Abstract:
A method for conditioning the circulatory system ( 1 ) of a power plant is especially suited for a nuclear power plant. An amine, which is a film-forming agent, is metered into the working medium circulating in the circulatory system. The film-forming agent forms a hydrophobic film on the surfaces of the circulatory system. During the process, the concentration of the film-forming agent is monitored in at least one measuring point by way of measurement, and metering of the film-forming agent is stopped once its concentration in the working medium has reached a value of 1 ppm to 2 ppm in at least one measuring point M 1.

Description:
CROSS-REFERENCE TO RELATED APPLICATION 
       [0001]    This application is a continuation, under 35 U.S.C. §120, of copending international application No. PCT/EP2013/053921, filed Feb. 27, 2013, which designated the United States; this application also claims the priority, under 35 U.S.C. §119, of German patent application No. DE 10 2012 203 010.7, filed Feb. 28, 2012; the prior applications are herewith incorporated by reference in their entirety. 
     
    
     BACKGROUND OF THE INVENTION 
     Field of the Invention 
       [0002]    The invention relates to a method for conditioning a power-generating circulatory system of a power plant. By way of example, such a circulatory system should be understood to mean the primary and secondary circuit of a pressurized water reactor, the coolant circuit of a boiling water reactor and the steam circuit of a conventional power plant. Here, the term “conditioning” should be understood to mean a measure by means of which the surfaces of the components of the circulatory system can be protected from corrosion. When surfaces are mentioned, this should be understood to mean, on the one hand, the inner surfaces of e.g. lines, heat exchangers and containers and, on the other hand, surfaces of components such as turbine blades around which a work medium (water, steam) of the circulatory system flows. By way of example, German published patent application DE 2625607 and German patent DD 107962 describe methods in which film-forming amines (FFA) are metered into the secondary circuit or the water/steam circuit of pressurized water reactors during power operation. 
         [0003]    The object of conditioning of the type in question is to generate a thin film on the surfaces which is as contiguous as possible, with the thickness of at most one to two molecule layers. However, conventional methods result in the risk in this context that thicker FFA deposits are formed, which, on the one hand, interfere with the process operation, by virtue, for example, of reducing heat transport in steam generators or other heat exchangers or narrowing flow cross sections. Moreover, there is the risk of parts of the deposits detaching and damaging turbine blades or adversely affecting mechanical filter installations and ion exchangers, so that the latter two have to be replaced. 
       SUMMARY OF THE INVENTION 
       [0004]    It is accordingly an object of the invention to provide a method of conditioning of a power-generating circulatory system of a power plant which overcome the above-mentioned disadvantages of the heretofore-known devices and methods of this general type. 
         [0005]    With the foregoing and other objects in view there is provided, in accordance with the invention, a method of cleaning and conditioning a circulatory system of a power plant, in particular a water/steam circuit of a nuclear power plant. The method comprises: 
         [0006]    adding an amine as a film-forming agent to a work medium circulating in the circulatory system, for the film-forming agent to form a hydrophobic film on surfaces of the circulatory system; 
         [0007]    monitoring a concentration of the film-forming agent by conducting measurements at a measurement point during a duration of the method; and 
         [0008]    terminating the step of adding the film-forming agent when the concentration of the film-forming agent in the work medium has reached a value between 1 ppm and 2 ppm at the measurement point. 
         [0009]    In other words, the above and other objects are achieved with a method of the type mentioned at the outset, in that preferably during power operation an amine is added to the work medium circulating in the circulatory system, which amine acts as film-forming agent and forms a hydrophobic film on the surfaces of the circulatory system which are in contact with the work medium. Here, the method is carried out in such a way that there is control in respect of the concentration of the film-forming agent or the progress of the film formation at practically any time during the method. This is achieved by virtue of the fact that the concentration of the film-forming agent is monitored at at least one measurement point by measurements during the duration of the method. Here, the film-forming agent is metered in such a way that in the water phase of the water/steam circuit, at least in the steam generator feed water, there is a concentration of 1 to 2 ppm, preferably of 1 to 1.5 ppm. If work is conducted within these boundaries, in particular with at most up to 1.5 ppm of film-forming agent, the formation of thick layers of the film-forming agent can be avoided. It was moreover found that, in many cases, an adequate film is already present on the surfaces when the aforementioned concentration or target concentration has been reached. 
