Method for measuring dissolution rate of cleaning agent to sediment

Abstract

The invention discloses a method for measuring the dissolution rate of a cleaning agent to sediments, and particularly, the method comprises the following steps: mixing a sediment sample with a first preset mass and a cleaning agent solution with a first preset volume, so that the sediments and the cleaning agent solution are subjected to a dissolution reaction under a preset cleaning condition to obtain a dissolved mixture; extracting supernate with different reaction durations from the dissolved mixture; determining the maximum concentration value of each target element in each supernatant and a target extraction moment corresponding to the maximum concentration value; according to the first preset volume, the maximum concentration value corresponding to each target element, the target extraction moment corresponding to each target element and the mass relation coefficient between each target element and the phase composition, the dissolution rate of the cleaning agent solution to the sediment is calculated. By measuring the concentration peak value of the target element and the time point when the peak value is reached, the dissolution rate of the cleaning agent solution is calculated, and the most effective cleaning agent can be selected to meet actual requirements.

Description

Technical Field

[0001] The present application relates to the field of cleaning technology, and in particular to a method for measuring the dissolution rate of a cleaning agent on a deposit. Background Art

[0002] At present, the cleaning agent is usually selected based on the product performance data of different cleaning agents. However, the cleaning agent selected by this selection method cannot ensure that it is suitable for the cleaning needs of the steam generator secondary side deposit sample to be cleaned, and thus cannot ensure its cleaning effect in actual application. Summary of the invention

[0003] In view of this, the present application provides a method for measuring the dissolution rate of deposits by a cleaning agent, the main purpose of which is to solve the technical problem that the existing method of selecting cleaning agents based on their product performance data cannot ensure the cleaning effect of the cleaning agent solution in actual applications.

[0004] According to the first aspect of the present application, a method for measuring the dissolution rate of a cleaning agent on a deposit is provided, the method comprising:

[0005] Obtaining multiple elements contained in the sediment sample to be cleaned, the phase composition corresponding to each element, and the mass content of each phase composition in the sediment sample;

[0006] Sort the multiple mass contents in descending order, add each mass content in sequence starting from the mass content of the first position, and when the sum of the mass contents reaches a preset threshold, obtain at least one target element corresponding to at least one phase composition contained in the sum of the mass contents;

[0007] Mixing a sediment sample of a first preset mass and a cleaning agent solution of a first preset volume, so that the sediment and the cleaning agent solution undergo a dissolution reaction under preset cleaning conditions to obtain a dissolved mixture, wherein the dissolved mixture includes a supernatant and undissolved sediments;

[0008] extracting a plurality of supernatants from the lysis mixture at predetermined time intervals and a second predetermined volume;

[0009] Diluting the plurality of supernatants with a cleaning agent solution according to a preset dilution multiple to obtain a plurality of dissolved solutions;

[0010] According to the quantitative standard curve of each target element, the preset dilution multiple and multiple dissolving solutions, the maximum concentration value of each target element in each supernatant and the target extraction time corresponding to the maximum concentration value are determined, wherein the quantitative standard curve shows the corresponding relationship between the signal intensity measured by the quantitative instrument and the concentration of the target element;

[0011] The dissolution rate of the deposit by the cleaning solution is calculated according to the first preset volume, the maximum concentration value corresponding to each target element, the target extraction time corresponding to each target element, and the mass relationship coefficient between each target element and the phase composition.

[0012] Optionally, the step of obtaining a plurality of elements contained in the sediment sample to be cleaned, the phase composition corresponding to each element, and the mass content of each phase composition in the sediment sample specifically includes:

[0013] Obtaining sediment samples in the equipment to be cleaned;

[0014] Using element quantitative analysis technology, the sediment samples are quantitatively analyzed to obtain multiple mass contents of multiple elements in the sediment samples;

[0015] X-ray diffraction (XRD) technology is used to analyze the phase of sediment samples and determine the phase composition corresponding to each element;

[0016] Calculate the mass relationship coefficient between each element and its corresponding phase composition;

[0017] The mass content of each element is multiplied by the mass relationship coefficient to obtain the mass content of the phase composition corresponding to each element in the sediment sample.

[0018] Optionally, the step of mixing a sediment sample of a first preset mass and a cleaning agent solution of a first preset volume so that the sediment and the cleaning agent solution undergo a dissolution reaction under preset cleaning conditions to obtain a dissolved mixture specifically includes:

[0019] Add a first preset volume of cleaning agent solution into a three-necked flask of preset specifications, and immerse the bottom solution portion of the three-necked flask below the silicone oil;

[0020] Heat the silicone oil to obtain the temperature value of the cleaning agent solution in the three-necked flask;

[0021] When the temperature reaches and maintains the preset temperature value of the preset cleaning condition of the cleaning agent, a first preset mass of the sediment sample is added into the three-necked flask and stirred, so that the cleaning agent solution dissolves the sediment sample to obtain a dissolved mixture.

[0022] Optionally, the step of extracting a plurality of supernatants from the dissolved mixture according to a preset time interval and a second preset volume specifically includes:

[0023] Determine multiple extraction moments according to preset time intervals;

[0024] When the sediment sample is added to the three-necked flask, start timing to obtain the dissolution time;

[0025] When the dissolution time reaches each extraction moment, a second preset volume of supernatant is extracted from the dissolution mixture into a centrifuge tube, and a second preset volume of cleaning agent solution is added into the three-necked flask.

[0026] Optionally, the step of diluting each supernatant with a detergent solution according to a preset dilution multiple to obtain a plurality of dissolved solutions specifically includes:

[0027] According to the preset dilution multiple, a detergent solution is added into each centrifuge tube to dilute the supernatant in each centrifuge tube to obtain a dissolved solution.

