EP0186009B1 - Utilisation de copolymères d'éthylène comme additifs pour huile brute - Google Patents

Utilisation de copolymères d'éthylène comme additifs pour huile brute Download PDF

Info

Publication number
EP0186009B1
EP0186009B1 EP85115541A EP85115541A EP0186009B1 EP 0186009 B1 EP0186009 B1 EP 0186009B1 EP 85115541 A EP85115541 A EP 85115541A EP 85115541 A EP85115541 A EP 85115541A EP 0186009 B1 EP0186009 B1 EP 0186009B1
Authority
EP
European Patent Office
Prior art keywords
crude oil
crude
weight
ethylene
ethylene copolymers
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.)
Expired
Application number
EP85115541A
Other languages
German (de)
English (en)
Other versions
EP0186009A3 (en
EP0186009A2 (fr
Inventor
John Dr. Dipl.-Chem. Hobes
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.)
Hoechst AG
Original Assignee
Hoechst AG
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 Hoechst AG filed Critical Hoechst AG
Publication of EP0186009A2 publication Critical patent/EP0186009A2/fr
Publication of EP0186009A3 publication Critical patent/EP0186009A3/de
Application granted granted Critical
Publication of EP0186009B1 publication Critical patent/EP0186009B1/fr
Expired legal-status Critical Current

