EP3051247B1 - Verfahren zur chemischen reinigung eines wärmetauschers - Google Patents

Verfahren zur chemischen reinigung eines wärmetauschers Download PDF

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Publication number
EP3051247B1
EP3051247B1 EP13802435.1A EP13802435A EP3051247B1 EP 3051247 B1 EP3051247 B1 EP 3051247B1 EP 13802435 A EP13802435 A EP 13802435A EP 3051247 B1 EP3051247 B1 EP 3051247B1
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EP
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Prior art keywords
heat exchangers
chemical cleaning
cleaning procedure
phase
procedure
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English (en)
French (fr)
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EP3051247A1 (de
Inventor
Marcelo Soto Tomas
José Tomás RUIZ MARTINEZ
Gaëtan BIGOIN
Bernard Joseph ROTTNER
Martine BURNEL ét ROTTNER
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Onet Technologies CN SAS
GD Energy Services SARL
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Comex Nucleaire SAS
GD Energy Services SARL
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Classifications

    • 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
    • F—MECHANICAL ENGINEERING; LIGHTING; HEATING; WEAPONS; BLASTING
    • F22—STEAM GENERATION
    • F22B—METHODS OF STEAM GENERATION; STEAM BOILERS
    • F22B1/00—Methods of steam generation characterised by form of heating method
    • F22B1/02—Methods of steam generation characterised by form of heating method by exploitation of the heat content of hot heat carriers
    • F22B1/023—Methods of steam generation characterised by form of heating method by exploitation of the heat content of hot heat carriers with heating tubes, for nuclear reactors as far as they are not classified, according to a specified heating fluid, in another group
    • 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
    • F22B37/483—Devices for removing water, salt, or sludge from boilers; Arrangements of cleaning apparatus in boilers; Combinations thereof with boilers specially adapted for nuclear steam generators