[0028] Optionally, according to the quantitative standard curve of the target element, the preset dilution multiple and the plurality of dissolving solutions, the maximum concentration value of each target element in each supernatant and the target extraction time corresponding to the maximum concentration value are determined, further comprising:

[0029] Obtaining a standard solution of a target element with a first preset concentration;

[0030] Diluting the standard solution with a cleaning solution to obtain a plurality of diluted solutions with a plurality of second preset concentrations;

[0031] Using a quantitative detection method, measuring a first signal intensity value of each diluted solution;

[0032] A quantitative standard curve of the target element is drawn according to the plurality of second preset concentrations and the plurality of first signal intensity values.

[0033] Optionally, the step of determining the maximum concentration value of each target element in each supernatant and the target extraction time corresponding to the maximum concentration value according to the quantitative standard curve of the target element, the preset dilution multiple and the plurality of dissolving solutions specifically includes:

[0034] Using a quantitative detection method, measuring the second signal intensity value of each dissolved solution;

[0035] Determine the first concentration value corresponding to each second signal intensity value according to the quantitative standard curve;

[0036] Multiplying each first concentration value by a preset dilution factor to obtain a second concentration value of the target element in the first dissolved solution;

[0037] The maximum concentration value of the target element in the first dissolving solution and the target extraction time corresponding to the maximum concentration value are obtained.

[0038] Optionally, the method further comprises:

[0039] Obtain the relative atomic mass of each element and the molar mass of its corresponding phase composition;

[0040] The mass relationship coefficient between each element and its corresponding phase composition is calculated through molar mass and relative atomic mass.

[0041] Optionally, the step of calculating the dissolution rate of the deposit by the cleaning solution according to the first preset volume, the maximum concentration value corresponding to each target element, the target extraction time corresponding to each target element, and the mass relationship coefficient between each target element and the phase composition specifically includes:

[0042] Multiplying the mass relationship coefficient, the maximum concentration value and the first preset volume of each target element, and dividing the multiplied value by the target extraction time to obtain the dissolution rate of the cleaning solution for the phase composition corresponding to each target element;

[0043] In the case where there are multiple at least one target element, multiple dissolution rates of multiple phase compositions corresponding to the multiple target elements are added together to obtain the dissolution rate of the deposit by the cleaning solution.

[0044] Optionally, the element quantitative analysis technique includes any one of the following: X-ray fluorescence analysis and inductively coupled plasma optical emission spectrometry.

[0045] By means of the above technical solution, the present application provides a method for measuring the dissolution rate of a cleaning agent on a sediment. Specifically, the sediment sample on the secondary side of the steam generator is subjected to a dissolution reaction using the cleaning agent solution to be evaluated, and the supernatant is taken as the measurement sample solution according to a preset time interval and a second preset volume. After determining the main elements and their phase composition in the sediment sample, the concentration changes of the main elements in the measurement sample solution are monitored, the peak concentration of the target element and the time point when the peak value is reached are measured, and then the dissolution rate of the cleaning agent solution is calculated as a reference for measuring the cleaning efficiency of the cleaning agent for cleaning sediments, thereby judging whether the cleaning agent being evaluated is suitable for real-time application scenarios, which helps to select the most effective cleaning agent to meet actual needs.

[0046] The above description is only an overview of the technical solution of the present application. In order to more clearly understand the technical means of the present application, it can be implemented in accordance with the contents of the specification. In order to make the above and other purposes, features and advantages of the present application more obvious and easy to understand, the specific implementation methods of the present application are listed below. BRIEF DESCRIPTION OF THE DRAWINGS

[0047] Various other advantages and benefits will become apparent to those of ordinary skill in the art by reading the detailed description of the preferred embodiments below. The accompanying drawings are only for the purpose of illustrating the preferred embodiments and are not to be considered as limiting the present application. Also, the same reference symbols are used throughout the accompanying drawings to represent the same components. In the accompanying drawings:

[0048] Figure 1 A schematic flow chart of a method for measuring the dissolution rate of a deposit by a cleaning agent provided in an embodiment of the present application is shown;

[0049] Figure 2 A schematic flow chart of another method for measuring the dissolution rate of a deposit by a cleaning agent provided in an embodiment of the present application is shown;

[0050] Figure 3 The XRD spectrum of the sediment sample provided in the embodiment of the present application and the Fe 3 O 4 Comparison chart of standard XRD data;

[0051] Figure 4 The quantitative standard curve of Fe element provided in the embodiment of the present application is shown;

[0052] Figure 5 A curve diagram showing the relationship between Fe concentration and extraction time during the cleaning process of the cleaning solution provided in the embodiment of the present application. DETAILED DESCRIPTION

[0053] The exemplary embodiments of the present application will be described in more detail below with reference to the accompanying drawings. Although the exemplary embodiments of the present application are shown in the accompanying drawings, it should be understood that the present application can be implemented in various forms and should not be limited by the embodiments set forth herein. On the contrary, these embodiments are provided in order to enable a more thorough understanding of the present application and to fully convey the scope of the present application to those skilled in the art.

[0054] The present application embodiment provides a method for measuring the dissolution rate of a cleaning agent on a deposit, such as Figure 1 As shown, the method includes:

[0055] S101, obtaining multiple elements contained in a sediment sample to be cleaned, a phase composition corresponding to each element, and a mass content of each phase composition in the sediment sample.