Links

Classifications

    • C—CHEMISTRY; METALLURGY
    • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10L—FUELS NOT OTHERWISE PROVIDED FOR; NATURAL GAS; SYNTHETIC NATURAL GAS OBTAINED BY PROCESSES NOT COVERED BY SUBCLASSES C10G, C10K; LIQUEFIED PETROLEUM GAS; ADDING MATERIALS TO FUELS OR FIRES TO REDUCE SMOKE OR UNDESIRABLE DEPOSITS OR TO FACILITATE SOOT REMOVAL; FIRELIGHTERS
    • C10L1/00—Liquid carbonaceous fuels
    • C10L1/10—Liquid carbonaceous fuels containing additives
    • C10L1/14—Organic compounds
    • C10L1/18—Organic compounds containing oxygen
    • C—CHEMISTRY; METALLURGY
    • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10L—FUELS NOT OTHERWISE PROVIDED FOR; NATURAL GAS; SYNTHETIC NATURAL GAS OBTAINED BY PROCESSES NOT COVERED BY SUBCLASSES C10G, C10K; LIQUEFIED PETROLEUM GAS; ADDING MATERIALS TO FUELS OR FIRES TO REDUCE SMOKE OR UNDESIRABLE DEPOSITS OR TO FACILITATE SOOT REMOVAL; FIRELIGHTERS
    • C10L1/00—Liquid carbonaceous fuels
    • C10L1/10—Liquid carbonaceous fuels containing additives
    • C10L1/14—Organic compounds
    • C10L1/143—Organic compounds mixtures of organic macromolecular compounds with organic non-macromolecular compounds
    • C—CHEMISTRY; METALLURGY
    • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10L—FUELS NOT OTHERWISE PROVIDED FOR; NATURAL GAS; SYNTHETIC NATURAL GAS OBTAINED BY PROCESSES NOT COVERED BY SUBCLASSES C10G, C10K; LIQUEFIED PETROLEUM GAS; ADDING MATERIALS TO FUELS OR FIRES TO REDUCE SMOKE OR UNDESIRABLE DEPOSITS OR TO FACILITATE SOOT REMOVAL; FIRELIGHTERS
    • C10L1/00—Liquid carbonaceous fuels
    • C10L1/10—Liquid carbonaceous fuels containing additives
    • C10L1/14—Organic compounds
    • C10L1/18—Organic compounds containing oxygen
    • C10L1/182—Organic compounds containing oxygen containing hydroxy groups; Salts thereof
    • C10L1/183—Organic compounds containing oxygen containing hydroxy groups; Salts thereof at least one hydroxy group bound to an aromatic carbon atom
    • C10L1/1832—Organic compounds containing oxygen containing hydroxy groups; Salts thereof at least one hydroxy group bound to an aromatic carbon atom mono-hydroxy
    • C—CHEMISTRY; METALLURGY
    • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10L—FUELS NOT OTHERWISE PROVIDED FOR; NATURAL GAS; SYNTHETIC NATURAL GAS OBTAINED BY PROCESSES NOT COVERED BY SUBCLASSES C10G, C10K; LIQUEFIED PETROLEUM GAS; ADDING MATERIALS TO FUELS OR FIRES TO REDUCE SMOKE OR UNDESIRABLE DEPOSITS OR TO FACILITATE SOOT REMOVAL; FIRELIGHTERS
    • C10L1/00—Liquid carbonaceous fuels
    • C10L1/10—Liquid carbonaceous fuels containing additives
    • C10L1/14—Organic compounds
    • C10L1/18—Organic compounds containing oxygen
    • C10L1/19—Esters ester radical containing compounds; ester ethers; carbonic acid esters
    • C—CHEMISTRY; METALLURGY
    • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10L—FUELS NOT OTHERWISE PROVIDED FOR; NATURAL GAS; SYNTHETIC NATURAL GAS OBTAINED BY PROCESSES NOT COVERED BY SUBCLASSES C10G, C10K; LIQUEFIED PETROLEUM GAS; ADDING MATERIALS TO FUELS OR FIRES TO REDUCE SMOKE OR UNDESIRABLE DEPOSITS OR TO FACILITATE SOOT REMOVAL; FIRELIGHTERS
    • C10L1/00—Liquid carbonaceous fuels
    • C10L1/10—Liquid carbonaceous fuels containing additives
    • C10L1/14—Organic compounds
    • C10L1/18—Organic compounds containing oxygen
    • C10L1/192—Macromolecular compounds
    • C10L1/195—Macromolecular compounds obtained by reactions involving only carbon-to-carbon unsaturated bonds
    • C10L1/197—Macromolecular compounds obtained by reactions involving only carbon-to-carbon unsaturated bonds derived from monomers containing a carbon-to-carbon unsaturated bond and an acyloxy group of a saturated carboxylic or carbonic acid
    • C10L1/1973—Macromolecular compounds obtained by reactions involving only carbon-to-carbon unsaturated bonds derived from monomers containing a carbon-to-carbon unsaturated bond and an acyloxy group of a saturated carboxylic or carbonic acid mono-carboxylic
    • C—CHEMISTRY; METALLURGY
    • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10L—FUELS NOT OTHERWISE PROVIDED FOR; NATURAL GAS; SYNTHETIC NATURAL GAS OBTAINED BY PROCESSES NOT COVERED BY SUBCLASSES C10G, C10K; LIQUEFIED PETROLEUM GAS; ADDING MATERIALS TO FUELS OR FIRES TO REDUCE SMOKE OR UNDESIRABLE DEPOSITS OR TO FACILITATE SOOT REMOVAL; FIRELIGHTERS
    • C10L1/00—Liquid carbonaceous fuels
    • C10L1/10—Liquid carbonaceous fuels containing additives
    • C10L1/14—Organic compounds
    • C10L1/22—Organic compounds containing nitrogen
    • C10L1/222—Organic compounds containing nitrogen containing at least one carbon-to-nitrogen single bond
    • C10L1/2222—(cyclo)aliphatic amines; polyamines (no macromolecular substituent 30C); quaternair ammonium compounds; carbamates
    • C10L1/2225—(cyclo)aliphatic amines; polyamines (no macromolecular substituent 30C); quaternair ammonium compounds; carbamates hydroxy containing
    • C—CHEMISTRY; METALLURGY
    • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10L—FUELS NOT OTHERWISE PROVIDED FOR; NATURAL GAS; SYNTHETIC NATURAL GAS OBTAINED BY PROCESSES NOT COVERED BY SUBCLASSES C10G, C10K; LIQUEFIED PETROLEUM GAS; ADDING MATERIALS TO FUELS OR FIRES TO REDUCE SMOKE OR UNDESIRABLE DEPOSITS OR TO FACILITATE SOOT REMOVAL; FIRELIGHTERS
    • C10L1/00—Liquid carbonaceous fuels
    • C10L1/10—Liquid carbonaceous fuels containing additives
    • C10L1/14—Organic compounds
    • C10L1/24—Organic compounds containing sulfur, selenium and/or tellurium
    • C10L1/2406—Organic compounds containing sulfur, selenium and/or tellurium mercaptans; hydrocarbon sulfides
    • C10L1/2412—Organic compounds containing sulfur, selenium and/or tellurium mercaptans; hydrocarbon sulfides sulfur bond to an aromatic radical
    • C—CHEMISTRY; METALLURGY
    • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10L—FUELS NOT OTHERWISE PROVIDED FOR; NATURAL GAS; SYNTHETIC NATURAL GAS OBTAINED BY PROCESSES NOT COVERED BY SUBCLASSES C10G, C10K; LIQUEFIED PETROLEUM GAS; ADDING MATERIALS TO FUELS OR FIRES TO REDUCE SMOKE OR UNDESIRABLE DEPOSITS OR TO FACILITATE SOOT REMOVAL; FIRELIGHTERS
    • C10L1/00—Liquid carbonaceous fuels
    • C10L1/10—Liquid carbonaceous fuels containing additives
    • C10L1/14—Organic compounds
    • C10L1/26—Organic compounds containing phosphorus
    • C10L1/2633—Organic compounds containing phosphorus phosphorus bond to oxygen (no P. C. bond)
    • C10L1/2641—Organic compounds containing phosphorus phosphorus bond to oxygen (no P. C. bond) oxygen bonds only

