EP1598629A1 - Method of chemical cleaning of a gas and vapor installation - Google Patents
Method of chemical cleaning of a gas and vapor installation Download PDFInfo
- Publication number
- EP1598629A1 EP1598629A1 EP04011890A EP04011890A EP1598629A1 EP 1598629 A1 EP1598629 A1 EP 1598629A1 EP 04011890 A EP04011890 A EP 04011890A EP 04011890 A EP04011890 A EP 04011890A EP 1598629 A1 EP1598629 A1 EP 1598629A1
- Authority
- EP
- European Patent Office
- Prior art keywords
- plant
- circulation
- volumes
- deionized water
- until
- 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
Links
Images
Classifications
-
- F—MECHANICAL ENGINEERING; LIGHTING; HEATING; WEAPONS; BLASTING
- F22—STEAM GENERATION
- F22B—METHODS OF STEAM GENERATION; STEAM BOILERS
- F22B37/00—Component parts or details of steam boilers
- F22B37/02—Component parts or details of steam boilers applicable to more than one kind or type of steam boiler
- F22B37/48—Devices for removing water, salt, or sludge from boilers; Arrangements of cleaning apparatus in boilers; Combinations thereof with boilers
- F22B37/52—Washing-out devices
-
- F—MECHANICAL ENGINEERING; LIGHTING; HEATING; WEAPONS; BLASTING
- F28—HEAT EXCHANGE IN GENERAL
- F28G—CLEANING OF INTERNAL OR EXTERNAL SURFACES OF HEAT-EXCHANGE OR HEAT-TRANSFER CONDUITS, e.g. WATER TUBES OR BOILERS
- F28G9/00—Cleaning by flushing or washing, e.g. with chemical solvents
Definitions
- the invention is therefore based on the object, the beginning to improve said method of chemical cleaning in such a way that its need for demineralised or fully desalted Water is significantly reduced and an economically water saving concept is set up.
- the pickling and cleaning chemicals of Stage e directly into the degreasing solution of stages c and d dosed in, without the degreasing solution previously from the Plant was removed. This eliminates numerous intermediate rinse steps; also, by heating the wetting agent or degreasing solution in stages c and d the effect of the same elevated.
- the method according to the invention achieves this Same procedural result as the prior art with lower plant volumes in that after the first Pre-rinse all treatments to be done in the circulation, what becomes possible by that between the network agent solution and the pickling / cleaning solution no negavtiven reactions occur, i. the hydrofluoric acid reacts with the inhibitor not with the wetting agent of degreasing.
- Fig. 1 is a schematic diagram of the system, with the inventive Procedure is chemically cleaned.
- the schematic sketch of FIG. 1 shows the boiler system to be cleaned, generally designated 3.
- the boiler plant 3 is from an external circulation pump 1 from the associated Mixing container 2 with the desired chemical dosage 7 (Wetting agent solution ((TS LT 711)) and / or inhibited with Rodine 31 A. Hydrofluoric acid) and the deionate 9. Other products for the surfactant solution and the inhibitor are commercially available.
- the line circuit has a by-pass with filter 4, which is backwashable. At the by-pass are backwash connections 5 and 6 connected.
- the exit for the to be disposed of Solutions is labeled 8. It's for control the method according to the invention provides numerous valves, which are indicated at 11 to 19. In the boiler plant 3 there is an evaporator 20, while in between a superheater 21 is provided. It will be clear that the system Display instruments for the desired parameters. Also belong to the deionized supply appropriate tanks and a corresponding water treatment plant (not shown).
- valves 11 - 19 After preparing the plant components to be treated and all temporary ports and connections have been created The system valves 11 - 19 must be in accordance with a valve position list closed or opened.
- the first step after filling the system is pre-wash with deionized, for coarse impurities and loose dirt particles to remove.
- the rinsing is done in the open-circuit method (OC method) with a pipe speed of> 0.5 m / s.
- the prewash is complete when the turbidity at the outlet 8 of System falls below the limit specified below.
- the aim is to reach the limit as soon as possible, to the water consumption as possible to a half to a maximum to limit an investment volume.
- the system is of the OC method (open circuit) switched to circuit switching.
- Pre-rinsing the system removes loose particles Service. As the pipeline surfaces and heating surfaces through However, transport and assembly are contaminated with oils and greases must be treated with wetting agents become.
- Wetting agents form hydrophobic surfaces converted into hydrophilic to the water-based cleaning solution Contact with all surfaces to be cleaned enable.
- the degreasing solution is at the circulation pump 1 directly into the Mixing container 2 dosed. It becomes a nonionic, biological degradable and suitable for a wide temperature range Wetting agent used. In addition, according to the invention ensured that the wetting agent with the inhibitor used Cleaning solution tolerates.
- the wetting agent is metered in the circulation process until the Wetting agent solution reaches a concentration of about 0.05% Has.
- the exposure time of the wetting agent solution should be at least 3 hours last for. During this exposure time, the wetting agent solution becomes heated to 50 - 80 ° C.
- the wetting agent solution becomes continued in the circulation circuit. While The circulation of the wetting agent solution can produce larger particles be detached from the surfaces. These particles> 100 ⁇ m be by means of a built-in by-pass microfilter. 4 removed from the system.
- the microfilter 4 has a capacity of 200 m 3 / h, filter size 100 microns.
- the system is heated in the circulation circuit, m the reaction rate and the efficiency of the acid solution too increase. Doubled with the increase in temperature by 10 ° C the reaction rate of a chemical reaction. It is therefore ensured that the highest possible temperature is reached.
- the system is heated to 50-80 ° C.
- a heat source Serves either by the operator provided auxiliary steam or a separate oil-fired hot water boiler.
- the heat exchanger is designed so that a temperature be reached from about 50 - 80 ° C within 6 - 10 hours can.
- the heating of the systems must be stopped as soon as a temperature from 50 - 80 ° C at the return 10 is detected.
- the circulation circuit will continue to be maintained.
- the cleaning solution consists of Rodine inhibited 1% Hydrofluoric acid.
- the hydrofluoric acid and the inhibitor Rodine are over the mixing container of the circulation pump 1 in the circulation process dosed directly into the wetting agent solution, with it It should be noted that the wetting agent and the inhibited hydrofluoric acid do not affect each other negatively.
- the flow rate of the cleaning solution in the too treated piping is usually 0.2 m / s.
- the concentration of dissolved iron must be the maximum iron concentration do not exceed.
- the monitoring values are given below.
- the cleaning is finished when the iron concentration at free acid is constant. With the achievement of constant Values, the circulation circulation is stopped. All valves (Inlet 20 and return 11) are closed. Yes according to plant type The acid can now remain in the system for up to 12 hours (Stance phase) to increase the cleaning performance.
- Stage g displacing the acid and purging for conductivity
- the acid is purged with deionized from the system repressed. After bleeding the system, all sections must and sections are checked for conductivity. This is using high-speed process with auxiliary pumps carried out.