[0056] The method for measuring the dissolution rate of deposits by a cleaning agent provided in the embodiment of the present application is mainly used in the test scenario of the cleaning efficiency of the cleaning agent on the deposits. Among them, the sediment sample to be cleaned can be the sediment extracted from the equipment to be cleaned. In the actual application scenario, the equipment to be cleaned can be the secondary side of the steam generator. During the operation of the reactor, the sediment in the secondary side of the steam generator will affect the heat transfer efficiency of the heat transfer tube, endanger the integrity of the heat transfer tube, and threaten the safe operation of the reactor. Therefore, when the sediment on the secondary side of the steam generator reaches a certain amount (such as 100g / m 2), cleaning work needs to be carried out. At present, cleaning agents are usually selected based on their product performance data, including cleaning efficiency, dissolution capacity, scope of application, etc. However, the deposits on the secondary side of different steam generators contain different materials, and have different reactions and tolerances to different cleaning agents. Product performance data may not be able to fully objectively and truly reflect the performance of cleaning agents under various actual conditions. In order to ensure the effectiveness of the selected cleaning agent in cleaning deposits, this application proposes measuring the dissolution rate of the cleaning agent to measure the cleaning efficiency of the cleaning agent, and provide a reference for selecting a suitable cleaning agent.

[0057] Specifically, different elements and their compounds in the sediment sample have different solubility and reactivity requirements for different cleaning agents. The elements contained in the sediment sample are determined by analytical methods, and the phase composition corresponding to each element is determined using X-ray diffraction technology. Afterwards, the mass content of each element in the sediment sample is measured. The relative atomic mass of each element and the molar mass of its corresponding phase composition are obtained, and the mass relationship coefficient between the element and the phase composition is calculated using the relative atomic mass and molar mass. Then, the mass content of each element is multiplied by the mass relationship coefficient to obtain the mass content of its corresponding phase composition in the sediment sample.

[0058] S102, sorting multiple mass contents in descending order, and adding each mass content in sequence starting from the mass content in the first position, and when the sum of the mass contents reaches a preset threshold, obtaining at least one target element corresponding to at least one physical phase composition contained in the sum of the mass contents.

[0059] In this step, in order to measure the main elements in the sediment sample, multiple mass contents of multiple phases are sorted in descending order, starting from the mass content of the first position, each mass content is added in turn, and the sum of the mass contents is calculated. When the sum of the mass contents reaches a preset threshold, it can be determined that at least one target element in the sum of the mass contents is the main element in the sediment sample.

[0060] Optionally, the preset threshold value can be 90%. After calculating the mass contents of multiple phase compositions, the mass contents are added in sequence starting from the largest mass content. When the sum of the mass contents reaches 90%, the calculation is stopped. At this time, one or more phase compositions contained in the sum of the mass contents are the main components in the sediment, and the corresponding target elements are the main elements in the sediment. Among them, if the maximum mass content is already greater than 90%, the target element corresponding to the mass content is determined to be the main element in the sediment, and no further addition calculation is required.

[0061] S103, mixing a sediment sample of a first preset mass and a cleaning agent solution of a first preset volume, so that the sediment and the cleaning agent solution undergo a dissolution reaction under preset cleaning conditions to obtain a dissolved mixture, wherein the dissolved mixture includes a supernatant and undissolved sediments.

[0062] In this step, a first preset mass of a sediment sample and a first preset volume of a cleaning agent solution are weighed, and after the weighed cleaning agent solution is added to a three-necked flask, the sediment sample is added to the three-necked flask containing the cleaning agent solution, and a dissolution reaction is carried out under preset cleaning conditions to obtain a dissolved mixture, wherein the dissolved mixture includes a liquid portion (i.e., a supernatant) produced when the sediment is mixed with the cleaning agent and the cleaning agent dissolves the metal oxides in the sediment during the cleaning process, and an undissolved solid portion (i.e., an undissolved sediment).

[0063] Optionally, based on experience, the mass of the sediment sample is accurately weighed. Thereafter, the amount of the cleaning solution added is set according to the mass of the sediment sample and the solubility of the selected cleaning solution to be measured. In an actual application scenario, if 5 g (first preset mass) of sediment sample is selected to be extracted, and the solubility of the cleaning agent to be evaluated is 200 ml, which can dissolve 5 g of sediment, then the first preset volume of the cleaning solution is determined to be 200 ml.

[0064] Furthermore, the preset cleaning conditions refer to presetting the cleaning temperature and stirring speed in the three-necked flask.

[0065] S104, extracting a plurality of supernatants from the dissolved mixture according to a preset time interval and a second preset volume.

[0066] S105 , diluting the plurality of supernatants using a cleaning solution according to a preset dilution multiple to obtain a plurality of dissolved solutions.

[0067] In steps S104 and S105, during the cleaning process, it takes a certain amount of time for the sediment to dissolve. When the concentration of the target element in the dissolving solution reaches a peak value over time, the cleaning agent exhibits the greatest dissolving ability and activity, which means that the cleaning agent has reached the highest efficiency and can effectively dissolve the chemical components indicated by the sediment. In order to measure the dissolution rate of the main elements in the sediment by the cleaning agent, it is necessary to detect the trend of the concentration of the main elements over time and measure the time point when the concentration peaks. Therefore, during the test, according to the preset time interval and the second preset volume, the supernatants of different reaction times are extracted from the dissolving mixture in turn and placed in centrifuge tubes to measure the concentrations of the target elements at different extraction times.

[0068] Furthermore, due to the large number of extractions, the volume of the supernatant is limited, so that the amount of supernatant sample that can be extracted at each extraction moment is small. In order to ensure the accuracy of the measurement results, the extracted supernatant is diluted according to a preset dilution multiple using a detergent solution to prepare a dissolved solution. The volume of the extracted dissolved solution and the stability of the measurement are increased, the errors introduced due to uneven sampling or sensitivity limitations of the measuring equipment are reduced, and at the same time, the amount of reagents used is reduced, saving measurement costs.

[0069] Optionally, when monitoring changes in the concentration of the target element, the value ranges of the second preset volume, the preset time interval, and the preset dilution multiple can be specifically set according to the experimental design and are not specifically limited here.

