number Priority Date Filing Date Title
EP96200115A EP0722999B1 (de) 1995-01-20 1996-01-18 Vorrichtung zum Kühlen von mit Feststoffen beladenen Gasen

Applications Claiming Priority (3)

Application Number Priority Date Filing Date Title
EP95200145 1995-01-20
EP95200145 1995-01-20
EP96200115A EP0722999B1 (de) 1995-01-20 1996-01-18 Vorrichtung zum Kühlen von mit Feststoffen beladenen Gasen

Publications (2)

Publication Number Publication Date
EP0722999A1 true EP0722999A1 (de) 1996-07-24
EP0722999B1 EP0722999B1 (de) 1999-12-29

Family

ID=8219967

Family Applications (1)

Application Number Title Priority Date Filing Date
EP96200115A Expired - Lifetime EP0722999B1 (de) 1995-01-20 1996-01-18 Vorrichtung zum Kühlen von mit Feststoffen beladenen Gasen

Country Status (8)

Country Link
EP (1) EP0722999B1 (de)
JP (1) JP3986101B2 (de)
KR (1) KR100390380B1 (de)
CN (1) CN1104625C (de)
CA (1) CA2167564C (de)
DE (1) DE69605825T2 (de)
ES (1) ES2142011T3 (de)
ZA (1) ZA96390B (de)

Cited By (8)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO2003013694A1 (en) * 2001-08-10 2003-02-20 Shell Internationale Research Maatschappij B.V. Process to recover energy form hot gas
US7597067B2 (en) 2001-10-22 2009-10-06 Shell Oil Company Process to reduce the temperature of a hydrogen and carbon monoxide containing gas and heat exchanger for use in said process
WO2010078254A2 (en) 2008-12-31 2010-07-08 Shell Oil Company Adiabatic reactor and a process and a system for producing a methane-rich gas in such adiabatic reactor
WO2010078252A2 (en) 2008-12-30 2010-07-08 Shell Oil Company Method and system for supplying synthesis gas
WO2010078256A1 (en) 2008-12-31 2010-07-08 Shell Oil Company Process for producing a methane-rich gas
US8461216B2 (en) 2009-08-03 2013-06-11 Shell Oil Company Process for the co-production of superheated steam and methane
US8927610B2 (en) 2009-08-03 2015-01-06 Shell Oil Company Process for the production of methane
RU2744704C2 (ru) * 2016-07-21 2021-03-15 Хальдор Топсёэ А/С Способ получения триоксида серы

Families Citing this family (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP4599291B2 (ja) * 2005-01-07 2010-12-15 三菱重工業株式会社 加圧高温ガス冷却器
US7803216B2 (en) 2005-12-28 2010-09-28 Mitsubishi Heavy Industries, Ltd. Pressurized high-temperature gas cooler
KR102316717B1 (ko) * 2021-02-25 2021-10-27 성일하이메탈(주) 열교환을 이용한 유해 가스 무해화 처리 장치

Citations (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US4520760A (en) * 1984-04-23 1985-06-04 Combustion Engineering, Inc. Heat exchanger outlet arrangement
EP0416242A1 (de) * 1989-09-07 1991-03-13 Krupp Koppers GmbH Anlage für die Erzeugung eines Produktgases aus einem feinteiligen Kohlenstoffträger
WO1991010107A1 (en) * 1990-01-05 1991-07-11 Burmeister & Wain Energi A/S Gas cooler for heat transfer by convection

Patent Citations (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US4520760A (en) * 1984-04-23 1985-06-04 Combustion Engineering, Inc. Heat exchanger outlet arrangement
EP0416242A1 (de) * 1989-09-07 1991-03-13 Krupp Koppers GmbH Anlage für die Erzeugung eines Produktgases aus einem feinteiligen Kohlenstoffträger
WO1991010107A1 (en) * 1990-01-05 1991-07-11 Burmeister & Wain Energi A/S Gas cooler for heat transfer by convection

Cited By (10)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO2003013694A1 (en) * 2001-08-10 2003-02-20 Shell Internationale Research Maatschappij B.V. Process to recover energy form hot gas
US6996989B2 (en) 2001-08-10 2006-02-14 Shell Oil Company Process to recover energy from hot gas
US7597067B2 (en) 2001-10-22 2009-10-06 Shell Oil Company Process to reduce the temperature of a hydrogen and carbon monoxide containing gas and heat exchanger for use in said process
WO2010078252A2 (en) 2008-12-30 2010-07-08 Shell Oil Company Method and system for supplying synthesis gas
WO2010078254A2 (en) 2008-12-31 2010-07-08 Shell Oil Company Adiabatic reactor and a process and a system for producing a methane-rich gas in such adiabatic reactor
WO2010078256A1 (en) 2008-12-31 2010-07-08 Shell Oil Company Process for producing a methane-rich gas
US8470059B2 (en) 2008-12-31 2013-06-25 Shell Oil Company Process for producing a methane-rich gas
US8461216B2 (en) 2009-08-03 2013-06-11 Shell Oil Company Process for the co-production of superheated steam and methane
US8927610B2 (en) 2009-08-03 2015-01-06 Shell Oil Company Process for the production of methane
RU2744704C2 (ru) * 2016-07-21 2021-03-15 Хальдор Топсёэ А/С Способ получения триоксида серы