- the monitoring values are given below. As soon as the Values at the drains / drains of the system detectable are there, high-speed rinsing is over.
- the entire system is after flushing with conductivity Deionat filled.
- the circulation circuit is resumed.
- ammonia water becomes metered into the system.
- ammonia is the pH raised to> 10.2.
- hydrogen peroxide becomes dosed into the circulation.
- This oxidizing agent causes the formation of a passive layer on the stained, neutralized Metal surface. Passivation is completed when a positive redox potential is measured. The monitoring values are listed below.
- the passivation solution is removed from the system and the sections statically, by geodetic height, emptied. If necessary, the auxiliary pumps for emptying used by the system.
- the wastewater basin serves as intermediate storage.
- the liquid acid concentration in the waste water is in the range between 0.01% to 0.2%.
- the wastewater contains the inhibitor used and dissolved iron ions (Fe ++ ).
- the pickling solution becomes online during the suppression with hydrated lime pre-neutralized. Following the pickling, the Waste water in the wastewater tank according to marre addition neutralized by hydrated lime.
- the organic components of the wastewater are adsorbed separated on activated charcoal by adding powdered activated carbon is added to the wastewater.
- the hydrofluoric acid reacts with the hydrated lime to form fluorspar (CaF 2 ) and water.
- fluorspar (CaF 2 )
- the water-insoluble fluorspar, the precipitated iron hydroxide Fe (OH) 3 and the activated carbon settle out.
- the waste water from the alkalization and passivation contains Ammonia and hydrogen peroxide. This wastewater is in one additional wastewater tank, since it does not match the Fluid wastewater from the dressing can be mixed.
- the wastewater is discharged via a water treatment plant in cation / anion exchange with upstream activated carbon filter. This ensures that both the dissolved ions retained, as well as the COD content of the water reduced becomes.
- the wastewater has a temperature of max. 35 ° C.
- the treated wastewater can be handled easily via the service or Raw water returned to the water cycle of the plant become.
- the precipitated calcium fluoride salts and the iron oxide forms together with the activated carbon a thin sludge mixture.
- This Thin sludge also contains the purged out of the plant Solids.
- the thin sludge is pressed off via a chamber filter press.
- the resulting filter cake (water content 45-55%) is in Covered containers until disposal on a suitable Landfill temporarily stored. An approved local waste disposal company is assigned with the professional disposal. If necessary, the filter cake is examined by laboratory chemistry.
- the permeate is discharged into the sewer. During the Delivery, the wastewater values are monitored.
- the inventive method ensures that the treated Surfaces free of rust, scale and imitation Magnetite are.
- the maximum total removal of iron during treatment will not exceed 20 g / m 2 , which also applies to chromium steels.
Landscapes
- Engineering & Computer Science (AREA)
- Mechanical Engineering (AREA)
- General Engineering & Computer Science (AREA)
- Physics & Mathematics (AREA)
- Thermal Sciences (AREA)
- Chemical & Material Sciences (AREA)
- Combustion & Propulsion (AREA)
- Cleaning And De-Greasing Of Metallic Materials By Chemical Methods (AREA)
- Cleaning By Liquid Or Steam (AREA)
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
Abstract
Description
Derartige Verfahren sind in unterschiedlichen Ausführungsformen im Stand der Technik bekannt. Es wird hierzu beispielsweise verwiesen auf die VGB-Richtlinie R 513, von 2002.Such methods are in different embodiments known in the art. It is for this purpose, for example referred to the VGB guideline R 513, from 2002.
Nachteilig hat sich bei diesen Anlagen, die üblicherweise eine Leistung von zur Zeit bis 1000 MW besitzen, der extrem hohe Wasserverbrauch bemerkbar gemacht, der aus den Maßnahmen der Beizung/chemischen Reinigung (VGB-Standard: ca. zwölf Anlagenvolumina Deionat) entsteht. Diese Anlagenvolumina verteilen sich auf das Füllen und Vorspülen, bei dem üblicherweise drei Anlagenvolumina erforderlich sind. Beim Entfetten und Spülen auf Trübung werden ein bzw. weitere drei Anlagenvolumina benötigt, sowie beim Beizen und Spülen auf Gleitfähigkeit zusätzlich ein bzw. vier Anlagenvolumina. Es sind also zahlreiche Zwischenspülschritte erforderlich. Häufig ist allerdings nur eine begrenzte Verfügbarkeit an demineralisiertem oder voll entsalztem Wasser (Deionat) oder eine nicht ausreichende Rohrwasserversorgung vorhanden. Des Weiteren wird auch aus wirtschaftlichen und ökologischen Gründen immer eine Reduzierung des Wasserverbrauchs angestrebt.The disadvantage of these systems, which is usually a Power of currently up to 1000 MW own, the extremely high Water consumption made noticeable, resulting from the measures of Pickling / dry cleaning (VGB standard: approx. Twelve plant volumes Deionate) is formed. Distribute these asset volumes on filling and prewashing, which is usually three Investment volumes are required. When degreasing and rinsing turbidity requires one or more three volumes of equipment, as well as for pickling and rinsing for lubricity in addition one or four investment volumes. So there are many Intermediate rinse steps required. Often, however, only limited availability of demineralized or full desalinated water (deionized water) or insufficient water supply available. Furthermore, also from economic and ecological reasons always a reduction of water consumption.
Der Erfindung liegt deshalb die Aufgabe zugrunde, das eingangs genannte Verfahren zum chemischen Reinigen derart zu verbessern, dass sein Bedarf an demineralisiertem oder voll entsalztem Wasser erheblich verringert und ein wirtschaftlich Wasser sparendes Konzept aufgestellt wird.The invention is therefore based on the object, the beginning to improve said method of chemical cleaning in such a way that its need for demineralised or fully desalted Water is significantly reduced and an economically water saving concept is set up.
In überraschender Weise wird diese Aufgabe oder das bestehende
Problem dadurch gelöst, dass das Verfahren die nachstehend beschriebenen
Stufen aufweist, die zusammen mit ihren Parametern
und Stoffen fein aufeinander abgestimmt sind und maximal sechs
Anlagenvolumina Deionat verbrauchen:
Erfindungsgemäß werden die Beiz- und Reinigungschemikalien der Stufe e direkt in die Entfettungslösung der Stufen c und d hineindosiert, ohne dass die Entfettungslösung vorher aus der Anlage entfernt wurde. Dadurch entfallen zahlreiche Zwischenspülschritte; auch wird durch das Aufheizen der Netzmittel- bzw. Entfettungslösung in den Stufen c und d die Wirkung derselben erhöht.According to the invention, the pickling and cleaning chemicals of Stage e directly into the degreasing solution of stages c and d dosed in, without the degreasing solution previously from the Plant was removed. This eliminates numerous intermediate rinse steps; also, by heating the wetting agent or degreasing solution in stages c and d the effect of the same elevated.