[0070] S106. Determine the maximum concentration value of each target element in each supernatant and the target extraction time corresponding to the maximum concentration value according to the quantitative standard curve of each target element, the preset dilution factor, and multiple dissolving solutions, wherein the quantitative standard curve shows the corresponding relationship between the signal intensity measured by the quantitative instrument and the concentration of the target element.

[0071] In this step, the quantitative standard curve provides a quantitative tool that shows the corresponding relationship between signal intensity and concentration. The quantitative standard curve can be used to accurately measure the concentration of the target element contained in different dissolved solutions. After the dissolved solutions are prepared in sequence according to the preset dilution multiples, for any target element, the concentration value of the target element in each dissolved solution is measured using the quantitative standard curve. Since the dissolved solution is a diluted solution, in order to obtain the concentration of the target element in the supernatant, it is also necessary to multiply the measured concentration value by the preset dilution multiple to obtain the concentration value of the target element in the supernatant at different extraction time points.

[0072] Furthermore, among the multiple concentration values ​​measured, the peak concentration value (i.e., the maximum concentration value) is obtained, which reflects the critical point of the reaction and dissolution of the cleaning agent solution and the sediment sample, which means that the dissolution capacity of the cleaning agent has reached its limit. The target extraction time of the peak concentration is obtained, that is, the time when the cleaning agent achieves the maximum cleaning effect. It provides quantitative data for calculating the dissolution rate of the cleaning agent, which is crucial for evaluating the cleaning efficiency of the cleaning agent for sediments.

[0073] S107, calculating the dissolution rate of the deposit by the cleaning solution according to the first preset volume, the maximum concentration value corresponding to each target element, the target extraction time corresponding to each target element, and the mass relationship coefficient between each target element and the phase composition.

[0074] In this step, for any target element, the mass of the dissolved sediment is calculated using the concentration value of the target element when the solubility of the cleaning agent solution reaches the limit and the cleaning agent volume. Combined with the extraction time of the peak concentration and the proportional relationship between the mass of the phase composition and the mass of the target element, the dissolution rate of the cleaning agent solution for each phase composition corresponding to the target element is calculated as the main basis for measuring the cleaning effect of the cleaning agent solution on the sediment sample. In the case of multiple target elements, the multiple dissolution rates of multiple phase compositions corresponding to the multiple target elements are added together to obtain the dissolution rate of the cleaning agent for cleaning the sediment.

[0075] The method for measuring the dissolution rate of a deposit by a cleaning agent provided in an embodiment of the present application uses a cleaning agent solution to be evaluated to dissolve a deposit sample on the secondary side of a steam generator, and prepares a dissolving solution as a measurement sample solution. After determining the main elements and their phase composition in the sediment sample, the concentration changes of the main elements in the measurement sample solution are monitored, the peak concentration of the target element and the time point when the peak value is reached are measured, and then the dissolution rate of the cleaning agent solution is calculated as a reference for measuring the cleaning efficiency of the cleaning agent for cleaning the deposit, thereby judging whether the cleaning agent being evaluated is suitable for real-time application scenarios, which helps to select the most effective cleaning agent to meet actual needs.

[0076] Further, as a refinement and expansion of the specific implementation of the above embodiment, in order to fully illustrate the specific implementation process of this embodiment, the embodiment of this application provides another method for measuring the dissolution rate of the deposit by the cleaning agent, such as Figure 2 As shown, the method includes:

[0077] S201. Obtain a sediment sample from the equipment to be cleaned.

[0078] In this step, an appropriate mass of sediment from the equipment to be cleaned is collected for evaluation of the cleaning efficiency of the cleaning agent.

[0079] In actual application scenarios, the equipment to be cleaned can be the secondary side of the steam generator. During the shutdown of a nuclear power plant, a high-pressure water gun is used to flush the secondary side sediments, and the mud sediments are collected and dried. Afterwards, a certain mass of sediment samples are extracted as samples to be cleaned.

[0080] S202. Perform element quantitative analysis on the sediment sample using element quantitative analysis technology to obtain multiple mass contents of multiple elements in the sediment sample.

[0081] S203. Using X-ray Diffraction (XRD) technology, perform phase analysis on the sediment sample to determine the phase composition corresponding to each element.

[0082] S204. Calculate the mass relationship coefficient between each element and its corresponding phase composition.

[0083] S205. Multiply the mass content of each element by the mass relationship coefficient to obtain the mass content of the phase composition corresponding to each element in the sediment sample.

[0084] S206, sorting the multiple mass contents in descending order, and adding each mass content in sequence starting from the mass content of the first position, and when the sum of the mass contents reaches a preset threshold, obtaining at least one target element corresponding to at least one physical phase composition contained in the sum of the mass contents.

[0085] In steps S202 to S206, the content of the component elements in the sediment sample is quantitatively analyzed using element quantitative analysis technology to obtain multiple mass contents of multiple elements in the sediment sample. Optionally, the element quantitative analysis technology can be X-ray fluorescence analysis or inductively coupled plasma emission spectrometry.

[0086] Furthermore, X-ray diffraction analysis can determine the various crystalline phases present in the sediment, including oxides, sulfides, salts, etc. By comparing the diffraction pattern of each element with the standard data of various crystalline phases in the database, the phase composition corresponding to each element in the sediment can be accurately determined.

[0087] Furthermore, the relative atomic mass of each element and the molar mass of its corresponding phase composition are obtained, and the mass relationship coefficient between the element and the phase composition is calculated using the relative atomic mass and molar mass. Then, the mass content of each element is multiplied by the mass relationship coefficient to obtain the mass content of its corresponding phase composition in the sediment sample. Thereafter, in order to measure the main elements in the sediment sample, the multiple mass contents of the various phase compositions are sorted in order from large to small, starting from the mass content of the first position, each mass content is added in turn, and the sum of the mass contents is calculated. When the sum of the mass contents reaches the preset threshold, it can be determined that at least one target element in the sum of the mass contents is the main element in the sediment sample.