         [0010]    However, a single-layer or substantially mono-molecular film is obtained with greater reliability on the surfaces, substantially covering the latter completely, if the method is continued under the aforementioned premises until the concentration of the film-forming agent at a constant metering rate at a plurality of measurement points distributed over the water/steam circuit remains constant averaged over time at a plurality of measurement points (M1, M2, M3), i.e. if an equilibrium concentration sets in at the measurement points. The mean averaged over time is understood to mean the profile of the trend which emerges if fluctuations due to the measurement technologies have been eliminated by suitable methods of conventional error calculation. 
         [0011]    The measurement points already mentioned above are, in the case of a water/steam circuit, distributed such that at least one measurement point is situated in the one-phase region and at least one measurement point is situated in the two-phase region of the circuit. 
         [0012]    In a preferred variant, the method is carried out in such a way that it can be possible, at practically any time during the method, to control not only the concentration of the film-forming agent or the progress of the film formation, but also the effects of the film-forming agent metering in respect of impurities mobilized thereby. This is achieved by virtue of the fact that the concentration of at least one impurity and the concentration of the film-forming agent are measured during the duration of the method and the concentration of the film-forming agent is modified depending on the concentration of at least one impurity. This ensures that, at any time during the method, predetermined guide values and limits of an impurity, in particular a corrosively acting ionic impurity such as e.g. chloride or sodium ions, are maintained or not exceeded. Moreover, it is possible to effectively prevent an impurity, immobilized at a locally restricted surface region of the water/steam circuit, from quickly being mobilized by metering of the film-forming agent and being distributed in large quantities in the whole circuit. 
         [0013]    As a countermeasure to an increase in the concentration of an impurity, the metering rate of the film-forming agent can be reduced or interrupted, in particular in view of maintaining limits. A further countermeasure consists of reducing the concentration of impurities that have passed into the work medium. This preferably occurs by virtue of the water/steam circuit being purged and, in the process, particulate impurities, inter alia, being removed by blowing down. This measure preferably occurs, for example for reasons of procedural economy, directly following an interruption of the metering of the film-forming agent. It is also feasible that, in order to remove impurities from the water/steam circuit, filters are employed, for example the filter installations of the condensate cleaning system, which is part of the power plant. 
         [0014]    Monoamines with a hydrocarbyl comprising 8 to 22 carbon atoms were found to be particularly effective for both the cleaning effect and for the film formation, with octadecylamine being particularly suitable in this case. Monoamines of the present type are available as waxy substance at room temperature. Conventional emulsions produced therefrom usually contain relatively large amounts of organic emulsifiers, which can have damaging effects in the water/steam circuit. Therefore, the FFA is preferably employed in the pure form in the method according to the invention, namely as an aqueous emulsion without the addition of emulsifiers, which can be obtained by pure mechanical mixing under the application of increased temperature. 
         [0015]    Other features which are considered as characteristic for the invention are set forth in the appended claims. 
         [0016]    Although the invention is illustrated and described herein as embodied in a method for conditioning a power-generating circulatory system of a power plant, it is nevertheless not intended to be limited to the details shown, since various modifications and structural changes may be made therein without departing from the spirit of the invention and within the scope and range of equivalents of the claims. 
         [0017]    The construction and method of operation of the invention, however, together with additional objects and advantages thereof will be best understood from the following description of specific embodiments when read in connection with the accompanying drawings. 
     
    
     
       BRIEF DESCRIPTION OF THE SEVERAL VIEWS OF THE DRAWING 
         [0018]      FIG. 1  shows, in a very schematic view, the water/steam circuit of a pressurized water reactor (PWR); 
           [0019]      FIG. 2  shows a diagram which reproduces the time profile of the concentration of ODA in the steam generator feed water due to ODA metering; and 
           [0020]      FIG. 3  shows a flowchart illustrating a conditioning process. 
       