Definitions

  • the present invention relates to additives for improving the flow behavior of crude oil. These additives remain effective even under high shear loads.
  • Crude oil is the crude oil that comes directly from the earth. Crude oil consists essentially of hydrocarbons, namely alkanes, cycloalkanes and alkylbenzene. In addition, it contains oxygen and sulfur-containing compounds such as naphthenic acids, phenols, aldehydes, thioethers and various heterocyclic compounds.
  • the alkanes are a mixture of straight-chain unbranched paraffins having 1 to about 30 carbon atoms, the gaseous and the solid hydrocarbons being dissolved in the liquid.
  • the separation of the paraffins is promoted by lowering the temperature and reducing the pressure. Both measures reduce the solubility of the solid in the liquid hydrocarbons. The result is a supersaturated solution from which the paraffin eventually crystallizes.
  • This process changes the rheological behavior of the crude oil. Its viscosity increases and its fluidity in the conveyor systems and lines is impaired accordingly. The increase in viscosity can lead to the crude oil stalling.
  • the pour point (according to DIN 51 583) or the pour point (yield point; according to DIN ISO 3016) is determined. They are determined in conventional test equipment.
  • paraffin inhibitors are also used, which influence the rheological properties of the extracted or transported oil and prevent the formation of paraffin crystals by incorporating them into the resulting structures or by their absorption. In both cases, crystal growth is counteracted, so that small particles are formed which do not allow the formation of networks.
  • the addition of paraffin inhibitors therefore enables crude oil to be extracted and transported below the pour point temperature.
  • Paraffin inhibitors or flow improvers predominantly have a paraffin-like structure and generally have polar groups in the side chains.
  • these branches have the task of counteracting the crystal formation of the inhibitor. Chemically, they belong to the group of polyethylenes, polymethacrylates and ethylene-vinyl acetate copolymers.
  • the dosage of paraffin inhibitors to crude oil is not always without side effects. For example, they can adversely affect the viscosity and pour point of the crude oil in plant parts such as orifices or centrifugal pumps that are subject to high shear stress.
  • This object is achieved by using 0.005 to 0.5% by weight (based on the crude oil) of a copolymer which consists of 65 to 80% by weight of ethylene units and 35 to 20% by weight of vinyl acetate units, together with 0 , 01 to 1.0 wt .-% (based on the crude oil) of an antioxidant and 0.001 to 1.0 wt .-% (based on the crude oil) of an amine as a flow improver for crude oil.
  • the preparation of the copolymers used according to the invention is known. It is carried out by polymerizing the monomer mixture at temperatures from 100 to 350 ° C. and pressures from 1000 to 8000 bar in the presence of free radical initiators. The polymerization does not require the presence of a solvent as the reaction medium.
  • the ethylene used as comonomer is used in the purity customary for polymerization reactions of at least 99%.
  • the polymerization takes place in the presence of catalytic amounts of free radical initiators, for example oxygen, in amounts of 2 to 250 mol.ppm, based on the ethylene to be polymerized.
  • free radical initiators for example oxygen
  • peroxides such as tert-butyl perbenzoate, dilauroyl peroxide, di-tert-butyl peroxide or azo-butyrononitrile in amounts of 2 to 200 mol.ppm, based on the ethylene, can also be used as initiators.
  • the molecular weight is adjusted using moderators, such as aliphatic alcohols and / or carbonyl compounds, saturated, unsaturated or chlorinated hydrocarbons or hydrogen.
  • copolymers used according to the invention have molecular weights of 500 to 25,000, determined according to K. Rast. Ber. 550, 1922.
  • Antioxidants in the sense of the invention are understood to mean substances which prevent or inhibit undesirable processes caused by the action of oxygen in plastics. These are organic compounds of very different structures. They essentially belong to the group of amines and phenols and also include sulfur and phosphorus compounds. What they have in common is that they intervene in the antioxidant mechanism in different ways. They are mainly used as free radical scavengers, as peroxide decomposers, as metal ion deactivators and as UV absorbers. 2,6-Di-tert.-buty!
  • Suitable amines correspond to the general formula R-NH 2 , where R represents saturated or monounsaturated, straight-chain or branched hydrocarbon radicals having 8 to 18 carbon atoms.
  • the copolymer, antioxidant and optionally amine can be added to the crude oil separately, in the form of the dissolved or undissolved substances. You can also dissolve the components in a solvent and add this solution to the crude oil.
  • Aromatic hydrocarbons are preferred as solvents, for example aromatic mixtures which are commercially available under the name solvent naphtha or heavy benzene.
  • the pour point of Montrose and Beatrice North Sea crude is determined before and after shear stress. The measurement is carried out according to DIN ISO 3016.