Anders ausgedrückt, das erfindungsgemäße Verfahren erzielt das gleiche verfahrenstechnische Ergebnis wie der Stand der Technik mit geringeren Anlagenvolumina dadurch, dass nach dem ersten Vorspülen alle Behandlungen im Kreislauf durchgeführt werden, was dadurch möglich wird, dass zwischen der Netzmittellösung und der Beiz-/Reinigungslösung keine negavtiven Reaktionen auftreten, d.h. die Flusssäure mit dem Inhibitor reagiert nicht mit dem Netzmittel der Entfettung.In other words, the method according to the invention achieves this Same procedural result as the prior art with lower plant volumes in that after the first Pre-rinse all treatments to be done in the circulation, what becomes possible by that between the network agent solution and the pickling / cleaning solution no negavtiven reactions occur, i. the hydrofluoric acid reacts with the inhibitor not with the wetting agent of degreasing.
Vorteilhafterweise werden im Extremfall nur 3,5 Anlagenvolumina Deionat insgesamt verbraucht, was gegenüber den zwölf Anlagenvolumina des Standes der Technik eine erhebliche Reduzierung darstellt.Advantageously, in extreme cases, only 3.5 system volumes Deionat consumed a total of, compared to the twelve plant volumes The prior art, a significant reduction represents.
Weitere Vorteile und Merkmale der vorliegenden Erfindung gehen aus den Unteransprüchen hervor, die auch gemeinsam mit dem Hauptanspruch von erfinderischer Bedeutung sein können.Further advantages and features of the present invention are going From the dependent claims, which also together with the Main claim may be of inventive importance.
Im folgenden wird ein bevorzugtes Ausführungsbeispiel anhand der Zeichnung zum besseren Verständnis der Erfindung erläutert. Es dürfte jedoch einleuchten, dass die Erfindung nicht auf dieses Ausführungsbeispiel beschränkt ist. Es zeigt:In the following, a preferred embodiment is based the drawing explained for a better understanding of the invention. However, it should be clear that the invention is not is limited to this embodiment. It shows:
Fig. 1 eine Schemaskizze der Anlage, die mit dem erfindungsgemäßen Verfahren chemisch gereinigt wird.Fig. 1 is a schematic diagram of the system, with the inventive Procedure is chemically cleaned.
Die Schemaskizze der Fig. 1 zeigt die zu reinigende Kesselanlage,
die allgemein mit 3 bezeichnet ist. Die Kesselanlage 3
wird von einer externen Umwälzpumpe 1 aus dem damit verbundenen
Mischbehälter 2 mit der gewünschten Chemikaliendosierung 7
(Netzmittellösung ((TS LT 711)) und/oder mit Rodine 31 A inhibierte
Flusssäure) und dem Deionat 9 versorgt. Andere Produkte
für die Netzmittellösung und den Inhibitor sind im Handel erhältlich.
Der Leitungskreislauf weist einen by-pass mit Filter
4 auf, der rückspülbar ist. An den by-pass sind Rückspülanschlüsse
5 und 6 angeschlossen. Der Austritt für die zu entsorgenden
Lösungen ist mit 8 bezeichnet. Es sind zur Steuerung
des erfindungsgemäßen Verfahrens zahlreiche Ventile vorgesehen,
die bei 11 bis 19 angedeutet sind. In der Kesselanlage 3
befindet sich ein Verdampfer 20, während dazwischen ein Überhitzer
21 vorgesehen ist. Es dürfte einleuchten, dass das System
Anzeigeinstrumente für die gewünschten Parameter aufweist.
Ebenso gehören zur Deionat-Versorgung entsprechende Tanks und
eine entsprechende Wasseraufbereitungsanlage (nicht gezeigt).The schematic sketch of FIG. 1 shows the boiler system to be cleaned,
generally designated 3. The
Nachfolgend wird das Wasser- bzw. Deionat sparende erfindungsgemäße Verfahren der chemischen Reinigung des Wasser-Dampf-Kreislaufs mit Flusssäure nach dem Zirkulationsverfahren beschrieben, wobei für sämtliche Verfahrensschritte vollentsalztes Wasser eingesetzt wird.Hereinafter, the water or deionized saving inventive Method of dry cleaning the water-steam cycle described with hydrofluoric acid according to the circulation method, demineralized for all process steps Water is used.
Nachdem die zu behandelnden Anlagenkomponenten vorbereitet und alle temporären Anschlüsse und Verbindungen erstellt worden sind, müssen die Anlagenventile 11 - 19 gemäß einer Ventilstellungsliste geschlossen, bzw. geöffnet werden.After preparing the plant components to be treated and all temporary ports and connections have been created The system valves 11 - 19 must be in accordance with a valve position list closed or opened.
Während des langsamen Füllens der Anlage mit Wasser wird die Dichtigkeit des Systems kontrolliert. Sobald das System gefüllt und entlüftet ist, werden alle Leitungen, einschl. der temporären Rohrleitungen und provisorischen Verbindungen mit dem maximalen Pumpendruck (oder max. 10 bar) abgedrückt.During the slow filling of the system with water, the Tightness of the system controlled. Once the system is filled and vented, all lines, including the temporary pipelines and temporary connections with Pressed down to the maximum pump pressure (or 10 bar max.).
Evtl. auftretende Undichtigkeiten werden beseitigt. Die Dichtigkeit des Systems wird in einem Druckprobenprotokoll festgehalten.Possibly. occurring leaks are eliminated. The tightness of the system is recorded in a pressure test record.
Der erste Schritt nach dem Füllen des Systems ist das Vorspülen mit Deionat, um grobe Verunreinigungen und lose Schmutzpartikel zu entfernen. Das Spülen erfolgt im Open-Circuit-Verfahren (OC-Verfahren) mit einer Rohrleitungsgeschwindigkeit von > 0,5 m/s. The first step after filling the system is pre-wash with deionized, for coarse impurities and loose dirt particles to remove. The rinsing is done in the open-circuit method (OC method) with a pipe speed of> 0.5 m / s.
Das Vorspülen ist beendet, wenn die Trübung am Austritt 8 des
Systems den weiter unten angegebenen Grenzwert unterschreitet.The prewash is complete when the turbidity at the
Es wird angestrebt, den Grenzwert schnellstmöglich zu erreichen, um den Wasserverbrauch möglichst auf ein halbes bis maximal ein Anlagevolumen zu begrenzen.The aim is to reach the limit as soon as possible, to the water consumption as possible to a half to a maximum to limit an investment volume.
Nachdem das Vorspülen beendet ist, wird das System vom OC-Verfahren (offener Kreislauf) auf Kreislaufschaltung umgestellt.After the pre-purge is completed, the system is of the OC method (open circuit) switched to circuit switching.
Durch das Vorspülen des Systems sind lose Partikel entfernt worden. Da die Rohrleitungsoberflächen und Heizflächen durch den Transport und die Montage jedoch mit Ölen und Fetten verschmutzt sein können, muss eine Behandlung mit Netzmittel vorgesehen werden.Pre-rinsing the system removes loose particles Service. As the pipeline surfaces and heating surfaces through However, transport and assembly are contaminated with oils and greases must be treated with wetting agents become.