Definitions

  • This invention concerns a chemical cleaning procedure for heat exchangers performed in different phases, including in particular an acid phase for dissolving metal oxide deposits, and a later decoppering stage.
  • the phases involved in the standard procedure are as follows:
  • the proposal is to perform a procedure for partially dissolving any metal oxide deposits (acid phase) followed by a decoppering stage, with a recirculation loop.
  • the steam generator consists of a heat exchanger, as well as its housing vessel and auxiliary items, in which water is made to circulate at high pressure and temperature from the reactor, or from another heat source, through a set of tubes, transferring said heat to the water in the secondary circuit.
  • US 5,154,197 discloses a chemical cleaning procedure according to the preamble of claim 1.
  • US 4632705 describes a process for eliminating deposits accumulated in the restricted areas of the steam generator of a nuclear power station, in which the concentration of a water-based organic cleaning agent is increased in restricted zones, in respect of the concentration existing in the other zones. The solution is heated with an initial pressure to prevent the solution from boiling and the pressure is then reduced to perform intermittent boiling. After some time has elapsed the cleaning agent is increased and removed with the dissolved deposits, and a phase for eliminating the copper at subatmospheric pressure is started, with the addition of an oxidising agent, in particular hydrogen peroxide.
  • an oxidising agent in particular hydrogen peroxide.
  • the operating temperatures vary depending on whether one is attempting to eliminate ferrous or copper residues, from about 120°C-130°C to 30°C-40°C.
  • the usage of citric acid as one of the reagents is described.
  • Nitrogen is used as an element for counter pressure in the steam generating chamber.
  • US 2010/0313913 A1 describes a physical-chemical method for cleaning the chamber of the secondary circuit of a heat exchanger in a nuclear installation, which includes drying the secondary circuit and inserting a cleaning solution into the chamber for treating the deposits.
  • EP 0 458 533 A1 describes a procedure for eliminating sludge and products of corrosion from a heat exchanging chamber, in which a chemical cleaning agent is introduced, and maintained for a period from 13 to 70 hours, the agent being based on iron containing chelate at a temperature of from -12oC to 10oC, with generation of pressure pulses.
  • US 5 764 717 discloses a procedure for eliminating scale, sludges, residues and other deposits from the inside of the vessel of a heat exchanger, such as a steam generator of a nuclear power station. It includes generating pressure pulses in a highly basic agent containing amines in a water solution. The solution is made to recirculate through a filter.
  • the invention being proposed describes a procedure for preventive chemical cleaning which eliminates the deposits found in:
  • from 200 Kg of deposits can be eliminated from the steam generator of a standard 900 MW power station in a conventional reloading operation.
  • the maximum admissible values for free corrosion and galvanic corrosion are from 1 ⁇ m for stainless materials and nickel-based alloys to 100 ⁇ m in low-alloy materials, carbon steels or welded joints. The intention is thus to ensure that metal oxide deposits are dissolved with a minimum corrosive effect on the base material of the installation, as is achieved with the procedure described herein.
  • One objective is for the amount of gaseous effluents to be as low as possible. The lowest possible amount of ammonia must specifically be obtained.
  • the effluents produced also meet the conditions required to be acceptable for installations for processing and conditioning nuclear waste. These installations can be at the plant itself or external.
  • the procedure for the invention is thus one of chemical cleaning of heat exchangers which mainly comprises the following phases:
  • the operations are carried out dynamically, with an initial filling and the injection of solvents in different stages over time, or by preparing the mixture and filling the exchanger chamber with this.
  • the previous table shows how the magnetite is dissolved by means of citric acid.
  • Ammonia can be added to obtain this pH. In an acid medium, the ammonia will start to form part of ammonium (NH 4 + ) ions which will be associated with the citrate ions to form an ammonium citrate compound.
  • the dissolution (equation 2) is very similar to the previous one.
  • the ascorbic acid is a reducing agent. It reduces the Fe 3+ ions to Fe 2+ .
  • the consumption of Fe 3+ ions displaces the equilibrium of equation 2 to the right, improving the efficiency and yield of the process.
  • Equation 5 can also be written as follows: 2 NH 4 FeO III O H ⁇ A + C 6 H 8 O 6 ⁇ C 6 H 6 O 6 + 2 NH 4 Fe II ⁇ A + 2 H 2 O
  • the ascorbic acid is also able to dissolve magnetite (Equation 7).
  • the citric acid has an important function as an agglutinant of the transition metal ions.
  • the formation of compounds of Cu(II) citrate can be represented by the general equilibrium: p Cu 2 + + q A 3 ⁇ + r H + ⁇ Cu p A q H r 2 p ⁇ 3 q ⁇ r +
  • the predominant phases between pH 3 and 4 are as follows: CuAH, Cu 2 A 2 2- Cu 2 A 2 H -1 3 .