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)
  • Health & Medical Sciences (AREA)
  • Emergency Medicine (AREA)
  • Compositions Of Macromolecular Compounds (AREA)
  • Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
  • Lubricants (AREA)
  • Addition Polymer Or Copolymer, Post-Treatments, Or Chemical Modifications (AREA)
  • Anti-Oxidant Or Stabilizer Compositions (AREA)

Claims (1)

  1. Utilisation de 0,005 à 0,5% en poids (par rapport au pétrole brut) d'un copolymère consistant en 65 à 80% en poids de motifs d'éthylène et 35 à 20% en poids de motifs d'acétate de vinyle, avec 0,01 à 1,0% en poids (par rapport au pétrole brut) d'un antioxydant et 0,001 à 1,0% en poids (par rapport au pétrole brut) d'une amine en tant qu'additifs améliorant les propriétés d'écoulement du pétrole brut.
EP85115541A 1984-12-15 1985-12-06 Utilisation de copolymères d'éthylène comme additifs pour huile brute Expired EP0186009B1 (fr)

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
DE3445811 1984-12-15
DE19843445811 DE3445811A1 (de) 1984-12-15 1984-12-15 Verwendung von ethylencopolymerisaten als rohoeladditive

Publications (3)

Publication Number Publication Date
EP0186009A2 EP0186009A2 (fr) 1986-07-02
EP0186009A3 EP0186009A3 (en) 1986-12-17
EP0186009B1 true EP0186009B1 (fr) 1989-09-27

Family

ID=6252874

Family Applications (1)

Application Number Title Priority Date Filing Date
EP85115541A Expired EP0186009B1 (fr) 1984-12-15 1985-12-06 Utilisation de copolymères d'éthylène comme additifs pour huile brute

Country Status (2)

Country Link
EP (1) EP0186009B1 (fr)
DE (2) DE3445811A1 (fr)

Families Citing this family (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
GB9200694D0 (en) * 1992-01-14 1992-03-11 Exxon Chemical Patents Inc Additives and fuel compositions

Family Cites Families (10)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US2696427A (en) * 1951-01-26 1954-12-07 Du Pont Stabilized fuel oil compositions
NL134313C (fr) * 1966-06-01
FR2067558A5 (en) * 1969-11-07 1971-08-20 Universal Oil Prod Co N-substituted alkoxyamines in resin-curing - catalyst systems
GB1413323A (en) * 1972-07-06 1975-11-12 United Lubricants Ltd Diesel fuel additives
US3850587A (en) * 1973-11-29 1974-11-26 Chevron Res Low-temperature flow improves in fuels
GB1473155A (fr) * 1974-09-04 1977-05-11
US3955940A (en) * 1975-01-06 1976-05-11 Exxon Research And Engineering Company Middle distillate petroleum oils containing cold flow improving additives
EP0003489B1 (fr) * 1977-12-20 1983-01-12 Imperial Chemical Industries Plc Huile brute ayant des propriétés améliorées d'écoulement à froid
US4405825A (en) * 1981-10-30 1983-09-20 Union Oil Company Of California Pour point reduction of syncrude
US4564460A (en) * 1982-08-09 1986-01-14 The Lubrizol Corporation Hydrocarbyl-substituted carboxylic acylating agent derivative containing combinations, and fuels containing same

Also Published As

Publication number Publication date
DE3573272D1 (en) 1989-11-02
EP0186009A3 (en) 1986-12-17
DE3445811A1 (de) 1986-06-19
EP0186009A2 (fr) 1986-07-02