Durch die Netzmittelbehandlung werden hydrophobe Oberflächen in hydrophile überführt, um der auf Wasser basierenden Reinigungslösung Kontakt mit allen zu reinigenden Oberflächen zu ermöglichen.Wetting agents form hydrophobic surfaces converted into hydrophilic to the water-based cleaning solution Contact with all surfaces to be cleaned enable.
Die Entfettungslösung wird an der Umwälzpumpe 1 direkt in den
Mischbehälter 2 dosiert. Es wird ein nichtionisches, biologisch
abbaubares und für einen großen Temperaturbereich geeignetes
Netzmittel verwendet. Zudem wird erfindungsgemäß darauf
geachtet, dass sich das Netzmittel mit dem Inhibitor der eingesetzten
Reinigungslösung verträgt.The degreasing solution is at the circulation pump 1 directly into the
Mixing
Das Netzmittel wird im Kreislaufverfahren dosiert, bis die Netzmittellösung eine Konzentration von ca. 0,05 % erreicht hat. The wetting agent is metered in the circulation process until the Wetting agent solution reaches a concentration of about 0.05% Has.
Die Einwirkzeit der Netzmittellösung sollte mindestens 3 Stunden andauern. Während dieser Einwirkzeit wird die Netzmittellösung auf 50 - 80°C aufgeheizt.The exposure time of the wetting agent solution should be at least 3 hours last for. During this exposure time, the wetting agent solution becomes heated to 50 - 80 ° C.
Das Verdrängen der Netzmittellösung nach dem Stand der Technik entfällt.The displacement of the wetting solution according to the prior art eliminated.
Nachdem das Netzmittel dosiert worden ist, wird die Netzmittellösung weiter im Zirkulationskreislauf gefahren. Während der Zirkulation der Netzmittellösung können größere Partikel von den Oberflächen gelöst werden. Diese Partikel > 100 µm werden mittels eines im by-pass installierten Mikrofilters 4 aus dem System entfernt.After the wetting agent has been metered, the wetting agent solution becomes continued in the circulation circuit. While The circulation of the wetting agent solution can produce larger particles be detached from the surfaces. These particles> 100 μm be by means of a built-in by-pass microfilter. 4 removed from the system.
Der Mikrofilter 4 hat eine Kapazität von 200 m3/h, Filtergröße
100 µm.The
Das System wird im Zirkulationskreislauf aufgeheizt, m die Reaktionsgeschwindigkeit und die Effizienz der Säurelösung zu erhöhen. Mit der Zunahme der Temperatur um 10°C verdoppelt sich die Reaktionsgeschwindigkeit einer chemischen Reaktion. Es wird daher darauf geachtet, dass eine möglichst hohe Temperatur erreicht wird.The system is heated in the circulation circuit, m the reaction rate and the efficiency of the acid solution too increase. Doubled with the increase in temperature by 10 ° C the reaction rate of a chemical reaction. It is therefore ensured that the highest possible temperature is reached.
Über einen im by-pass installierten Wärmeaustauscher (nicht gezeigt) wird das System auf 50 - 80°C erhitzt. Als Wärmequelle dient entweder vom Betreiber bereitgestellter Hilfsdampf oder ein eigener ölgefeuerter Warmwasserkessel.About a by-pass installed heat exchanger (not shown), the system is heated to 50-80 ° C. As a heat source Serves either by the operator provided auxiliary steam or a separate oil-fired hot water boiler.
Der Wärmeaustauscher ist so ausgelegt, dass eine Temperatur von ca. 50 - 80°C innerhalb von 6 - 10 Stunden erreicht werden kann.The heat exchanger is designed so that a temperature be reached from about 50 - 80 ° C within 6 - 10 hours can.
Es ist zu beachten, dass alle Öffnungen der Kesselanlage 1, einschließlich der Rauchgasklappe (nicht gezeigt), geschlossen sind. Werden diese Öffnungen nicht vollständig geschlossen, entsteht durch die Anwärmung der Kessel- und Rohrleitungsflächen eine Kaminwirkung, die einen Durchzug entstehen lässt. Dieser Durchzug würde die erwärmten Rohrleitungen schnell wieder auskühlen, so dass die spezifizierte Temperatur mit einem Hilfskessel nicht erreicht werden kann.It should be noted that all the openings of the boiler system 1, including the flue gas flap (not shown), closed are. If these openings are not completely closed, is created by the heating of the boiler and piping surfaces a fireplace effect that creates a draft. This draft would quickly return the heated piping cool down so that the specified temperature with a Auxiliary boiler can not be reached.
Während das Hauptsystem erhitzt wird, werden nacheinander auch die Nebensysteme durchströmt, um diese ebenfalls zu erhitzen.While the main system is being heated, so will one after another flows through the auxiliary systems in order to heat them as well.
Die Beheizung der Systeme ist zu beenden, sobald eine Temperatur
von 50 - 80°C am Rücklauf 10 festgestellt wird. Der Zirkulationskreislauf
wird weiterhin aufrecht erhalten.The heating of the systems must be stopped as soon as a temperature
from 50 - 80 ° C at the
Die Reinigungslösung besteht mit Rodine aus inhibierter 1%iger Flusssäure. Die Flusssäure und der Inhibitor Rodine werden über den Mischbehälter der Umwälzpumpe 1 im Zirkulationsverfahren direkt in die Netzmittellösung hineindosiert, wobei darauf zu achten ist, dass das Netzmittel und die inhibierte Flusssäure sich nicht gegenseitig negativ beeinflussen.The cleaning solution consists of Rodine inhibited 1% Hydrofluoric acid. The hydrofluoric acid and the inhibitor Rodine are over the mixing container of the circulation pump 1 in the circulation process dosed directly into the wetting agent solution, with it It should be noted that the wetting agent and the inhibited hydrofluoric acid do not affect each other negatively.
Die Strömungsgeschwindigkeit der Reinigungslösung in den zu behandelnden Rohrleitungen beträgt in der Regel 0,2 m/s.The flow rate of the cleaning solution in the too treated piping is usually 0.2 m / s.
Während der Kreislauf weiterhin aufrecht erhalten wird, und die einzelnen Teilsysteme durchströmt werden, werden sowohl die Eisenkonzentration als auch die Konzentration der Flusssäure in regelmäßigen Abständen und herkömmlicher Weise bestimmt . While the circulation continues to be sustained, and the individual subsystems are traversed, both the iron concentration as well as the concentration of hydrofluoric acid determined at regular intervals and conventionally ,
Die Konzentration an gelöstem Eisen darf die maximale Eisenkonzentration nicht überschreiten. Die Überwachungswerte sind weiter unten angegeben.The concentration of dissolved iron must be the maximum iron concentration do not exceed. The monitoring values are given below.