[0088] In the actual application scenario, a certain mass of sediment samples from the secondary side of the steam generator is weighed with an analytical balance, and the contents of the main component elements of the sediment samples are quantitatively analyzed using instrumental analysis techniques (such as X-ray fluorescence spectroscopy, inductively coupled plasma emission spectroscopy, etc.). As shown in Table 1, the results of the element content analysis in the sediment samples show that the mass proportion of iron is 70.11%.

[0089] Inspection elements Test results (%) Iron (Fe) 70.11 Nickel (Ni) 0.45 Manganese (Mn) 0.42 Chromium (Cr) 0.29 Titanium (Ti) 0.24 Zinc (Zn) 0.16 Silicon (Si) 0.15 Cobalt (Co) 0.11 Aluminum (Al) 0.10

[0090] Table 1

[0091] Furthermore, the elements in the sediment may exist in various forms. For example, iron oxides (such as FeO, Fe 2 O 3 , Fe 3 O 4 The most common form is iron carbonate, iron sulfide and other forms. The XRD spectrum of the iron element in the sediment sample is obtained by using an X-ray diffractometer to analyze the physical properties of the sediment sample to show the physical phase information of the iron element in the sediment sample. Afterwards, the standard XRD data of the various forms of iron that may exist are compared with the sample XRD spectrum one by one, and the position and intensity of the diffraction peaks are compared to find the standard data that matches the XRD spectrum. Figure 3 The XRD patterns of the sediment samples and Fe 3 O 4 The comparison chart of standard XRD data from Figure 3 It can be seen that the experimental data are consistent with Fe 3 O 4 The standard XRD data is very consistent with that of Fe, and it is thus determined that the iron element in the sediment sample is Fe 3 O 4 exists in the form of.

[0092] Further, the calculation of iron and Fe 3 O 4 The mass relationship coefficient between them is 1.378. The mass content of iron (70.11%) is multiplied by 1.378 to obtain Fe 3 O 4 The mass content of Fe in the sediment is 96.61%. 3 O 4 If the mass content of has exceeded the preset threshold, it can be determined that iron is the main component in the sediment. Therefore, the cleaning efficiency of the cleaning solution on the sediment sample can be measured by the dissolution rate of iron.

[0093] S207, adding a first preset volume of cleaning agent solution into a three-necked flask of preset specifications, and immersing the liquid part of the three-necked flask below the silicone oil liquid level.

[0094] S208, heating the silicone oil to obtain the temperature value of the cleaning agent solution in the three-necked flask.

[0095] S209, when the temperature value reaches and maintains the preset temperature value of the preset cleaning condition of the cleaning agent, adding a first preset mass of the sediment sample into the three-necked flask and stirring, so that the cleaning agent solution dissolves the sediment sample to obtain a dissolved mixture.

[0096] In steps S207 to S209, a cleaning solution of a first preset volume is weighed and added to a three-necked flask of preset specifications, the solution at the bottom of the flask is immersed below the silicone oil liquid level, and the silicone oil is heated to a preset temperature value so that the temperature of the cleaning solution reaches and maintains the temperature required by the cleaning process. Thereafter, a sediment sample of a first preset mass is added to the three-necked flask so that the cleaning solution in the flask dissolves the sediment sample. The dissolution of the sediment requires a certain amount of time. During the dissolution process, the three-necked flask includes a supernatant obtained by mixing the cleaning solution and the sediment sample, and a portion of the sediment that has not yet dissolved at the bottom of the supernatant.

[0097] In actual application scenarios, the specification of the three-necked flask is 500 ml. The top opening of the three-necked flask is used to place the stirring shaft and impeller of the mechanical stirrer, and the other two openings are used to place the thermometer and analyze the sample sampling. The preset cleaning conditions include the rotation speed of the stirring shaft and the temperature of the cleaning agent. When the temperature in the three-necked flask reaches and maintains the cleaning agent temperature, the sediment sample is placed in the three-necked flask, and the stirring shaft is controlled to stir at the set speed to fully mix the sediment and the cleaning agent.

[0098] S210, determining multiple extraction times according to a preset time interval;

[0099] S211. When the sediment sample is added into the three-necked flask, start timing to obtain the dissolution time;

[0100] S212, when the dissolution time reaches each extraction moment, extract a second preset volume of supernatant from the dissolution mixture into a centrifuge tube, and add a second preset volume of cleaning agent solution into the three-necked flask.

[0101] In S210 to S212, in order to measure the peak concentration and the time of arrival during the dissolution process, multiple extraction times are determined according to a preset time interval. When the sediment sample is added to the three-necked flask, the cleaning solution begins to dissolve the sediment sample, and the timing of obtaining the dissolution time of the cleaning solution begins. When the dissolution time reaches any extraction time, a second preset volume of supernatant is extracted from the dissolved mixture to measure the ion concentration at each extraction time. After the supernatant is extracted each time, the cleaning solution is added to the three-necked flask according to the second preset volume to prevent the reduction of the supernatant volume from affecting the dissolution reaction rate.

[0102] Optionally, the value range of the preset time interval can be set according to the experimental design and the reference time range of the cleaning agent dissolution. For example, under normal circumstances, the cleaning process of the cleaning agent may need to be maintained for 8 to 12 hours. The initial dissolution reaction is faster, so the range of the preset time interval can be set shorter in the initial stage. For example, the extraction time intervals for the first three times are every 10 minutes, that is, when the dissolution time is 10 minutes, 20 minutes and 30 minutes, the dissolved solution is extracted once respectively. Thereafter, the dissolution reaction tends to stabilize, and the extraction time interval can be stabilized at 30 minutes, that is, the dissolved solution is extracted every 30 minutes thereafter until 8.5 hours.

[0103] S213. Add a detergent solution into each centrifuge tube according to a preset dilution multiple to dilute the supernatant in each centrifuge tube to obtain a dissolved solution.

