EP0807696B1 - Procédé pour le conditionnement de l'eau d'alimentation de chaudieres à passage unique et circulation forcée. - Google Patents

Procédé pour le conditionnement de l'eau d'alimentation de chaudieres à passage unique et circulation forcée. Download PDF

Info

Publication number
EP0807696B1
EP0807696B1 EP96810289A EP96810289A EP0807696B1 EP 0807696 B1 EP0807696 B1 EP 0807696B1 EP 96810289 A EP96810289 A EP 96810289A EP 96810289 A EP96810289 A EP 96810289A EP 0807696 B1 EP0807696 B1 EP 0807696B1
Authority
EP
European Patent Office
Prior art keywords
feed water
polyamine
cyclohexylamine
mixture
aqueous solution
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 - Lifetime
Application number
EP96810289A
Other languages
German (de)
English (en)
Other versions
EP0807696A1 (fr
Inventor
Anton Graf
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.)
Faborga SA
Original Assignee
Faborga SA
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 Faborga SA filed Critical Faborga SA
Priority to EP96810289A priority Critical patent/EP0807696B1/fr
Priority to AT96810289T priority patent/ATE182633T1/de
Priority to DE59602547T priority patent/DE59602547D1/de
Publication of EP0807696A1 publication Critical patent/EP0807696A1/fr
Application granted granted Critical
Publication of EP0807696B1 publication Critical patent/EP0807696B1/fr
Anticipated expiration legal-status Critical
Expired - Lifetime legal-status Critical Current

Links

Classifications

    • C—CHEMISTRY; METALLURGY
    • C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
    • C23F—NON-MECHANICAL REMOVAL OF METALLIC MATERIAL FROM SURFACE; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL; MULTI-STEP PROCESSES FOR SURFACE TREATMENT OF METALLIC MATERIAL INVOLVING AT LEAST ONE PROCESS PROVIDED FOR IN CLASS C23 AND AT LEAST ONE PROCESS COVERED BY SUBCLASS C21D OR C22F OR CLASS C25
    • C23F11/00—Inhibiting corrosion of metallic material by applying inhibitors to the surface in danger of corrosion or adding them to the corrosive agent
    • C23F11/08—Inhibiting corrosion of metallic material by applying inhibitors to the surface in danger of corrosion or adding them to the corrosive agent in other liquids
    • C23F11/10—Inhibiting corrosion of metallic material by applying inhibitors to the surface in danger of corrosion or adding them to the corrosive agent in other liquids using organic inhibitors
    • C23F11/14—Nitrogen-containing compounds
    • C23F11/141—Amines; Quaternary ammonium compounds