Die Reinigung ist beendet, wenn die Eisenkonzentration bei
freier Säure konstant ist. Mit dem Erreichen der konstanten
Werte wird der Zirkulationskreislauf gestoppt. Alle Ventile
(Zulauf 20 und Rücklauf 11) werden geschlossen. Ja nach Anlagentyp
kann die Säure jetzt bis zu 12 h im System verbleiben
(Standphase), um die Reinigungsleistung zu erhöhen.The cleaning is finished when the iron concentration at
free acid is constant. With the achievement of constant
Values, the circulation circulation is stopped. All valves
(
Die Säure wird im Durchstoßverfahren mit Deionat aus dem System verdrängt. Nach dem Entlüften des Systems müssen alle Abschnitte und Teilabschnitte auf Leitfähigkeit geprüft werden. Dieses wird im Hochgeschwindigkeitsverfahren mit Hilfs-Pumpen durchgeführt.The acid is purged with deionized from the system repressed. After bleeding the system, all sections must and sections are checked for conductivity. This is using high-speed process with auxiliary pumps carried out.
Die Überwachungswerte sind weiter unten angegeben. Sobald die Werte an den Entwässerungen / Entleerungen des Systems feststellbar sind, ist da Hochgeschwindigkeitsspülen beendet.The monitoring values are given below. As soon as the Values at the drains / drains of the system detectable are there, high-speed rinsing is over.
Für das Verdrängen der Säure und das anschließende Hochgeschwindigkeitsspülen werden etwa min. drei bis max. vier Anlagenvolumina Deionat benötigt.For displacing the acid and then high speed rinsing be about min. three to max. four plant volumes Deionat needed.
Das gesamte System ist nach dem Spülen auf Leitfähigkeit mit Deionat gefüllt. Der Zirkulationskreislauf wird wieder aufgenommen.The entire system is after flushing with conductivity Deionat filled. The circulation circuit is resumed.
Um die gebeizte Metalloberfläche zu neutralisieren, wird Ammoniakwasser in das System dosiert. Durch das Ammoniak wird der pH-Wert auf > 10,2 angehoben. Zeitgleich wird Wasserstoffperoxyd in den Kreislauf dosiert. Dieses Oxidationsmittel bewirkt die Ausbildung einer Passivschicht auf der gebeizten, neutralisierten Metalloberfläche. Die Passivierung ist abgeschlossen, wenn ein positives Redox-Potential gemessen wird. Die Überwachungswerte sind weiter unten aufgeführt.To neutralize the stained metal surface, ammonia water becomes metered into the system. By the ammonia is the pH raised to> 10.2. At the same time, hydrogen peroxide becomes dosed into the circulation. This oxidizing agent causes the formation of a passive layer on the stained, neutralized Metal surface. Passivation is completed when a positive redox potential is measured. The monitoring values are listed below.
Nach der Alkalisierung und Passivierung müssen alle anlageneigenen am System angeschlossenen Mess- und Dosierleitungen gespült werden.After alkalization and passivation, all plant-owned Rinsed the measuring and metering lines connected to the system become.
Wenn möglich, wird die Passivierungslösung aus dem System und den Teilabschnitten statisch, durch geodätische Höhe, entleert. Gegebenenfalls werden die Hilfs-Pumpen zur Entleerung des Systems eingesetzt.If possible, the passivation solution is removed from the system and the sections statically, by geodetic height, emptied. If necessary, the auxiliary pumps for emptying used by the system.
In der nachfolgenden Tabelle werden die erfindungsgemäßen
Überwachungswerte während des Reinigungsverfahrens angegeben:
alle 30 Minuten
Redox-Potential >+10 mV (positiv) (Handmessgerät m. pH-/Redox-elektrode)
every 30 minutes
Redox potential> +10 mV (positive) (handheld instrument with pH / redox electrode)
Bei den erf. Verfahren der Reinigung des Wasser-Dampf-Kreislaufs fällt Abwasser an. Dieses Abwasser wird aufgefangen und nach einer Behandlung bei Bedarf wieder in den Wasserkreislauf des Kraftwerks zurückgegeben. Der ausgefällte Dünnschlamm wird mit einer Kammerfilterpresse entwässert und deponiert.In the erf. Method of cleaning the water-steam cycle wastewater accumulates. This wastewater is collected and after treatment, if needed, back into the water cycle returned to the power plant. The precipitated thin sludge is drained with a chamber filter press and dumped.
Das gesamte Vorspülwassser, die Beizlösung und das Spülwasser werden in einem Abwasserbecken gesammelt. Durch das Wasser sparende Konzept wird nun das ca. 3,5 - 6-fache Anlagevolumina an Deinonat verwendet. Damit das gesamte Abwasser aufgefangen werden kann, ist das Abwasserbecken entsprechend auszulegen. Das Abwasserbecken dient als Zwischenlagerung.All pre-rinse water, pickling solution and rinse water are collected in a wastewater basin. Through the water saving concept is now about 3.5 - 6 times the investment volume used on deionate. So that the entire wastewater collected the wastewater tank is to be designed accordingly. The wastewater basin serves as intermediate storage.
Die Flüsssäurekonzentration im Abwasser liegt in dem Bereich zwischen 0,01 % bis 0,2 %. Zusätzlich befinden sich im Abwasser der eingesetzte Inhibitor und gelöste Eisenionen (Fe++).The liquid acid concentration in the waste water is in the range between 0.01% to 0.2%. In addition, the wastewater contains the inhibitor used and dissolved iron ions (Fe ++ ).
Die Beizlösung wird während des Verdrängens online mit Kalkhydrat vorneutralisiert. Im Anschluss an die Beizung wird das Abwasser im Abwasserbecken entsprechend durch weitre Zugabe von Kalkhydrat neutralisiert.The pickling solution becomes online during the suppression with hydrated lime pre-neutralized. Following the pickling, the Waste water in the wastewater tank according to weitre addition neutralized by hydrated lime.
Um den Neutralisationsvorgang und die Oxidation der Fe++-Ionen zu beschleunigen, wird Pressluft aus kleinen Schlauchöffnungen in das Abwasser eingedüst.In order to accelerate the neutralization process and the oxidation of the Fe ++ ions, compressed air from small tube openings is injected into the wastewater.
Die organischen Bestandteile des Abwassers werden durch Adsorption an Aktivkohle abgetrennt, indem pulverförmige Aktivkohle dem Abwasser zugegeben wird.The organic components of the wastewater are adsorbed separated on activated charcoal by adding powdered activated carbon is added to the wastewater.
Die Flusssäure reagiert mit dem Kalkhydrat zu Flussspat (CaF2) und Wasser. Der wasserunlösliche Flussspat, das ausgefällte Eisenhydroxid Fe(OH)3 und die Aktivkohle setzen sich ab. The hydrofluoric acid reacts with the hydrated lime to form fluorspar (CaF 2 ) and water. The water-insoluble fluorspar, the precipitated iron hydroxide Fe (OH) 3 and the activated carbon settle out.