Similar Documents

Publication Publication Date Title
EP2935346B1 (fr) Compositions polymères en copolymère éthylène-ester de vinyle alkyl(méth)acrylates, procédé pour la préparation et l'utilisation desdites compositions comme produits améliorant le point d'écoulement pour les huiles brutes, les huiles minérales ou les produits pétroliers
EP0463518B1 (fr) Terpolymères de l'éthylène, leur préparation et leur utilisation pour les distillats d'huile minérale
EP0807642B1 (fr) Terpolymères de l'éthylène, leur préparation et leur utilisation pour les distillats d'huile minérale
DE3320720C2 (fr)
EP0493769B1 (fr) Terpolymères de l'éthylène, leur préparation et leur utilisation pour les distillats d'huile minérale
EP0203554B1 (fr) Utilisation de terpolymères d'éthylène, comme additifs pour huiles minérales et distillats d'huiles minérales
DE2557793A1 (de) Mitteldestillat-brennstoffzusammensetzungen mit verbesserten kaltfliesseigenschaften sowie diese eigenschaften verbessernde zusaetze
EP2935345B1 (fr) Formulations de polymères dans des solvants à haut point d'éclair, procédé pour la préparation et l'utilisation desdites formulations comme produits améliorant le point d'écoulement pour les huiles brutes, les huiles minérales et les produits pétroliers
DE2810364A1 (de) Paraffinhaltiges erdoeldestillatgemisch mit fliessfaehigkeitsverbesserndem kombinationszusatz aus oelloeslichen aliphatischen copolymeren mit stickstoffderivaten von kohlenwasserstoffsubstituierten bernsteinsaeureverbindungen
EP0258572B1 (fr) Procédé pour améliorer la fluidité d'huiles minérales et de distillats d'huiles minérales
DE2519577C2 (de) Additive und diese enthaltende brenn- und treibstoffe
EP0061696B1 (fr) Procédé d'amélioration de l'écoulement des huiles minérales
DE3921279A1 (de) Verfahren zur verbesserung der fliessfaehigkeit von mineraloelen und mineraloeldestillaten
EP3394122A1 (fr) Compositions de polymère à maniabilité améliorée
EP0190553B1 (fr) Procédé d'amélioration de la fluidité des huiles minérales et des distillats d'huiles minérales
DD236940A5 (de) Additivkonzentrat zur einbeziehung in erdoel-destillatbrennstoffe
EP0186009B1 (fr) Utilisation de copolymères d'éthylène comme additifs pour huile brute
EP0055355B1 (fr) Distillats de pétrole à fonctionnement amélioré à basse température
EP0105529A1 (fr) Copolymères, procédé de leur préparation et leur usage
EP0309897B1 (fr) Copolymères d'éthylène et d'ester vinylique de l'acide méthoxy-acétique et application comme additifs aux distillats d'huile minérale
EP0251002B1 (fr) Procédé pour améliorer la fluidité d'huiles minérales et de distillats d'huiles minérales
DE1770011C3 (fr)
DE2426504A1 (de) Zusatzkombination fuer mineraloele
DE1545337C (de) Die Verwendung neuer Stabilisatoren fur die Stabilisierung von Brenn und Kraftstoffen
LU93040B1 (de) Additiv zur Verbesserung der Fliesseigenschaften von paraffinhaltigen Rohölen

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: A2

Designated state(s): DE FR GB

PUAL Search report despatched

Free format text: ORIGINAL CODE: 0009013

AK Designated contracting states

Kind code of ref document: A3

Designated state(s): DE FR GB

17P Request for examination filed

Effective date: 19870108

17Q First examination report despatched

Effective date: 19880603

RAP1 Party data changed (applicant data changed or rights of an application transferred)

Owner name: HOECHST AKTIENGESELLSCHAFT

GRAA (expected) grant

Free format text: ORIGINAL CODE: 0009210

AK Designated contracting states

Kind code of ref document: B1

Designated state(s): DE FR GB

REF Corresponds to:

Ref document number: 3573272

Country of ref document: DE

Date of ref document: 19891102

ET Fr: translation filed
GBT Gb: translation of ep patent filed (gb section 77(6)(a)/1977)
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
PGFP Annual fee paid to national office [announced via postgrant information from national office to epo]

Ref country code: GB

Payment date: 19921124

Year of fee payment: 8

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

Ref country code: FR

Payment date: 19921127

Year of fee payment: 8

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

Ref country code: GB

Effective date: 19931206

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

Effective date: 19931206

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

Ref country code: FR

Effective date: 19940831

REG Reference to a national code

Ref country code: FR

Ref legal event code: ST

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

Ref country code: DE

Payment date: 19950117

Year of fee payment: 10

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

Ref country code: DE

Effective date: 19960903