Definitions

  • the present invention relates to a method for Conditioning feed water for once-through boiler systems, in which a mixture of the boiler feed water at least one alkalizing amine and one aliphatic polyamine with at least 12 carbon atoms in the aliphatic residue.
  • the conditioning agent is for use in water-steam cycles of power plants provided that as a steam generator Have a once-through boiler.
  • a very common way to Conditioning is the alkalization of the water-steam cycle, which is based on the fact that the Dissolution of iron from the parts of the apparatus at high Temperatures are observed by raising the pH is reduced.
  • An overview of conditioning of feed water with conditioning agents can be found in the VGB guideline for boiler feed water, boiler water and Steam from steam generators over 68 bar permitted Operating pressure (VGB-R 450 L), published by VGB technical association of large power plant operators, Essen 1988.
  • Forced-flow boiler systems are particularly found in Power plants of the electricity supply companies and in large industrial plants because they are in large units allow, even under supercritical conditions, i.e. at very high pressures and high temperatures, steam too produce. It is known that the thermal Efficiency of power plants with increasing operating temperature improved.
  • Ammonia is often used as a volatile conditioning agent been used. However, it has been found to be disadvantageous exposed it because of its high volatility and its unfavorable distribution between water and steam is not possible, a uniform alkalization of all To reach parts of the cycle. -You're after wanted less volatile bases and already mixtures of different volatile amines used to the special conditions of the phase transition at Evaporation, condensation and in the two-phase area of wet steam to the respective forms of corrosion inhibit.
  • the European reveals Patent application No. EP-A1-0'134'365 a means for Corrosion inhibition in steam generators or for Conditioning of boiler feed water for power plants.
  • the Agent consists of a "film-forming" amine, for example an aliphatic polyamine with 12 to 22 carbon atoms in the aliphatic rest, and at least one alkalizing Amine, for example cyclohexylamine, and an amino alcohol.
  • An attempt at a once-through boiler (100 bar, 305 ° C) using a conditioning agent from 63.5 % Stearylaminopropylene amine, 31.7% 2-amino-2-methyl-1-propanol and 4.8% of a dispersant is given.
  • EP-A1-0'463'714 describes a ternary composition of dihydroxyacetone, catalytic amounts of hydroquinone and volatile amines for the removal of oxygen from feed water and for the prevention of CO 2 corrosion.
  • the composition may further contain a "film-forming" amine. Use in forced flow boilers is not mentioned or suggested.
  • the object of the invention was to provide a method for Specify conditioning of feed water where one adds an amine mixture mentioned above, which the meets the requirements discussed above and at Use in once-through steam boiler systems is suitable.
  • the corrosion protection effect in the steam boiler be achieved, and on the other hand, everyone should downstream components, especially the turbine, protected against corrosion.
  • the role of the first component namely the Monoethanolamine is seen in the first place Line for permanent alkalization of the aqueous phase including the condensate.
  • the second component of the present conditioning agent is optionally substituted cyclohexylamine. It is an amine volatile with water vapor, which forms an amine-containing, ie basic, protective layer and stabilizes the magnetite protective layer. It was found that the layer mentioned consists predominantly of dicyclohexylamine, which, under the conditions of use in a steam boiler, was formed from two molecules of cyclohexylamine according to the following scheme: 2 C 6 H 11 NH 2 ⁇ (C 6 H 11 ) 2 NH + NH 3
  • the present invention proposes use unsubstituted cyclohexylamine; but it will come also inert substituted cyclohexylamines, such as e.g. B. dicyclohexylamine, methylcyclohexylamine, Ethylcyclohexylamine, dimethylcyclohexylamine and others.