    
    
     DETAILED DESCRIPTION OF THE INVENTION 
       [0021]    Referring now to the figures of the drawing in detail and first, particularly, to  FIG. 1  thereof, there is shown an exemplary circulatory system, in the form of a water/steam circuit  1  (abbreviated WSC in the following text) of a pressurized water reactor (PWR). The circuit comprises a piping system  2 , a plurality of steam generators  3 , normally a plurality of turbines, for example a high-pressure (HP) turbine  4  and a low-pressure (LP) turbine  5 , a water separator intermediate superheater  17  between the HP and LP turbines, a condenser  6 , a feed water container  7 , a condensate pump  8  arranged between the condenser  6  and the feed water container  7 , a plurality of feed water preheaters  16  and a feed water pump  9  arranged between the feed water container  7  and the steam generator. Moreover, downstream of the condenser  6 , there is a condensate cleaning system  10 , which can comprise mechanical filters and, likewise, ion exchangers. On the primary side, the steam generator  3  is connected to the primary circuit  13  of the nuclear reactor, which comprises the reactor pressure container  14  and a main coolant pump  15 . 
         [0022]    As mentioned above, the cleaning and conditioning method is preferably carried out during power operation. This also comprises phases during the startup and shutdown of the power plant. In the exemplary embodiment described below, the conditioning of the water/steam circuit or the metering of a film-forming amine (abbreviated to FFA in the following), namely octadecylamine (ODA), is carried out just before shutting down the nuclear reactor. The continuous monitoring of concentrations or concentration changes in FFA and impurities (see step II in  FIG. 3 ), carried out from the start of the method, is brought about by a plurality of measurement points arranged at different positions within the WSC  1 . Some of these measurement points M1, M2, M3 are depicted in  FIG. 1  in an exemplary manner. 
         [0023]    The film-forming agent may be metered in at any expedient location within the circulatory system. Here, the injection point is illustrated in  FIG. 1  by way of the arrow just upstream of the condenser  6 . 
         [0024]    As a result of the surfactant-like properties of the ODA (octadecylamine), there is a mobilization of impurities from the start of the FFA metering. Thus, as already mentioned above, limits which may not be exceeded are set for the concentration of these impurities. In the case of ionic impurities, the concentration is measured directly, i.e. in relation to a very specific ion with known wet-chemical or physical-chemical measurement methods. However, the concentration can also be determined indirectly, i.e. by the increase in the electrical conductivity of the work medium caused by the mobilization or the passage of ions into the work medium. The measurement methods used in the process are well known to a person skilled in the art, and so these do not have to be discussed in detail. A further parameter important for carrying out the method in a controlled manner is the FFA or ODA concentration in the work medium—the water present in the WSC. 
         [0025]    Finally, as a result of the ODA metering, corrosion products are also released, i.e. very fine particles of magnetite, which adhere to the surfaces and, as a result of the effect of ODA, go into colloidal solution. Since the majority of corrosion products can be traced back to metal oxides such as magnetite, it is normally sufficient only to carry out measurements in this respect. In the process, e.g. the iron content of the feed water is determined in a known fashion and, as a result of the known stoichiometry of the magnetite, the concentration thereof in the feed water is deduced. Finally, the pH-value is also monitored in order to prevent corrosion of the metallic components of the WSC  1 . It is also feasible for the TOO (total organic carbon) value to be monitored in order to exclude a possible decomposition of the added ODA at the prevalent conditions, i.e. temperatures of over 250°, and hence the formation of decomposition products which could act corrosively. 
         [0026]    The ODA metering or the amount of ODA metered into the WSC  1  per unit time is—on the basis of the measurement data established at the measurement points M1 to M3 regulated such that the concentrations of the type of impurities that have passed into the work medium due to the ODA metering remain below predetermined limits (see step III in  FIG. 3 ). Moreover, by monitoring the aforementioned concentration values, it is already possible to identify a trend in a timely fashion such that a countermeasure can be introduced in a timely fashion. By way of example, the metering-in of ODA can be reduced or interrupted. Here, it should be noted that a change in metering only has an effect a couple of hours later due to the volume of water and the length of the piping of the WSC  1 . However, this time delay plays practically no role in a method according to the invention since a change of a critical concentration value is identified by permanent whole control at a plurality of measurement points M1 to M3, long before said value has reached its critical limit. 