Nachdem sich die Klarphase vom Schlamm getrennt hat, wird der geklärte und pH-neutrale Überstand abgepumpt.After the clear phase has separated from the mud, the clarified and pumped neutral pH supernatant.
Das Abwasser aus der Alkalisierung und Passivierung enthält Ammoniak und Wasserstoffperoxid. Dieses Abwasser wird in einem zusätzlichen Abwassertank aufgefangen, da es nicht mit dem fluoridhaltigen Abwasser aus der Beizung gemischt werden kann.The waste water from the alkalization and passivation contains Ammonia and hydrogen peroxide. This wastewater is in one additional wastewater tank, since it does not match the Fluid wastewater from the dressing can be mixed.
Die Abwasserabgabe erfolgt über eine Wasseraufbereitungsanlage im Kationen/Anionenaustausch mit vorgeschaltetem AktivkohleFilter. Dadurch wird erreicht, dass sowohl die gelösten Ionen zurückgehalten, als auch der CSB-Gehalt des Wassers reduziert wird.The wastewater is discharged via a water treatment plant in cation / anion exchange with upstream activated carbon filter. This ensures that both the dissolved ions retained, as well as the COD content of the water reduced becomes.
Folgende Grenzwerte werden eingehalten:
Das Abwasser hat eine Temperatur von max. 35°C.The wastewater has a temperature of max. 35 ° C.
Das so aufbereitete Abwasser kann problemlos über das Service-oder Rohwasser in den Wasserkreislauf der Anlage zurückgegeben werden.The treated wastewater can be handled easily via the service or Raw water returned to the water cycle of the plant become.
Die ausgefällten Kalziumfluoridsalze und das Eisenoxid bildet zusammen mit der Aktivkohle ein Dünnschlammgemisch. Dieser Dünnschlamm enthält auch die aus der Anlage heraus gespülten Feststoffe.The precipitated calcium fluoride salts and the iron oxide forms together with the activated carbon a thin sludge mixture. This Thin sludge also contains the purged out of the plant Solids.
Der Dünnschlamm wird über eine Kammerfilterpresse abgepresst. The thin sludge is pressed off via a chamber filter press.
Der entstandene Filterkuchen (Wassergehalt 45 - 55%) wird in abgedeckten Containern bis zur Entsorgung auf einer geeigneten Deponie zwischengelagert. Ein zugelassenes lokales Entsorgungsunternehmen wird mit der fachgerechten Entsorgung beauftrag. Gegebenenfalls wird der Filterkuchen laborchemisch untersucht.The resulting filter cake (water content 45-55%) is in Covered containers until disposal on a suitable Landfill temporarily stored. An approved local waste disposal company is assigned with the professional disposal. If necessary, the filter cake is examined by laboratory chemistry.
Das Permeat wird in die Kanalisation abgegeben. Während der Abgabe werden die Abwasserwerte überwacht.The permeate is discharged into the sewer. During the Delivery, the wastewater values are monitored.
Folgende Grenzwerte zum Abpumpen in die öffentliche Kanalisation
oder in die vorhandene Aufbereitungsanlage werden eingehalten:
Das erfindungsgemäße Verfahren gewährleistet, dass die behandelten Oberflächen frei von Rost, Zunder und nachgebildetem Magnetit sind.The inventive method ensures that the treated Surfaces free of rust, scale and imitation Magnetite are.
Der während der Behandlung maximale Gesamtabtrag an Eisen wird 20 g/m2 nicht übersteigen, gilt auch für Chromstähle.The maximum total removal of iron during treatment will not exceed 20 g / m 2 , which also applies to chromium steels.
Maximaler Leitfähigkeitszuwachs nach einem Kationenfilter, gemessen
in der Frischdampfleitung nach 10 h durchgehenden Vollastbetrieb
= 0,3 µS/cm. Maximaler Eisenanstieg, gemessen in
der Frischdampfleitungen nach 10 h durchgehenden Vollastbetrieb
= 20 µS/l, nach 50 h durchgehenden Schwachlastbetrieb =
20 µS/l.Maximum increase in conductivity after a cation filter, measured
in the main steam line after 10 h continuous full load operation
= 0.3 μS / cm. Maximum iron increase, measured in
the main steam lines after 10 h continuous full load operation
= 20 μS / l, after 50 h continuous
Claims (6)
Priority Applications (4)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
EP04011890A EP1598629B1 (en) | 2004-05-19 | 2004-05-19 | Method of chemical cleaning of a gas and vapor installation |
AT04011890T ATE313056T1 (en) | 2004-05-19 | 2004-05-19 | METHOD FOR CHEMICAL CLEANING A GAS AND STEAM SYSTEM |
ES04011890T ES2255694T3 (en) | 2004-05-19 | 2004-05-19 | CHEMICAL CLEANING PROCEDURE OF A GAS AND STEAM INSTALLATION. |
DE502004000183T DE502004000183D1 (en) | 2004-05-19 | 2004-05-19 | Process for the chemical cleaning of a gas and steam plant |
Applications Claiming Priority (1)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
EP04011890A EP1598629B1 (en) | 2004-05-19 | 2004-05-19 | Method of chemical cleaning of a gas and vapor installation |
Publications (2)
Publication Number | Publication Date |
---|---|
EP1598629A1 true EP1598629A1 (en) | 2005-11-23 |
EP1598629B1 EP1598629B1 (en) | 2005-12-14 |
Family
ID=34925064
Family Applications (1)
Application Number | Title | Priority Date | Filing Date |
---|---|---|---|
EP04011890A Expired - Lifetime EP1598629B1 (en) | 2004-05-19 | 2004-05-19 | Method of chemical cleaning of a gas and vapor installation |
Country Status (4)
Country | Link |
---|---|
EP (1) | EP1598629B1 (en) |
AT (1) | ATE313056T1 (en) |
DE (1) | DE502004000183D1 (en) |
ES (1) | ES2255694T3 (en) |
Cited By (5)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
CN102269400A (en) * | 2011-07-26 | 2011-12-07 | 西安热工研究院有限公司 | Feeding device for hydrogen peroxide in chemical cleaning of power plant boiler |
CN102944137A (en) * | 2012-11-09 | 2013-02-27 | 青海电力科学试验研究院 | Pipeline device for chemically cleaning boiler |
CN103063082A (en) * | 2012-12-31 | 2013-04-24 | 江苏肯创环境科技股份有限公司 | Cleaning and anti-scaling process without shut-down of gas-gas heater (GGH) and device thereof |
CN103090700A (en) * | 2013-03-04 | 2013-05-08 | 杨铭 | Baffle high-efficient heat exchanger |
CN114951159A (en) * | 2022-06-02 | 2022-08-30 | 中天钢铁集团(南通)有限公司 | Thermal-state cleaning method for metallurgical oxygen production pipeline |
Families Citing this family (1)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
CN102537930B (en) * | 2010-12-17 | 2015-04-01 | 冯伟忠 | Cleaning method for concurrent boiler |
Citations (3)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
GB1198693A (en) * | 1966-08-02 | 1970-07-15 | Beratherm A G | Process for the Chemical Cleansing of Water and Steam Contacted Metal Surfaces. |
US4720306A (en) * | 1985-04-16 | 1988-01-19 | Kraftwerk Union Aktiengesellschaft | Cleaning method |
DE19843442C1 (en) * | 1998-09-22 | 2000-03-02 | Siemens Ag | Steam boiler unit components cleaning arrangement e.g. for power station equipment |