  • the citric acid can also be used for dissolving copper oxide (equation).
  • H + ions are generated from the combination as in the following reaction. 2 H + + Fe ⁇ Fe 2 + + H 2
  • Fe III Fe 3+
  • Fe 3+ ions are produced through the dissolution of magnetite, and have the ability to oxidise iron (Equation 11: Corrosion reaction) and copper.
  • 2 Fe 3 + + Fe ⁇ 3 Fe 2 + K 2.
  • 10 40 2 Fe 3 + + Cu ⁇ Cu 2 + + 3 Fe 2 + K 2. 10 14
  • the Cu 2+ turned into a solution could later be redeposited on the steels, possibly generating losses through corrosion.
  • Coppering is when metal copper is deposited on a metal surface. The dissolved Cu 2+ ions are released through the deposits being dissolved.
  • Cu 3 + + Fe ⁇ Fe 2 + + Cu K 1. 10 26
  • Citrate ions are commonly used in electrolytic baths for depositing conductive metal copper. The combination with the ions does indeed seem to favour copper depositing and improve the homogeneity of the deposit.
  • ascorbic acid reduces the Fe 3+ ions in Fe 2+ .
  • the reduction of the amount of Fe 3+ ions also implies that of Cu 2+ ions in solution form (Equation 12), thus reducing the coppering phenomenon.
  • Ascorbic acid should reduce corrosion.
  • the main anodic reaction is as follows: Fe ⁇ Fe 2 + + 2 e ⁇ Anodic reaction Or also Fe ⁇ Fe 3 +
  • the main cathodic reactions are the same ones as the corrosion reactions mentioned in the previous paragraphs (Equation 10, Equation 11, Equation 12, Equation 13, Equation 14, and Equation 15).
  • the decoppering phase has the aim of dissolving the metal copper liable to be redeposited in the acid phase.
  • the hydrogen peroxide H 2 O 2
  • H 2 O 2 allows the oxidation of copper in the following reactions: HO ⁇ + H 2 O 2 ⁇ HO 2 ⁇ + H 2 O Cu ⁇ Cu 2 + + 2 e ⁇ HO 2 ⁇ + H 2 O + 2 e ⁇ ⁇ 3 HO ⁇ Cu + H 2 O 2 ⁇ Cu 2 + + 2 HO ⁇ ⁇
  • This compound is very stable for a pH > 9.5.
  • the ammonia has a combining function whilst the ammonium ion (resulting from the ammonium bicarbonate) has a function as a catalyst of the combination reaction.
  • the general procedure involves at least the following phases:
  • the first chemical cleaning phase is filling the circulation loop assembly.
  • This stage is performed in two acts, filling up to just under the connections of the steam generator (GV) (loop/GV interfaces) and then up to the first target level before the injection of chemical reagents, in order to:
  • GV steam generator
  • the boiler and the recirculation system are started up until the required temperature for the acid phase is reached through an external heating system made up of plate exchangers fed by a boiler located on the loop set in the outside of the reactor building.
  • the circulation loop is equipped with check valves. Anti-foaming agent will be added just before the injection of the reagents of the acid stage.
  • the aim of this first phase is to partially dissolve the deposits of oxides made up mainly of magnetite, present in the steam generator on the level of the separator plates and in the free part of the tubes, as well as obstructing the passages of the four-leaved supports of said tubes.
  • the operating action procedure according to the invention has two variants:
  • the formic acid can complement the ascorbic acid or the mixture of citric acid with ascorbic acid, especially in the case of the absence of copper in the alloys used.
  • Another criterion of the end of phase or control alert for end of phase is when a certain threshold in the amount of iron obtained on the electrolyte is reached.
  • This phase takes place immediately after the sealing tests, the heating of the solution circulating in the steam generator and the nitrogen bubbling.
  • the loop including the steam generator is filled with water to the level of the recirculation pump, and demineralised water is added with an anti-foaming agent.
  • the temperature of the solution is around 25 and 70°C or 20 and 65°C depending on the procedure applied.
  • the simultaneous injection of the mixture of citric-ascorbic acids and the inhibitor is done through their respective injection pump on the suction level of the recirculation pumps.
  • Ammonia is injected in order to adjust the pH to the required pH level, which is done in the same way as that of the mixture of acids and inhibitor, i.e. at the suction level of the pumps.
  • the solvent is inserted at the top of the steam generator with a burst jet system located over the bundle of tubes.
  • the solution recirculates from the top of the steam generator downwards.
  • the nitrogen bubbling is done by means of injection cannula located at the bottom of the steam generator.
  • the temperature is maintained around the reference temperature for the entire phase.
  • Homogenising the solution is considered to take 20 minutes depending on the speed of recirculation and the nitrogen bubbling. This duration was determined by extrapolating the results of the tests performed with the aid of a propagation model with a proven recirculation flow of 30 m 3 /h and a propagation flow of 30Nm 3 /h.
  • the physical-chemical parameters are monitored (at intervals of from half to one hour for the samples) in order to monitor the evolution of the acid phase and to ensure its proper development until one of the criteria for the end of the phase is attained.