  • Such compounds are by hydrogenation of the corresponding aromatic amines or nitro compounds easily accessible.
  • the optionally substituted also acts Cyclohexylamine as hydrotrope in the manufacture of the present means and also has the Property, the water vapor volatility of the below described third component to increase and this in to bring larger quantities to the turbine than before.
  • the present conditioning agent works accordingly not only for setting the desired pH in the feed water and in the boiler, but forms Corrosion protection layers in all parts of the system.
  • polyamines examples include dodecylaminomethyleneamine, Dodecylaminodimethyleneamine, dodecylaminotrimethyleneamine, the corresponding tetradecyl, hexadecyl and octadecyl amines, Octadecenylaminotrimethyleneamine, octadecenylaminodi- (trimethylamino) trimethyleneamine, Palmitylaminotrimethyleneamine, Hexadecenylaminotrimethyleneamine, dodecenylaminotrimethyleneamine, etc.
  • N-oleyl is 1,3-propanediamine (i.e. octadecen (9) ylaminotrimethyleneamine) prefers.
  • Components of the conditioning agent used according to the invention can depend on the application conditions and the respective selected individual substances within wide limits vary. If, for example, as component (a) monoethanolamine, as component (b) cyclohexylamine and as Component (c) oleylaminopropylene amine can be selected, see above the proportions by weight of components (a), (b) behave and (c), based on pure, i.e. 100%, compounds, such as (40-70) :( 30-50) :( 4-10), the sum of the three Ingredients add up to 100.
  • the present conditioning agent can in contain other additional ingredients, generally in very small amounts so as not to have the effect affect.
  • the present conditioning agent will preferably as an aqueous, relatively concentrated solution formulated that the system to be conditioned easily can be added.
  • An aqueous mixture which about Contains 4 to 25 wt .-% of the conditioning agent is a clear, stable solution, although up to about 4 % By weight of fatty alkyl polyamine, which in itself only is slightly water soluble.
  • the Cyclohexylamine an effective solubilizer, so one Hydrotropic substance for which fat polyamine represents.
  • aqueous solution of the agent For Production of the aqueous solution of the agent is done Advantageously, so that you first have a relative produces a concentrated aqueous solution of monoethanolamine, which is miscible with water, and then a previously prepared mixture of the fatty aminoalkylene amine and the cyclohexylamine stirred. You get this way a relatively concentrated aqueous solution, which then unlimited with water, preferably pure, demineralized and non-carbonated water, dilutable is, preferably to an approximately 15% solution. This the latter has a pH of about 12 to 12.5.
  • the present conditioning agent was tested in a large-scale test for its effectiveness.
  • a solution of the conditioning agent described above was added to the feed water in the metering station for conditioning agent of a power plant block, containing a once-through boiler, operating pressure 180 bar (18 MPa), main steam temperature 540 ° C, and a steam turbine with an output of 311 MW, such that a Concentration of 1 to 2 mg / l (1 to 2 ppm) was set and maintained.
  • Steam samples were continuously taken from the live steam line, the samples were condensed by cooling, the condensate was passed through a strongly acidic ion exchanger and finally the conductance was measured in the outlet of the ion exchanger.
  • the pH value of the condensate (in front of the ion exchanger) was in the range from 8.7 to 9.5 with a most common value of 9.4.
  • the conductivity was approximately 0.15 to 0.16 ⁇ S ⁇ cm -1 . It must be said that the guidelines of the VGB (Technical Association of Large Power Plant Operators eV) for boiler feed water for corresponding power plants have a pH of 9.5 ⁇ 0.2 and for conductivity a value of ⁇ 0.2 ⁇ S ⁇ cm -1 provide.