Also Published As

Publication number Publication date
CA2167564C (en) 2007-05-15
ZA96390B (en) 1996-08-15
ES2142011T3 (es) 2000-04-01
CN1104625C (zh) 2003-04-02
JP3986101B2 (ja) 2007-10-03
KR100390380B1 (ko) 2003-09-06
JPH08231966A (ja) 1996-09-10
DE69605825T2 (de) 2001-07-19
DE69605825D1 (de) 2000-02-03
CN1153286A (zh) 1997-07-02
KR960028962A (ko) 1996-08-17
EP0722999B1 (de) 1999-12-29
CA2167564A1 (en) 1996-07-21

Similar Documents

Publication Publication Date Title
EP0722999B1 (de) Vorrichtung zum Kühlen von mit Feststoffen beladenen Gasen
EP0440258B1 (de) Dampfreformierungsverfahren mit Wärmeaustausch und Reaktorsystem
EP0617230B1 (de) Verfahren zum Betreiben eines Abhitzekessels
JP2005531673A (ja) 固体炭素質原料のガス化方法及び該方法で使用する反応器
CN107427787B (zh) 废热锅炉系统、混合室和用于冷却工艺气体的方法
GB2166155A (en) An apparatus for the gasification of coal dust
JPS5850134B2 (ja) 流動床反応器
US4731097A (en) Gas cooling device for a gasifer
US20210148652A1 (en) Shell-and-tube heat exchanger
JPH05111617A (ja) 化学工業的工程の冷却されたキヤリヤガス中の環境に有害な成分を接触酸化する装置
EP0774103B1 (de) Vorrichtung zur kühlung von heissem gas
US4796570A (en) Apparatus for heating steam formed from cooling water
US4602677A (en) Convection cooler
US4436701A (en) Adsorption reactor and method for removing SO2 from waste gases
KR100961597B1 (ko) 열 교환기
RU2139471C1 (ru) Котел-утилизатор
US5840100A (en) Apparatus for purifying hot flue gas and for receiving thermal energy therefrom
EP1756506B1 (de) Vorrichtung zum abkühlen von heissem gas
CA1303824C (en) Device for nitrogen and hydrogen treatment with the aid of a catalyst
US4958680A (en) Apparatus for particulate solids regeneration
US5251691A (en) Device for the indirect heating of air
GB2082309A (en) Heat Exchangers
US10131856B2 (en) Gasification quench system
US4398504A (en) Steam generating heat exchanger
SU1085622A2 (ru) Конвертор аммиака

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 ES FR GB IT NL SE

17P Request for examination filed

Effective date: 19961108

GRAG Despatch of communication of intention to grant

Free format text: ORIGINAL CODE: EPIDOS AGRA

17Q First examination report despatched

Effective date: 19990310

GRAG Despatch of communication of intention to grant

Free format text: ORIGINAL CODE: EPIDOS AGRA

GRAH Despatch of communication of intention to grant a patent

Free format text: ORIGINAL CODE: EPIDOS IGRA

GRAH Despatch of communication of intention to grant a patent

Free format text: ORIGINAL CODE: EPIDOS IGRA

GRAA (expected) grant

Free format text: ORIGINAL CODE: 0009210

AK Designated contracting states

Kind code of ref document: B1

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

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

Ref country code: SE

Free format text: THE PATENT HAS BEEN ANNULLED BY A DECISION OF A NATIONAL AUTHORITY

Effective date: 19991229

ITF It: translation for a ep patent filed
REF Corresponds to:

Ref document number: 69605825

Country of ref document: DE

Date of ref document: 20000203

ET Fr: translation filed
REG Reference to a national code

Ref country code: ES

Ref legal event code: FG2A

Ref document number: 2142011

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: FR

Payment date: 20041118

Year of fee payment: 10

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

Ref country code: BE

Payment date: 20041221

Year of fee payment: 10

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: 20050118

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

Ref country code: NL

Payment date: 20050121

Year of fee payment: 10

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: 20060131

Ref country code: BE

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

Effective date: 20060131

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: 20060801

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

Effective date: 20060801

REG Reference to a national code

Ref country code: FR

Ref legal event code: ST

Effective date: 20060929

BERE Be: lapsed

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

Effective date: 20060131

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

Ref country code: IT

Payment date: 20071112

Year of fee payment: 13

PGRI Patent reinstated in contracting state [announced from national office to epo]

Ref country code: IT

Effective date: 20091201

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

Ref country code: GB

Payment date: 20101129

Year of fee payment: 16

PGRI Patent reinstated in contracting state [announced from national office to epo]

Ref country code: IT

Effective date: 20091201

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

Ref country code: DE

Payment date: 20101103

Year of fee payment: 16

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

Ref country code: ES

Payment date: 20110125

Year of fee payment: 16

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

Effective date: 20120118

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

Ref country code: DE

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

Effective date: 20120801

Ref country code: GB

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

Effective date: 20120118

REG Reference to a national code

Ref country code: DE

Ref legal event code: R119

Ref document number: 69605825

Country of ref document: DE

Effective date: 20120801

REG Reference to a national code

Ref country code: ES

Ref legal event code: FD2A

Effective date: 20130708

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: 20120119