  • the maximum length of this phase is 24 hours, including the previous filling and later emptying times.
  • Corrosion test pieces will be located inside the steam generator and in the connected circuits.
  • a limit is defined for activating the system for monitoring corrosion (early emptying) in order to guarantee the harmlessness of the process in the event of there being excessively high corrosion kinetics. This limit could be reviewed after the first stage in the phase.
  • On-line monitoring of corrosion would complement the supervision of the total concentration of dissolved iron enabling estimating the efficiency and corrosion in real time and guaranteeing the procedure. It enables stopping depending on the amount of magnetite dissolved and/or of the corrosion.
  • the rinsing stage is made up of 1 to 3 low volume rinses (filling the steam generator at the level of the dividing plate 1) followed by a full volume rinse (filling level of the steam generator over or equal to that of the acid stage).
  • an intermediate spraying stage can be performed in order to eliminate the sludges found in the waste at the bottom part of the steam generator, in order to prevent the structural embrittlement and redepositing of magnetite through gravity after the acid phase. This means an optimum decoppering effectiveness can be guaranteed. In the event of spraying being carried out a televisual examination will be performed.
  • the decoppering stage will take place only when the cleaning is done on alloys with copper content.
  • the solvent for decoppering has the aim of eliminating any copper that could be deposited during the stage for dissolving the deposits of oxides in the internal parts of the steam generator, and more specifically on the tubes, as well as part of the copper present in the deposits.
  • a water solution of ammonia is added, and possibly also of ammonium bicarbonate, as well as a strong oxidiser, such as hydrogen peroxide.
  • the decoppering phase is performed in two stages.
  • the steam generator is filled continuously with the ammonia/ammonium bicarbonate mixture and demineralised water while the hydrogen peroxide is injected very slowly in order to control the temperature as far as possible.
  • the injection of the decoppering mixture starts to be done at the top of the steam generator.
  • the recirculation then takes place from the top downwards. Only the injection of hydrogen peroxide takes place in parallel through the upper and lower part of the steam generator, for example with a distribution of affluent of 30 and 70% respectively (in flow).
  • the following table shows the execution conditions, according to a non-limiting form of embodiment: Minimum values Operating ranges Parameters With intermediate spraying Without intermediate spraying Amount of deposits ( ⁇ 0.5 to 8% copper) 6 to 50g/l Ammonia or Ammonium Hydroxide (water solution of ammonia) (g/l) 5-20 Ammonium bicarbonate (g/l) 0-10 Hydrogen peroxide (% mass) 0.1-0.5 pH ⁇ 8.0 Temperature (°C) (initial, before the first injection of hydrogen peroxide) 10-75 Duration (h) (t 0 represents the injection of hydrogen peroxide.
  • the duration means the duration between t 0 and emptying) ⁇ 8 [8 ; 18] (including the rinse) ⁇ 9 [9 ; 18] Recirculation flow(m 3 /h) 0 to X Air bubbling (Nm 3 /h) [10; 80] Minimum level Niv2 ⁇ Niv3 ⁇ dome of the exchanger
  • the physical-chemical parameters are monitored (at intervals of half to one hour for the samples) to monitor the evolution of the decoppering stage and ensure its proper development until one of the end of phase criteria is attained.
  • the duration of the decoppering stage will be adapted depending on the level of scale and the amount of copper in each location.
  • Parameters monitored Justification Concentration of dissolved copper (sample) monitoring the efficiency of the decoppering phase (copper from the coppering or from the copper found in the deposits) - verification of the stability of the decoppering stage and maintenance of its efficiency pH (sample) - verification of the stability of the pH and particularly for the pH to be ⁇ 8 throughout the phase
  • Temperature continuously measured
  • Flows (continuously measured) governing the durations of injection as well as the volumes injected required to learn the initial concentrations of the reagents in the steam generator
  • Level in the steam generator continuously measured
  • the rinsing stage consists of from 1 to 3 low volume rinses, followed by a full volume rinse (filling the steam generator from the top over the low connections), followed by a full volume rinse (filling level of the steam generator equal to or over that of the decoppering phase.
  • the characteristics of the liquid effluents as well as the estimated amounts of the liquid and gaseous effluents will be determined at the outlet of the first stage in each series.
  • gaseous species which could be issued during execution of the procedure are:
  • the species to be covered by monitoring by an accredited laboratory will be determined during the on-site execution in order to ensure, amongst others, that the amount of ammonia rejected is under 50 Kg per intervention.
  • the volumes of liquid effluents will range from about 1500 to 2200 m 3 depending on the type of power station being operated on.