Landscapes

  • Chemical & Material Sciences (AREA)
  • Engineering & Computer Science (AREA)
  • Materials Engineering (AREA)
  • Mechanical Engineering (AREA)
  • Metallurgy (AREA)
  • Organic Chemistry (AREA)
  • Preventing Corrosion Or Incrustation Of Metals (AREA)
  • Macromolecular Compounds Obtained By Forming Nitrogen-Containing Linkages In General (AREA)
  • Steam Or Hot-Water Central Heating Systems (AREA)
  • Jet Pumps And Other Pumps (AREA)

Claims (12)

  1. Procédé pour le conditionnement de l'eau d'alimentation de chaudières à passage forcé unique, comprenant l'addition à l'eau d'alimentation, d'un mélange contenant au moins une amine alcalinisante et une polyamine aliphatique comprenant au moins 12 atomes de carbone dans son radical aliphatique, caractérisé en ce qu'on ajoute à l'eau d'alimentation de chaudières à passage forcé unique et à haute puissance, ayant une pression de service dépassant 150 bars et des températures de service dépassant 500 °C, un mélange ternaire d'amines aux fins de protection contre la corrosion et d'établissement d'une conductivité du condensat inférieure à 0,2 µS·cm-1, le mélange étant constitué par la monoéthanolamine, la cyclohexylamine éventuellement substituée, et une polyamine aliphatique à chaíne longue répondant à la formule R-[NH-(CH2)p-]n-NH2 dans laquelle
    R
    est un radical aliphatique hydrocarboné comportant de 12 à 24 atomes de carbone,
    p
    est un nombre entier de 1 à 6, et
    n
    est un nombre entier de 1 à 6,
    et que les trois dites amines, calculées comme matière sèche, sont présentes dans un rapport pondéral de 40 à 70% de monoéthanolamine, de 30 à 50% de cyclohexylamine, et de 4 à 10% de polyamine de formule (I), la somme des trois constituants se complétant à 100%.
  2. Procédé selon la revendication 1, caractérisé en ce qu'on utilise de la N-oléyl-1,3-propanediamine comme polyamine aliphatique à chaíne longue de formule (I).
  3. Procédé selon l'une des revendications précédentes, caractérisé en ce que la quantité du mélange des amines est dosée de sorte à obtenir et à maintenir dans l'eau d'alimentation de chaudière une concentration en mélange comprise entre 0,5 et 5 ppm.
  4. Procédé selon l'une des revendications précédentes, caractérisé en ce que le mélange d'amines est utilisé sous forme de solution aqueuse.
  5. Procédé selon la revendication 4, caractérisé en ce que la solution aqueuse contient de 4 à 25% en poids de mélange d'amines.
  6. Procédé selon la revendication 1, caractérisé en ce qu'on utilise un mélange d'amines contenant des amines purifiées.
  7. Procédé de préparation d'une solution aqueuse d'un mélange d'amines pour l'utilisation dans le procédé selon la revendication 4, caractérisé en ce qu'on prépare d'abord une solution aqueuse relativement concentrée de monoéthanolamine, on incorpore dans cette solution sous agitation un mélange préalablement préparé de la polyamine de formule (I) et de cyclohexylamine, et on dilue le mélange obtenu avec de l'eau déminéralisée et exempte d'acide carbonique, tout en utilisant des matières de départ purifiées et en travaillant à l'abri de l'acide carbonique atmosphérique, et en ce que les trois dites amines, calculées comme matière sèche, sont présentes dans un rapport pondéral de 40 à 70% de monoéthanolamine, de 30 à 50% de cyclohexylamine, et de 4 à 10% de polyamine de formule (I), la somme des trois constituants se complétant à 100%.
  8. Procédé selon la revendication 7, caractérisé par la préparation d'une solution aqueuse d'environ 15%.
  9. Utilisation d'une composition de conditionnement composée de monoéthanolamine, de cyclohexylamine et d'une polyamine aliphatique à chaíne longue répondant à la formule R-[NH-(CH2)p-]n-NH2 dans laquelle
    R
    est un radical aliphatique hydrocarboné comportant de 12 à 24 atomes de carbone,
    p
    est un nombre entier de 1 à 6, et
    n
    est un nombre entier de 1 à 6,
    les trois dites amines, calculées comme matière sèche, étant présentes dans un rapport pondéral de 40 à 70% de monoéthanolamine, de 30 à 50% de cyclohexylamine, et de 4 à 10% de polyamine de formule (I), la somme des trois constituants se complétant à 100%, comme additif à l'eau d'alimentation de chaudières à passage forcé unique ayant une pression de service dépassant 150 bars et une température de service dépassant 500 °C pour protection contre la corrosion et établissement d'une conductivité inférieure à 0,2 µS·cm-1 dans le condensat.
  10. Utilisation selon la revendication 9, caractérisée en ce que la composition de conditionnement est sous forme de solution aqueuse.
  11. Utilisation selon la revendication 10, caractérisée en ce que la composition de conditionnement est sous forme d'une solution aqueuse d'environ 15%.
  12. Utilisation selon la revendication 9, caractérisée en ce que la composition de conditionnement est composée d'amines purifiées.
EP96810289A 1996-05-06 1996-05-06 Procédé pour le conditionnement de l'eau d'alimentation de chaudieres à passage unique et circulation forcée. Expired - Lifetime EP0807696B1 (fr)

Priority Applications (3)

Application Number Priority Date Filing Date Title
EP96810289A EP0807696B1 (fr) 1996-05-06 1996-05-06 Procédé pour le conditionnement de l'eau d'alimentation de chaudieres à passage unique et circulation forcée.
AT96810289T ATE182633T1 (de) 1996-05-06 1996-05-06 Verfahren zur konditionierung von speisewasser fur zwang durchlaufkessel anlagen
DE59602547T DE59602547D1 (de) 1996-05-06 1996-05-06 Verfahren zur Konditionierung von Speisewasser fur Zwang durchlaufkessel Anlagen

Applications Claiming Priority (1)

Application Number Priority Date Filing Date Title
EP96810289A EP0807696B1 (fr) 1996-05-06 1996-05-06 Procédé pour le conditionnement de l'eau d'alimentation de chaudieres à passage unique et circulation forcée.

Publications (2)

Publication Number Publication Date
EP0807696A1 EP0807696A1 (fr) 1997-11-19
EP0807696B1 true EP0807696B1 (fr) 1999-07-28

Family

ID=8225601

Family Applications (1)

Application Number Title Priority Date Filing Date
EP96810289A Expired - Lifetime EP0807696B1 (fr) 1996-05-06 1996-05-06 Procédé pour le conditionnement de l'eau d'alimentation de chaudieres à passage unique et circulation forcée.