-
2004
- 2004-05-19 ES ES04011890T patent/ES2255694T3/en not_active Expired - Lifetime
- 2004-05-19 AT AT04011890T patent/ATE313056T1/en active
- 2004-05-19 EP EP04011890A patent/EP1598629B1/en not_active Expired - Lifetime
- 2004-05-19 DE DE502004000183T patent/DE502004000183D1/en not_active Expired - Lifetime
Patent Citations (3)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
GB1198693A (en) * | 1966-08-02 | 1970-07-15 | Beratherm A G | Process for the Chemical Cleansing of Water and Steam Contacted Metal Surfaces. |
US4720306A (en) * | 1985-04-16 | 1988-01-19 | Kraftwerk Union Aktiengesellschaft | Cleaning method |
DE19843442C1 (en) * | 1998-09-22 | 2000-03-02 | Siemens Ag | Steam boiler unit components cleaning arrangement e.g. for power station equipment |
Cited By (7)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
CN102269400A (en) * | 2011-07-26 | 2011-12-07 | 西安热工研究院有限公司 | Feeding device for hydrogen peroxide in chemical cleaning of power plant boiler |
CN102944137A (en) * | 2012-11-09 | 2013-02-27 | 青海电力科学试验研究院 | Pipeline device for chemically cleaning boiler |
CN103063082A (en) * | 2012-12-31 | 2013-04-24 | 江苏肯创环境科技股份有限公司 | Cleaning and anti-scaling process without shut-down of gas-gas heater (GGH) and device thereof |
CN103063082B (en) * | 2012-12-31 | 2014-07-16 | 江苏肯创环境科技股份有限公司 | Cleaning and anti-scaling process without shut-down of gas-gas heater (GGH) and device thereof |
CN103090700A (en) * | 2013-03-04 | 2013-05-08 | 杨铭 | Baffle high-efficient heat exchanger |
CN103090700B (en) * | 2013-03-04 | 2015-04-01 | 杨铭 | Baffle high-efficient heat exchanger |
CN114951159A (en) * | 2022-06-02 | 2022-08-30 | 中天钢铁集团(南通)有限公司 | Thermal-state cleaning method for metallurgical oxygen production pipeline |
Also Published As
Publication number | Publication date |
---|---|
DE502004000183D1 (en) | 2006-02-02 |
ATE313056T1 (en) | 2005-12-15 |
EP1598629B1 (en) | 2005-12-14 |
ES2255694T3 (en) | 2006-07-01 |
Similar Documents
Publication | Publication Date | Title |
---|---|---|
DE102006010460B4 (en) | Method for cleaning a cooking appliance | |
CN105753105B (en) | A kind of the reason during electric power plant circulating water blowdown Water circulation, counter-infiltration system is dirty stifled analysis determination method and its chemical cleaning method | |
CN101455945A (en) | Reverse osmosis membrane on-line chemical cleaning method and cleaning agent | |
DE3022924A1 (en) | METHOD FOR REMOVING BOILER | |
EP1598629B1 (en) | Method of chemical cleaning of a gas and vapor installation | |
DE102015114481A1 (en) | AQUEOUS-NEUTRAL DEROUGING, DEFROSTING, PASSIVATION AND DECONTAMINATION SOLUTIONS AND METHOD FOR THEIR USE | |
EP2885578B1 (en) | Method for recovering process wastewater from a steam power plant | |
AT411359B (en) | CLEANING PROCEDURE AND CLEANING LIQUID FOR FAN BODY | |
AT413032B (en) | CLEANING, DISINFECTION AND INDICATORS | |
CN110577859A (en) | Cleaning agent for DTRO (draw texturing yarn) membrane and preparation and use methods thereof | |
DE69000266T2 (en) | METHOD AND DEVICE FOR IMPROVING THE LANGELIER INDEX OF URBAN WATER. | |
EP2426322A1 (en) | Fluid circuit for a power plant and method for chemical cleaning of same | |
DE10142933A1 (en) | Membrane filtration of zinc phosphation bath overflow or washing water, e.g. in car, domestic appliance or steel industry, involves adding reagent inhibiting membrane blocking and/or cleaning membrane with acid | |
DE10306722A1 (en) | Reverse osmosis process and assembly to render a spent dilute etching agent from a boiler pipe system fit for disposal | |
RU2304317C1 (en) | Method for controlling decontamination of pressure-tube power reactor coolant circuit | |
DE102017005695A1 (en) | Method and device for detecting biofilms in production plants for food and / or beverage production | |
Mohan et al. | Restoring submerged UF membrane performance using an innovative patent-pending chemical cleaning procedure | |
DD131132B1 (en) | PROCESS FOR CLEANING AND / OR DISINFECTION OF PLANTS | |
DE102006014601B4 (en) | Method, device, container and means for the treatment of acid condensed water from combustion plants | |
DE19743933A1 (en) | Method for surface treatment of components, in particular, automobile body structures | |
DE4312701A1 (en) | Process and plant for regenerating ion exchangers | |
DE2203008B1 (en) | METHOD AND DEVICE FOR PROCESSING WASTE WATER | |
CH291826A (en) | Process to prevent corrosion in warm and hot water heating systems. | |
DE2117511A1 (en) | Method of operating an automatic cleaning machine for reusable food containers | |
EP3715335A1 (en) | Surface treatment system, preconditioning device and method for preparing process medium and/or flushing medium |
Legal Events
Date | Code | Title | Description |
---|---|---|---|
GRAP | Despatch of communication of intention to grant a patent |
Free format text: ORIGINAL CODE: EPIDOSNIGR1 |
|
GRAS | Grant fee paid |
Free format text: ORIGINAL CODE: EPIDOSNIGR3 |
|
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 |
|
GRAA | (expected) grant |
Free format text: ORIGINAL CODE: 0009210 |
|
17P | Request for examination filed |
Effective date: 20050307 |
|
AK | Designated contracting states |
Kind code of ref document: A1 Designated state(s): AT BE BG CH CY CZ DE DK EE ES FI FR GB GR HU IE IT LI LU MC NL PL PT RO SE SI SK TR |
|
AX | Request for extension of the european patent |
Extension state: AL HR LT LV MK |
|
AK | Designated contracting states |
Kind code of ref document: B1 Designated state(s): AT BE BG CH CY CZ DE DK EE ES FI FR GB GR HU IE IT LI LU MC NL PL PT RO SE SI SK TR |
|
AX | Request for extension of the european patent |
Extension state: AL HR LT LV MK |
|
PG25 | Lapsed in a contracting state [announced via postgrant information from national office to epo] |
Ref country code: SK Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT Effective date: 20051214 Ref country code: SI Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT Effective date: 20051214 Ref country code: NL Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT Effective date: 20051214 Ref country code: FI Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT Effective date: 20051214 Ref country code: CZ Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT Effective date: 20051214 Ref country code: PL Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT Effective date: 20051214 |
|
REG | Reference to a national code |
Ref country code: GB Ref legal event code: FG4D Free format text: NOT ENGLISH |
|
REG | Reference to a national code |
Ref country code: CH Ref legal event code: EP |
|
REG | Reference to a national code |