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  • Engineering & Computer Science (AREA)
  • Physics & Mathematics (AREA)
  • Mechanical Engineering (AREA)
  • General Engineering & Computer Science (AREA)
  • Thermal Sciences (AREA)
  • Life Sciences & Earth Sciences (AREA)
  • Sustainable Development (AREA)
  • Sustainable Energy (AREA)
  • High Energy & Nuclear Physics (AREA)
  • Chemical & Material Sciences (AREA)
  • Combustion & Propulsion (AREA)
  • Preventing Corrosion Or Incrustation Of Metals (AREA)

Claims (14)

  1. Verfahren zur chemischen Reinigung von Wärmetauschern, wie Dampferzeugern, in thermonuklearen Kraftwerken des DWR-Typs, in denen der Dampferzeuger ein Wärmetauscher ist, welcher aus einem Satz von Rohren aus dem Primärkreislauf hergestellt ist, wobei diese Rohre durch Trennplatten getrennt sind, die Rohre und die Platten im Betrieb mit Ablagerungen, die an ihnen anhaften, von Materialien aus Erosionen, Korrosionen und Verunreinigungen in dem Sekundärkreislauf beschichtet werden, wobei diese Materialien insbesondere aus Metallen und Metalloxiden, wie Magnetit, und Metallen, wie Kupfer, gebildet sind, wobei dieses Verfahren zwei Hauptstufen umfasst, eine erste Phase des Entfernens der Metalloxide und im Falle, dass die Reinigung auf Kupfer enthaltenden Materialien erfolgt, eine zweite Phase zum Entkupfern und Entfernen jeglicher Kupferverbindungen, dadurch gekennzeichnet, dass:
    in der ersten Phase eine Wasserlösung in den Dampferzeuger mit den folgenden Reagenzien eingeführt wird:
    • Zitronensäure, 0,5 - 10 Masse-%
    • Ascorbinsäure 0,3 - 5 Masse-%
    • der Vorgang wird bei einer Temperatur von 20 °C - 70 °C durchgeführt
    • und der pH-Wert für das Verfahren beginnt bei Werten von 1 - 4,5
  2. Verfahren zur chemischen Reinigung von Wärmetauschern nach Anspruch 1, dadurch gekennzeichnet, dass dieses auch die Zugabe von Ameisensäure bis zu 6 % umfasst.
  3. Verfahren zur chemischen Reinigung von Wärmetauschern nach Anspruch 1 bis 2, dadurch gekennzeichnet, dass dieses auch die Zugabe eines Korrosionsinhibitors umfasst.
  4. Verfahren zur chemischen Reinigung von Wärmetauschern nach Anspruch 1 bis 3, dadurch gekennzeichnet, dass dieses auch die Zugabe eines Schaumverhütungsmittels umfasst.
  5. Verfahren zur chemischen Reinigung von Wärmetauschern nach einem der Ansprüche 1 bis 4, dadurch gekennzeichnet, dass dieses auch das Einspritzen und das Durchblasen von Stickstoff als Mittel zum Homogenisieren der Reagenzien und zum Mitreißen der gelösten Metallverbindungen und zur Erhaltung des Reduktionscharakters der Lösung umfasst.
  6. Verfahren zur chemischen Reinigung von Wärmetauschern nach einem der Ansprüche 1 bis 5, dadurch gekennzeichnet, dass die erste Phase höchstens 24 Stunden dauert.
  7. Verfahren zur chemischen Reinigung von Wärmetauschern nach einem der Ansprüche 1 bis 6, dadurch gekennzeichnet, dass dieses das Überwachen des Gesamteisens und das Überwachen des Verfahrens auf der Basis der Konzentration umfasst.
  8. Verfahren zur chemischen Reinigung von Wärmetauschern nach einem der Ansprüche 1 bis 7, dadurch gekennzeichnet, dass die erste Phase des Entfernens von Metalloxiden dynamisch in einem kontinuierlichen Zyklus erfolgt.
  9. Verfahren zur chemischen Reinigung von Wärmetauschern nach einem der Ansprüche 1 bis 8, dadurch gekennzeichnet, dass eine Wasserlösung, welche die folgenden Reagenzien umfasst, in der zweiten Phase zum Entkupfern und Kupferverbindungen eingeführt wird:
    Ammoniak oder Ammoniumhydroxid 5 - 20 g/l
    Ammoniumhydrogencarbonat 0 - 5 g/l
    Wasserstoffperoxid 0,1 - 0,5 Mass-%
    Der Vorgang wird bei einer Temperatur von 10 °C - 75 °C durchgeführt.
    Der pH-Wert für das Verfahren wird bei Werten von > 8 gehalten.
  10. Verfahren zur chemischen Reinigung von Wärmetauschern, nach Anspruch 9, dadurch gekennzeichnet, dass das Gemisch der wässrigen Lösung aus Ammoniak und Ammoniumhydrogencarbonat zunächst durchgeführt wird, weil Wasserstoffperoxid sehr langsam abhängig von der sich ergebenden Temperatur der Lösung zugegeben wird.
  11. Verfahren zur chemischen Reinigung von Wärmetauschern nach einem der Ansprüche 9 bis 10, dadurch gekennzeichnet, dass die Stufe des Entkupferns mindestens 4 Stunden und höchstens 24 Stunden, einschließlich des Spülens, dauert.
  12. Verfahren zur chemischen Reinigung von Wärmetauschern nach einem der Ansprüche 1 bis 11, dadurch gekennzeichnet, dass die zweite Stufe des Entkupferns dynamisch in einem kontinuierlichen Zyklus ausgeführt wird.
  13. Verfahren zur chemischen Reinigung von Wärmetauschern nach einem der Ansprüche 1 bis 12, dadurch gekennzeichnet, dass dieses eine oder mehrere Spülstufen nach der Säurephase, die auf einen basischen pH eingestellt ist, umfasst.
  14. Verfahren zur chemischen Reinigung von Wärmetauschern nach einem der Ansprüche 1 bis 13, dadurch gekennzeichnet, dass dieses eine Spülstufe nach der Stufe des Entkupferns umfasst, für welche die Spüllösung durch lonenaustauschharze gefiltert wird, um Leitfähigkeit zu reduzieren, bis die erforderliche Leitfähigkeit erreicht ist.
EP13802435.1A 2013-09-24 2013-09-24 Verfahren zur chemischen reinigung eines wärmetauschers Active EP3051247B1 (de)