[0104] In this step, since the volume of the solution sample is limited, the volume of the supernatant extracted each time is small. In order to ensure the concentration measurement result, the supernatant is diluted with a cleaning agent solution according to a preset dilution multiple to obtain a diluted dissolved solution.

[0105] Optionally, the preset dilution multiple can be five times, ten times, etc. According to the preset dilution multiple, the added volume of the cleaning agent is calculated, and the cleaning agent solution is dripped into the centrifuge tube according to the added volume to dilute the supernatant. In an embodiment of the present application, optionally, in order to ensure the accuracy of the concentration value measurement result, according to the quantitative standard curve of the target element, the preset dilution multiple and a plurality of dissolving solutions, the maximum concentration value of each target element in each supernatant, and before the target extraction time corresponding to the maximum concentration value are determined, it also includes: obtaining a standard solution of the target element of a first preset concentration; diluting the standard solution with a cleaning agent solution to obtain a plurality of dilution solutions of a plurality of second preset concentrations; using a quantitative detection method, measuring the first signal intensity value of each dilution solution; drawing a quantitative standard curve of the target element according to the plurality of second preset concentrations and the plurality of first signal intensity values.

[0106] In this embodiment, in order to accurately measure the concentration change of the target element in the dissolved solution, it is necessary to construct a quantitative standard curve in advance using a standard solution of the target element. Specifically, the first preset concentration is the concentration value of the required standard solution of the target element, and the concentration value needs to be higher than the maximum concentration of the target element in the dissolved solution, so that the concentration in the drawn quantitative standard curve can cover the concentration change range of the target element in the dissolved solution. Thereafter, in order to ensure that the curve has enough data points to characterize the correspondence between concentration and signal intensity, multiple different second preset concentration values ​​are selected to prepare a dilution solution, and these concentrations cover three concentration ranges of lower concentration, medium concentration and higher concentration. After selecting multiple second preset concentration values, the standard solution is diluted with a detergent solution based on each second preset concentration value to obtain a dilute solution.

[0107] Furthermore, the fluorescence intensity value (first signal intensity value) of each diluted solution is measured by X-ray fluorescence spectrometry or other appropriate quantitative methods, and the first signal intensity value of each diluted solution and the corresponding second preset concentration are recorded. Thereafter, the first signal intensity value of the target element of each diluted solution is used as the y-axis, and the corresponding second preset concentration is used as the x-axis to draw a quantitative standard curve, ensuring that the curve has a good linear relationship within the concentration range.

[0108] In actual application scenarios, the maximum concentration of the target element in the dissolved solution is confirmed by prior analysis data or literature, and the first preset concentration is determined based on the maximum concentration to ensure that the first preset concentration exceeds the maximum concentration of the target element. For example, if the maximum concentration of the target element is 15000 mg / L, then the first preset concentration of the purchased standard solution can be 20000 mg / L. Then, according to the first preset concentration and the first preset volume, a standard solution of the target element is purchased. Thereafter, according to the first preset concentration, multiple second preset concentrations are set, such as 2000 mg / L, 5000 mg / L, 10000 mg / L, 15000 mg / L and 20000 mg / L, and the corresponding cleaning agent solutions are weighed according to the multiple second preset concentrations, and the standard solution is adjusted to each second preset concentration through appropriate mixing and dilution steps to obtain multiple diluted solutions.

[0109] S214. Measure the second signal intensity value of each dissolved solution using a quantitative detection method.

[0110] S215 . Determine the first concentration value corresponding to each second signal intensity value according to the quantitative standard curve.

[0111] S216. Multiply each first concentration value by the preset dilution factor to obtain a second concentration value of the target element in the first dissolved solution.

[0112] S217, obtaining the maximum concentration value of the target element in the first dissolving solution, and the target extraction time corresponding to the maximum concentration value.

[0113] In steps S214 to S217, the second signal intensity value of each dissolved solution is measured by X-ray fluorescence spectrometry or other appropriate quantitative methods, and the first concentration value corresponding to each second signal intensity value is determined in the quantitative standard curve. Since the first concentration value is the ion concentration in the diluted dissolved solution, in order to obtain the concentration of the target element in the first dissolved solution before dilution, it is necessary to multiply each second concentration value by the preset dilution multiple to obtain the concentration of the target element in the first dissolved solution before dilution. Thereafter, the peak concentration value and the extraction time point when the cleaning solution has the strongest dissolving ability are obtained. Then, the dissolution rate of the deposit by the cleaning solution is calculated using the peak concentration value and the target extraction time.

[0114] In an embodiment of the present application, optionally, in order to ensure the accuracy of the dissolution rate calculation, the method also includes: obtaining the relative atomic mass of each element and the molar mass of its corresponding phase composition; and calculating the mass relationship coefficient between each element and its corresponding phase composition through the molar mass and relative atomic mass.

[0115] In this embodiment, the relative atomic mass of the main target element can be determined by the molar mass of the constituent phase, and then the relationship coefficient between the mass of the constituent phase and the mass of the target element in the dissolved solution can be obtained. The dissolved amount of the constituent phase can be inferred from the concentration data of the target element obtained experimentally, thereby achieving quantitative measurement of the dissolution rate.

[0116] S218, multiplying the mass relationship coefficient, the maximum concentration value and the first preset volume of each target element, and dividing the multiplied value by the target extraction time to obtain the dissolution rate of the cleaning solution for the phase composition corresponding to each target element;

[0117] S219. In the case where there are multiple at least one target element, multiple dissolution rates of multiple phase compositions corresponding to the multiple target elements are added together to obtain the dissolution rate of the deposit by the cleaning solution.