Ref country code: IE Ref legal event code: FG4D Free format text: LANGUAGE OF EP DOCUMENT: GERMAN |
|
GBT | Gb: translation of ep patent filed (gb section 77(6)(a)/1977) |
Effective date: 20060110 |
|
REF | Corresponds to: |
Ref document number: 502004000183 Country of ref document: DE Date of ref document: 20060202 Kind code of ref document: P |
|
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 FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT Effective date: 20060314 Ref country code: DK Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT Effective date: 20060314 Ref country code: BG Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT Effective date: 20060314 |
|
REG | Reference to a national code |
Ref country code: GR Ref legal event code: EP Ref document number: 20060400539 Country of ref document: GR |
|
PG25 | Lapsed in a contracting state [announced via postgrant information from national office to epo] |
Ref country code: MC Free format text: LAPSE BECAUSE OF NON-PAYMENT OF DUE FEES Effective date: 20060531 |
|
NLV1 | Nl: lapsed or annulled due to failure to fulfill the requirements of art. 29p and 29m of the patents act | ||
PG25 | Lapsed in a contracting state [announced via postgrant information from national office to epo] |
Ref country code: HU Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT Effective date: 20060615 |
|
REG | Reference to a national code |
Ref country code: ES Ref legal event code: FG2A Ref document number: 2255694 Country of ref document: ES Kind code of ref document: T3 |
|
AKX | Designation fees paid |
Designated state(s): AT BE BG CH CY CZ DE DK EE ES FI FR GB GR HU IE IT LI LU MC NL PL PT RO SE SI SK TR |
|
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 |
Effective date: 20060915 |
|
PG25 | Lapsed in a contracting state [announced via postgrant information from national office to epo] |
Ref country code: EE Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT Effective date: 20051214 |
|
PG25 | Lapsed in a contracting state [announced via postgrant information from national office to epo] |
Ref country code: LU Free format text: LAPSE BECAUSE OF NON-PAYMENT OF DUE FEES Effective date: 20060519 |
|
PG25 | Lapsed in a contracting state [announced via postgrant information from national office to epo] |
Ref country code: RO Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT Effective date: 20051214 |
|
PGFP | Annual fee paid to national office [announced via postgrant information from national office to epo] |
Ref country code: TR Payment date: 20080507 Year of fee payment: 5 |
|
PG25 | Lapsed in a contracting state [announced via postgrant information from national office to epo] |
Ref country code: CY Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT Effective date: 20051214 |
|
REG | Reference to a national code |
Ref country code: CH Ref legal event code: PL |
|
PG25 | Lapsed in a contracting state [announced via postgrant information from national office to epo] |
Ref country code: LI Free format text: LAPSE BECAUSE OF NON-PAYMENT OF DUE FEES Effective date: 20080531 Ref country code: CH Free format text: LAPSE BECAUSE OF NON-PAYMENT OF DUE FEES Effective date: 20080531 |
|
PG25 | Lapsed in a contracting state [announced via postgrant information from national office to epo] |
Ref country code: TR Free format text: LAPSE BECAUSE OF NON-PAYMENT OF DUE FEES Effective date: 20090519 |
|
PGFP | Annual fee paid to national office [announced via postgrant information from national office to epo] |
Ref country code: IE Payment date: 20140529 Year of fee payment: 11 Ref country code: GB Payment date: 20140528 Year of fee payment: 11 |
|
PGFP | Annual fee paid to national office [announced via postgrant information from national office to epo] |
Ref country code: AT Payment date: 20140530 Year of fee payment: 11 Ref country code: PT Payment date: 20140616 Year of fee payment: 11 Ref country code: IT Payment date: 20140528 Year of fee payment: 11 Ref country code: ES Payment date: 20140528 Year of fee payment: 11 Ref country code: GR Payment date: 20140529 Year of fee payment: 11 Ref country code: DE Payment date: 20140618 Year of fee payment: 11 |
|
PGFP | Annual fee paid to national office [announced via postgrant information from national office to epo] |
Ref country code: BE Payment date: 20140528 Year of fee payment: 11 |
|
PGFP | Annual fee paid to national office [announced via postgrant information from national office to epo] |
Ref country code: FR Payment date: 20140528 Year of fee payment: 11 |
|
REG | Reference to a national code |
Ref country code: PT Ref legal event code: MM4A Free format text: LAPSE DUE TO NON-PAYMENT OF FEES Effective date: 20151119 |
|
REG | Reference to a national code |
Ref country code: DE Ref legal event code: R119 Ref document number: 502004000183 Country of ref document: DE |
|
REG | Reference to a national code |
Ref country code: AT Ref legal event code: MM01 Ref document number: 313056 Country of ref document: AT Kind code of ref document: T Effective date: 20150519 |
|
GBPC | Gb: european patent ceased through non-payment of renewal fee |
Effective date: 20150519 |
|
PG25 | Lapsed in a contracting state [announced via postgrant information from national office to epo] |
Ref country code: GR Free format text: LAPSE BECAUSE OF NON-PAYMENT OF DUE FEES Effective date: 20151208 Ref country code: IT Free format text: LAPSE BECAUSE OF NON-PAYMENT OF DUE FEES Effective date: 20150519 |
|
REG | Reference to a national code |
Ref country code: IE Ref legal event code: MM4A |
|
REG | Reference to a national code |
Ref country code: FR Ref legal event code: ST Effective date: 20160129 |
|
PG25 | Lapsed in a contracting state [announced via postgrant information from national office to epo] |
Ref country code: PT Free format text: LAPSE BECAUSE OF NON-PAYMENT OF DUE FEES Effective date: 20151119 Ref country code: AT Free format text: LAPSE BECAUSE OF NON-PAYMENT OF DUE FEES Effective date: 20150519 |
|
REG | Reference to a national code |
Ref country code: GR Ref legal event code: ML Ref document number: 20060400539 Country of ref document: GR Effective date: 20151208 |
|
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: 20151201 Ref country code: GB Free format text: LAPSE BECAUSE OF NON-PAYMENT OF DUE FEES Effective date: 20150519 Ref country code: IE Free format text: LAPSE BECAUSE OF NON-PAYMENT OF DUE FEES Effective date: 20150519 |
|
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: 20150601 |
|
REG | Reference to a national code |
Ref country code: ES Ref legal event code: FD2A Effective date: 20160829 |
|
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: 20150520 |
|
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: 20150531 |