         [0027]    In order to have an indication of which ODA amounts are required for a given WSC  1 , it is expedient to estimate what approximate amount of ODA is necessary to generate a mono-molecular hydrophobic film on the surfaces of the WSC. This amount can then still be multiplied by a factor in order to take into account the roughness of the surfaces, which, after all, is significant in the case of sub-microscopic observation, and effects which use up ODA, for example the degree of contamination of the WSC. On the basis of this estimate, it is possible, in the case of a given ODA metering rate, to specify a defined period of time in which an ODA film which completely covers the surfaces, e.g. a mono-molecular ODA film, has been created. 
         [0028]    When a critical concentration of an impurity is reached (step III in  FIG. 3 ), an effective measure for reducing the critical concentration lies in interrupting the FFA metering and a subsequent purging or blowing down, during which the impurity is removed from the WSC (step VII in  FIG. 3 ). In the process, there is continuous monitoring of whether the installation-specific control parameters or concentrations lie in an admissible range (step VIII in  FIG. 3 ). If this is the case, the conditioning is continued by resuming the FFA metering. 
         [0029]    The concentration of ODA in the aqueous phase is regulated by appropriate metering rates in such a way that this value, practically until the end of the method, does not exceed an upper absolute safety limit of 2 ppm, preferably 1.5 ppm. As a result, this prevents too strong a mobilization of impurities, which goes beyond the set limits, or a no longer controllable massive ODA precipitation from occurring. It also ensures that no unwanted massive ODA deposits are formed. In so doing, metering is such that initially there is a low ODA concentration, which only rises to a target concentration of above 1 ppm, at most up to 1.5 ppm or 2 ppm (C Target  in  FIG. 2 ), toward the end of the process. The addition preferably continues until the ODA concentration with increasing tendency has reached the maximum values of 2 ppm or 1.5 ppm (step VI in  FIG. 3 ). 
         [0030]    In order to identify when a complete substantially mono-molecular film is formed on the surfaces, the concentration profile of the ODA concentration is observed at an unchanging ODA metering rate. If the equilibrium concentration of the FFA is reached at a plurality of measurement points, preferably at all measurement points M1 to M3, i.e., if an unchanging or slightly falling FFA concentration is to be observed (step V in  FIG. 3 ), the time has been reached to end the ODA metering-in or the conditioning method (step VI in  FIG. 3 ; line CP in  FIG. 2 ). The unchanging or sinking ODA concentration toward the end of forming the film could be traced back to the fact that the formation of ODA double and multiple layers is favored for kinetic and/or thermodynamic reasons and therefore occurs more quickly than the initial film formation on the metallic surfaces of the WSC  1 . 
         [0031]    The ODA film applied to the surfaces of the WSC can lose or reduce its effectiveness over time, for example by virtue of it in part detaching from surfaces or for instance it being subjected to thermal or chemical decomposition processes. It is therefore expedient to undertake a refresh conditioning at a given time. To this end, permanent monitoring of the work medium for the presence of corrosion products, i.e. products connected with the formation of oxidation layers, for example metal ions originating from the component materials of the WSC, is expedient. As soon as it is possible to identify a (significant) increase of corrosion products (step X in  FIG. 3 ), a conditioning of the type described above is put into motion. 
         [0032]    The following summarizes and lists the various steps illustrated in the flowchart of  FIG. 3 . 
         [0033]    Step I Start of FFA conditioning 
         [0034]    Step II Process monitoring
       FFA concentration (M 1 -M 3  in  FIG. 1 )   Control parameters as per installation specification       
 
         [0037]    Step III Limits of control parameters reached? 
         [0038]    Step IV Target concentration of FFA reached at M 1 ? 
         [0039]    Step V Equilibrium concentration of FFA reached over M 1 -M 3 ? 
         [0040]    Step VI End of FFA conditioning 
         [0041]    Step VII Interrupt metering, purging 
         [0042]    Step VIII Values of the control parameters in an admissible range? 
         [0043]    Step IX Process monitoring of corrosion products 
         [0044]    Step X Increase in the concentration of corrosion products?