[0118] In steps S218 and S219, for any target element, the first preset volume of the cleaning agent is multiplied by the maximum concentration value to obtain the mass of the dissolved sediment, and then the mass of the sediment is multiplied by the mass relationship coefficient and divided by the target extraction time (expressed in minutes) corresponding to the maximum concentration value to obtain the dissolution rate of the cleaning agent solution for the phase composition corresponding to the target element.

[0119] Furthermore, if there is only one main target element in the sediment, the dissolution rate of the phase composition corresponding to the main element is directly used as the cleaning efficiency of the cleaning agent for cleaning the sediment; if the main target elements in the sediment contain two or more, after calculating the dissolution rate of the phase composition corresponding to each target element, the multiple dissolution rates are added together as the dissolution rate of the cleaning agent solution for cleaning the sediment.

[0120] Further, as a refinement and extension of the specific implementation of the above embodiment, in order to fully illustrate the specific implementation process of this embodiment, the embodiment of the present application provides another method for measuring the dissolution rate of the deposit by the cleaning agent, which includes the following six steps:

[0121] Step 1: Collection of sediment samples and quantitative analysis of main component elements and phase analysis of sediment samples.

[0122] Step 2: Prepare the cleaning solution.

[0123] Specifically, the chemical cleaning agent solution for the secondary side of the steam generator can be prepared according to the literature, or the cleaning agent solution can be directly purchased from the market.

[0124] Step 3: Preparation of experimental instruments.

[0125] Specifically, 200 ml of the cleaning agent solution is extracted and added to a 500 ml three-necked flask, and the bottom of the flask is immersed below the silicone oil level. The top opening of the three-necked flask is used to place the stirring shaft and impeller of the mechanical stirrer, and the other two openings are used as the opening for placing the thermometer and the sampling opening for the analysis sample. The silicone oil is heated to make the temperature of the cleaning agent solution reach and maintain the temperature required by the cleaning process.

[0126] Step 4: After the cleaning solution reacts with the sediment sample, the concentration of iron in the supernatant is determined.

[0127] Specifically, 6 grams of dry secondary sediment sample was placed in a three-necked flask, and the preset time intervals were obtained. Every 10 minutes, 20 minutes and 0.5, 1, 1.5, 2, 2.5, 3, 3.5, 4, 4.5, 5, 5.5, 6, 6.5, 7, 7.5, 8, 8.5 hours, 1 ml of the supernatant in the three-necked flask was placed in a centrifuge tube and diluted. Thereafter, a standard solution of Fe element was prepared using the detergent solution as a matrix. A quantitative standard curve of Fe element was established by X-ray fluorescence spectrometry. Figure 4As shown, it is a quantitative standard curve of the Fe element, wherein, based on the 8 preset second concentrations, the signal intensity value corresponding to each second preset concentration is measured, and then the standard curve is drawn according to the corresponding relationship between the signal intensity value and the concentration. Finally, the Fe element concentration in the centrifuge tube sampled at different extraction time points is measured using the quantitative standard curve, and then the Fe concentration in the three-necked flask is obtained.

[0128] Step 5: Draw a curve of the relationship between Fe concentration and time in the three-necked flask to determine the peak Fe concentration and its extraction time.

[0129] Specifically, Figure 5 As shown, it is a curve diagram of the relationship between Fe concentration and extraction time during the cleaning process of the cleaning solution. Multiple extraction times are used as the x-axis and multiple Fe concentrations are used as the y-axis to draw a relationship curve diagram. From the figure, the dissolution change of the cleaning solution can be clearly seen, and then the extraction time when the Fe element concentration reaches the peak can be determined.

[0130] Step 6: Calculation of sediment cleaning efficiency.

[0131] Specifically, the mass of the dissolved Fe element is calculated based on the peak concentration of the Fe element in the first dissolving solution when the Fe element no longer increases and the first preset volume extracted by the cleaning solution, and then the mass of the dissolved Fe element, the Fe 3 O 4 The relationship coefficient between the mass of the Fe element and the time point when the dissolving power is the strongest is used to calculate the dissolution rate of the cleaning agent, that is, the dissolution rate of the cleaning agent on Fe 3 O 4 cleaning efficiency.

[0132] Cleaning agent for Fe 3 O 4 The calculation formula for the cleaning efficiency is:

[0133]

[0134] Wherein, the above p is the cleaning efficiency, in mg / min; the above c is the maximum concentration value, in μg / ml; the above v is the first preset volume (ignoring the change in the cleaning agent volume caused by sampling), in ml; the above k is the dissolved Fe 3 O 4 The relationship coefficient between the mass of and the mass of Fe element in the solution is a constant 1.378, with the unit of 1; the above t is the target extraction time when the Fe element concentration reaches the peak value, with the unit of minutes.

[0135] By the above method, the concentration of related ions in the dissolved solution is measured, the relationship between the ion concentration and time is established, the dissolution rate of the cleaning agent is calculated, and the cleaning efficiency of the cleaning agent on the secondary side of the steam generator is determined.

[0136] Those skilled in the art will appreciate that the accompanying drawings are merely schematic diagrams of a preferred implementation scenario, and the modules or processes in the accompanying drawings are not necessarily required for implementing the present application.

[0137] The above application serial numbers are for description only and do not represent the advantages or disadvantages of the implementation scenarios.

[0138] The above disclosure only discloses several specific implementation scenarios of the present application. However, the present application is not limited thereto, and any changes that can be conceived by technicians in this field should fall within the scope of protection of the present application.