Country Status (3)

Country Link
EP (1) EP0807696B1 (fr)
AT (1) ATE182633T1 (fr)
DE (1) DE59602547D1 (fr)

Families Citing this family (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
DE69906249T2 (de) * 1999-04-12 2004-01-22 Faborga S.A. Zusammensetzung und Verfahren zur Konditionierung von Industriewasser
WO2011144230A1 (fr) * 2010-05-18 2011-11-24 Bk Giulini Gmbh Moyen destiné à améliorer le transfert de chaleur dans des installations de production de vapeur
FR2979915B1 (fr) * 2011-09-13 2014-11-07 Ceca Sa Inhibiteurs de corrosion de voute de conduites de transport de bruts d'extraction d'hydrocarbures
DE102012203010A1 (de) 2012-02-28 2013-08-29 Areva Gmbh Verfahren zur Reinigung und Konditionierung des Wasser-Dampfkreislaufes eines Kraftwerkes, insbesondere eines Kernkraftwerkes
EP3628922A1 (fr) * 2018-09-28 2020-04-01 Siemens Aktiengesellschaft Procédé de conditionnement d'une turbine basse pression

Family Cites Families (8)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US3860430A (en) * 1973-11-05 1975-01-14 Calgon Corp Filming amine emulsions
US4206172A (en) * 1978-10-13 1980-06-03 Betz Laboratories, Inc. Alkanolamines and ethylene polyamines as cold-end additives
EP0134365B1 (fr) * 1983-08-03 1987-06-16 UNION CHIMIQUE ET INDUSTRIELLE DE L'OUEST S.A. Société anonyme dite: Composition inhibitrice de corrosion pour protéger les surfaces métalliques d'installations utilisant de l'eau comme fluide thermique ou énergétique, procédé pour protéger lesdites surfaces
US4657785A (en) * 1985-12-11 1987-04-14 Nalco Chemical Company Use of benzo and tolyltriazole as copper corrosion inhibitors for boiler condensate systems
CA1339761C (fr) * 1988-07-11 1998-03-24 Anthony M. Rossi Compose et methode pour controler la corrosion dand une chaudiere a vapeur
JPH02209493A (ja) * 1989-02-09 1990-08-20 Kurita Water Ind Ltd 蒸気又は凝縮水系用防食剤
US5094814A (en) * 1990-06-15 1992-03-10 Nalco Chemical Company All-volatile multi-functional oxygen and carbon dioxide corrosion control treatment for steam systems
US5091108A (en) * 1991-02-21 1992-02-25 Nalco Chemical Company Method of retarding corrosion of metal surfaces in contact with boiler water systems which corrosion is caused by dissolved oxygen

Also Published As

Publication number Publication date
EP0807696A1 (fr) 1997-11-19
DE59602547D1 (de) 1999-09-02
ATE182633T1 (de) 1999-08-15

Similar Documents

Publication Publication Date Title
US4562042A (en) Anticorrosive composition
DE69706810T2 (de) Sauerstoffentfernungsmittel als Verbindung für die Behandlung von Kesselsteinspeisewasser
DE1937617C3 (de) Korrosionshemmendes Mittel
DE69514468T2 (de) Verfahren zur Verhinderung von Sulphatablagerung in wässerigen Systemen
DE3136491C2 (fr)
DE69223732T2 (de) Korrosionsinhibierung mit wasserlöslichen Chelaten von seltenen Erden
DE69100500T2 (de) Multifunktionale Behandlung von Dampferzeugersystemen zum Schutz vor Korrosion durch Sauerstoff und Kohlendioxid.
DE2447895A1 (de) Korrosions-schutzmittel
DE2055779A1 (de) Korrosionsschutzmittel fur Metall oberflachen
DE69012540T2 (de) Korrosionskontrolle in wässrigen Systemen durch bestimmte Phosphonomethylaminoxide.
DE3904733C2 (de) Korrosionsinhibitor
DE3137525A1 (de) Behandlung von waessrigen systemen zur korrosionshemmung
DE69209739T2 (de) Mehrzweckmittel zur Verhinderung und Entfernung von Inkrustationen
EP0127132A1 (fr) Utilisation de monoamides d'acides alcénylsucciniques comme inhibiteurs de corrosion
DE102007041216B3 (de) Verwendung von Zusammensetzungen als Korrosionsinhibitoren enthaltend kationische Tenside und die Zusammensetzungen
DE60036899T2 (de) Chemikalie und verfahren zur wasserbehandlung
EP0807696B1 (fr) Procédé pour le conditionnement de l'eau d'alimentation de chaudieres à passage unique et circulation forcée.
EP1117621A1 (fr) Substances de traitement d'eau
DE69225669T2 (de) Zusammensetzung und Verfahren zur Kesselstein- und Korrosionsinhibierung, unter Verwendung von Naphtylaminpolykarbonsäuren
DE69906249T2 (de) Zusammensetzung und Verfahren zur Konditionierung von Industriewasser
DE2330340A1 (de) Korrosionsinhibierende zubereitung
EP0184558B1 (fr) Procédé et agent antitartre
DE69007822T2 (de) Methode zur Korrosionsverhütung von Dampf-/Kondensatwasser-Systemen.
DE19648843C2 (de) Melamin-polycarbonsäureamide und ihre Verwendung als Korrosionsschutzmittel
DE2016686A1 (de) Korrosionsschutzmittel