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PCT/IB2013/058816 WO2015044709A1 (es) 2013-09-24 2013-09-24 Procedimiento de limpieza quimica de intercambiadores de calor

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US4190463A (en) * 1979-02-05 1980-02-26 Nalco Chemical Company Method of removing iron oxide deposits from heat transfer surfaces
US4632705A (en) 1984-03-20 1986-12-30 Westinghouse Electric Corp. Process for the accelerated cleaning of the restricted areas of the secondary side of a steam generator
JPH04227487A (ja) 1990-05-18 1992-08-17 Westinghouse Electric Corp <We> スラッジ及び腐食生成物の除去方法
US5154197A (en) * 1990-05-18 1992-10-13 Westinghouse Electric Corp. Chemical cleaning method for steam generators utilizing pressure pulsing
US5764717A (en) 1995-08-29 1998-06-09 Westinghouse Electric Corporation Chemical cleaning method for the removal of scale sludge and other deposits from nuclear steam generators
US6740168B2 (en) * 2001-06-20 2004-05-25 Dominion Engineering Inc. Scale conditioning agents
EP1751068B1 (de) * 2004-04-01 2018-12-05 Westinghouse Electric Company LLC Verbesserte kesselsteinkonditionierungsmittel und behandlungsverfahren
DE102008005199B4 (de) 2008-01-18 2014-01-23 Areva Gmbh Verfahren zur Reinigung eines Wärmetauschers
ES2711924T3 (es) * 2010-01-25 2019-05-08 Westinghouse Electric Co Llc Procedimiento y composición para eliminar depósitos de cal formados en una superficie metálica dentro de un sistema generador de vapor

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WO2015044709A1 (es) 2015-04-02
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