Claims

1. A method for measuring the dissolution rate of a cleaning agent on a sediment, characterized in that: include: Obtaining multiple elements contained in the sediment sample to be cleaned, the phase composition corresponding to each element, and the mass content of each phase composition in the sediment sample; Sort the multiple mass contents in descending order, add each mass content in sequence starting from the mass content of the first position, and when the sum of the mass contents reaches a preset threshold, obtain at least one target element corresponding to at least one phase composition contained in the sum of the mass contents; Mixing a first preset mass of the sediment sample and a first preset volume of a cleaning agent solution, so that the sediment and the cleaning agent solution undergo a dissolution reaction under preset cleaning conditions to obtain a dissolved mixture, wherein the dissolved mixture includes a supernatant and undissolved sediments; extracting a plurality of supernatants from the dissolved mixture according to a preset time interval and a second preset volume; Diluting a plurality of supernatants using the cleaning agent solution according to a preset dilution multiple to obtain a plurality of dissolved solutions; Determine the maximum concentration value of each target element in each supernatant and the target extraction time corresponding to the maximum concentration value according to the quantitative standard curve of each target element, the preset dilution factor and the multiple dissolving solutions, wherein the quantitative standard curve shows the corresponding relationship between the signal intensity measured by the quantitative instrument and the concentration of the target element; The dissolution rate of the deposit by the cleaning solution is calculated according to the first preset volume, the maximum concentration value corresponding to each target element, the target extraction time corresponding to each target element, and the mass relationship coefficient between each target element and the phase composition.

2. The method according to claim 1, characterized in that The step of obtaining a plurality of elements contained in the sediment sample to be cleaned, the phase composition corresponding to each element, and the mass content of each phase composition in the sediment sample specifically includes: obtaining the sediment sample in the equipment to be cleaned; Using element quantitative analysis technology, performing element quantitative analysis on the sediment sample to obtain multiple mass contents of multiple elements in the sediment sample; Using X-ray Diffraction (XRD) technology, the sediment sample is subjected to phase analysis to determine the phase composition corresponding to each element; Calculating the mass relationship coefficient between each element and its corresponding phase composition; The mass content of each element is multiplied by the mass relationship coefficient to obtain the mass content of the phase composition corresponding to each element in the sediment sample.

3. The method according to claim 1, characterized in that The step of mixing the sediment sample of a first preset mass and the cleaning agent solution of a first preset volume so that the sediment and the cleaning agent solution undergo a dissolution reaction under preset cleaning conditions to obtain a dissolved mixture specifically includes: Adding the first preset volume of the cleaning agent solution into a three-necked flask of preset specifications, and immersing the bottom solution portion of the three-necked flask below the silicone oil; Heating the silicone oil to obtain the temperature value of the cleaning agent solution in the three-necked flask; When the temperature value reaches and maintains the preset temperature value of the preset cleaning condition of the cleaning agent, the first preset mass of the sediment sample is added into the three-necked flask and stirred, so that the cleaning agent solution dissolves the sediment sample to obtain the dissolved mixture.

4. The method according to claim 3, characterized in that The step of extracting a plurality of supernatants from the dissolved mixture according to a preset time interval and a second preset volume specifically comprises: Determining multiple extraction moments according to the preset time interval; When the sediment sample is added into the three-necked flask, the timing is started to obtain the dissolution time; When the dissolution time reaches each extraction moment, the second preset volume of supernatant is extracted from the dissolution mixture into a centrifuge tube, and the second preset volume of the cleaning agent solution is added into the three-necked flask.

5. The method according to claim 4, characterized in that The step of diluting each supernatant with the cleaning solution according to a preset dilution multiple to obtain a plurality of dissolved solutions specifically includes: According to the preset dilution multiple, the cleaning agent solution is added into each centrifuge tube to dilute the supernatant in each centrifuge tube to obtain a dissolved solution.

6. The method according to claim 1, characterized in that The method further comprises: determining the maximum concentration value of each target element in each supernatant according to the quantitative standard curve of each target element, the preset dilution multiple and the plurality of dissolving solutions, and before the target extraction time corresponding to the maximum concentration value. Obtaining a standard solution of a target element with a first preset concentration; Diluting the standard solution with the cleaning solution to obtain a plurality of diluted solutions with a plurality of second preset concentrations; Using a quantitative detection method, measuring a first signal intensity value of each diluted solution; The quantitative standard curve of the target element is drawn according to the multiple second preset concentrations and the multiple first signal intensity values.

7. The method according to claim 1, characterized in that The step of determining the maximum concentration value of each target element in each supernatant and the target extraction time corresponding to the maximum concentration value according to the quantitative standard curve of the target element, the preset dilution multiple and the multiple dissolving solutions specifically includes: Using a quantitative detection method, measuring the second signal intensity value of each dissolved solution; Determining the first concentration value corresponding to each second signal intensity value according to the quantitative standard curve; Multiplying the preset dilution factor by each first concentration value to obtain a second concentration value of the target element in the first dissolved solution; The maximum concentration value of the target element in the first dissolving solution and the target extraction time corresponding to the maximum concentration value are obtained.

8. The method according to any one of claims 1 to 7, characterized in that Also includes: Obtain the relative atomic mass of each element and the molar mass of its corresponding phase composition; The mass relationship coefficient between each element and its corresponding phase composition is calculated through the molar mass and the relative atomic mass.

9. The method according to any one of claims 1 to 7, characterized in that The step of calculating the dissolution rate of the deposit by the cleaning solution according to the first preset volume, the maximum concentration value corresponding to each target element, the target extraction time corresponding to each target element, and the mass relationship coefficient between each target element and the phase composition specifically includes: Multiplying the mass relationship coefficient of each target element, the maximum concentration value and the first preset volume, and dividing the multiplied value by the target extraction time to obtain the dissolution rate of the cleaning solution for the phase composition corresponding to each target element; In the case where there are multiple at least one target element, multiple dissolution rates of multiple phase compositions corresponding to the multiple target elements are added together to obtain the dissolution rate of the deposit by the cleaning solution.

10. The method according to any one of claims 1 to 7, characterized in that Elemental quantitative analysis techniques include any of the following: X-ray fluorescence analysis and inductively coupled plasma optical emission spectrometry.

Images