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

17P Request for examination filed

Effective date: 19960529

AK Designated contracting states

Kind code of ref document: A1

Designated state(s): AT BE CH DE FR LI NL

AX Request for extension of the european patent

Free format text: SI

GRAG Despatch of communication of intention to grant

Free format text: ORIGINAL CODE: EPIDOS AGRA

GRAG Despatch of communication of intention to grant

Free format text: ORIGINAL CODE: EPIDOS AGRA

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

RBV Designated contracting states (corrected)

Designated state(s): AT BE CH DE FR LI NL

AK Designated contracting states

Kind code of ref document: B1

Designated state(s): AT BE CH DE FR LI NL

REF Corresponds to:

Ref document number: 182633

Country of ref document: AT

Date of ref document: 19990815

Kind code of ref document: T

REG Reference to a national code

Ref country code: CH

Ref legal event code: NV

Representative=s name: IPTO S.A.

Ref country code: CH

Ref legal event code: EP

REF Corresponds to:

Ref document number: 59602547

Country of ref document: DE

Date of ref document: 19990902

ET Fr: translation filed
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: CH

Ref legal event code: PUE

Owner name: HELAMIN HOLDING S.A. C/O ECA EXPERTS COMPTABLES A

Free format text: FABORGA S.A.#AVENUE PICTET-DE ROCHEMONT 30#1211 GENF 6 (CH) -TRANSFER TO- HELAMIN HOLDING S.A. C/O ECA EXPERTS COMPTABLES ASSOCIES S.A.#BOULEVARD DE PEROLLES 37#1700 FRIBOURG (CH)

REG Reference to a national code

Ref country code: CH

Ref legal event code: PFA

Owner name: HELAMIN HOLDING S.A. C/O ECA EXPERTS COMPTABLES A

Free format text: HELAMIN HOLDING S.A. C/O ECA EXPERTS COMPTABLES ASSOCIES S.A.#BOULEVARD DE PEROLLES 37#1700 FRIBOURG (CH) -TRANSFER TO- HELAMIN HOLDING S.A. C/O ECA EXPERTS COMPTABLES ASSOCIES S.A.#BOULEVARD DE PEROLLES 37#1700 FRIBOURG (CH)

REG Reference to a national code

Ref country code: FR

Ref legal event code: PLFP

Year of fee payment: 20

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

Ref country code: CH

Payment date: 20150527

Year of fee payment: 20

Ref country code: DE

Payment date: 20150521

Year of fee payment: 20

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

Ref country code: BE

Payment date: 20150520

Year of fee payment: 20

Ref country code: FR

Payment date: 20150521

Year of fee payment: 20

Ref country code: AT

Payment date: 20150521

Year of fee payment: 20

Ref country code: NL

Payment date: 20150520

Year of fee payment: 20

REG Reference to a national code

Ref country code: FR

Ref legal event code: TP

Owner name: HELAMIN TECHNOLOGY HOLDING SA, CH

Effective date: 20151201

Ref country code: FR

Ref legal event code: CD

Owner name: HELAMIN TECHNOLOGY HOLDING SA, CH

Effective date: 20151201

REG Reference to a national code

Ref country code: DE

Ref legal event code: R071

Ref document number: 59602547

Country of ref document: DE

REG Reference to a national code

Ref country code: NL

Ref legal event code: MK

Effective date: 20160505

REG Reference to a national code

Ref country code: CH

Ref legal event code: PL

REG Reference to a national code

Ref country code: AT

Ref legal event code: MK07

Ref document number: 182633

Country of ref document: AT

Kind code of ref document: T

Effective date: 20160506