CN113155719A - Method for obtaining steam oxidation kinetic data of power station material in actual working condition - Google Patents
Method for obtaining steam oxidation kinetic data of power station material in actual working condition Download PDFInfo
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Abstract
The invention discloses a method for acquiring steam oxidation kinetic data of a power station material in an actual working condition. The method meets the rule of an Arrhenius formula by utilizing the relation between the thickness of an oxidation layer of a heat-resistant material of the power station and oxidation time and temperature, samples and collects unit operation data by selecting a specific position, converts the operation time at the actual operation temperature into the equivalent operation time at the temperature to be calculated by utilizing the Arrhenius formula, obtains steam oxidation kinetic data of the boiler material of the power station in the actual operation condition, and has important significance for the service life evaluation of key parts of the unit, the service life of the unit and the like.
Description
Technical Field
The invention belongs to the field of metal material corrosion test methods, and particularly relates to a method for acquiring steam oxidation kinetic data of a power station material in an actual working condition.
Background
Steam oxidation kinetic curves of heat-resistant materials at different temperatures are of great significance to material selection design of a thermal power generating unit and service life evaluation of components in the operation process, the current obtaining method is generally obtained by establishing a test device in a laboratory and placing the materials in steam at a specific temperature for oxidation for different times, the data have certain significance, but due to great difference from actual operation conditions, the method has the defects which are difficult to overcome, and the main problems comprise: 1) some materials form volatile oxides in steam, and in an actual boiler, the volatile oxides can be taken away by the steam, but if the steam flow of a laboratory test device is too low, the partial pressure of the volatile oxides in the steam is increased to inhibit the continuous volatilization of the oxides, so that the oxidation rate and the structure of an oxide layer are possibly obviously different from those under the actual operation condition; 2) the water chemical conditions of a laboratory are greatly different from those of an actual boiler, for example, in order to solve the problem of flow accelerated corrosion of water side parts, the boilers above the supercritical state mostly adopt an oxygenation process, although a laboratory device can simulate the oxygenation or total volatilization treatment conditions of water by removing oxygen through inert gas or adding oxygen into the water, the PH value, trace ion content and the like of the water are still greatly different from the water quality of the actual power station boiler; 3) the pressure of the laboratory steam is difficult to reach the operating steam pressure in the actual power station boiler, so that the oxygen partial pressure of the steam in the laboratory test and the actual boiler is greatly different; 4) because 24 hours of uninterrupted time is needed in a laboratory test, a large amount of labor and material load is caused, the cost is high, the test can be generally carried out for thousands of hours at the longest, the long-time test cannot be carried out, and the reliability of extrapolated data is poor. Due to the mutual influence of the factors, the oxidation dynamics data obtained in a laboratory are large in limitation in actual use, and even great errors can be generated on part material selection and service life evaluation results, so that risks are brought to unit operation.
The relation between the thickness of the oxide layer of some materials and the operation time can be obtained through sampling and analyzing the operated components, but because the unit is influenced by the requirements of a power grid end, coal types and the like in the operation process, the operation condition of the unit is continuously changed, and the temperature and the pressure are in disorder fluctuation in a certain range along with the time, the oxide layer data obtained by pipe cutting are scattered, and the accurate relation between the thickness of the oxide layer and the temperature and the operation time cannot be obtained.
Disclosure of Invention
The invention aims to solve the problems in the prior art and provides a method for acquiring steam oxidation kinetic data of a power station material in actual working conditions.
The invention is realized by the following technical scheme:
the method for obtaining the steam oxidation kinetic data of the power station material in the actual working condition comprises the following steps:
1) selecting a sampling position according to the installation position of the boiler temperature measuring point, the temperature level under the operation condition and the field condition;
2) cutting a pipe at a preset sampling position for sampling in the unit maintenance process;
3) cutting the sample to a proper size, preparing a metallographic specimen, and observing and measuring the average thickness of an oxide layer by using a microscope;
4) obtaining the temperature record of the time from the beginning of the sample operation to the tube cutting through the operation monitoring system, and converting the equivalent time at the required calculated temperature by using an Arrhenius formula;
5) and drawing the equivalent time of a plurality of samples as an abscissa and the average thickness of the oxide layer as an ordinate to obtain an oxidation kinetic curve.
A further development of the invention is that, in step 1), the selection of the sampling position follows the following principle:
the furnace is provided with a part with stronger heat exchange, and the distance from the sampling position to the temperature measuring point is not more than 0.5 m;
the distance from the sampling position to a temperature measuring point is not more than 1 meter, the distance to the ceiling is not less than 0.5 meter, and the distance to the header is not less than 0.5 meter;
the sampling location includes a pipe with a relatively high temperature level, resulting in longer equivalent time data;
if conditions allow for multiple tube samples to be taken simultaneously, there is a significant difference in temperature level at each sampling location, so that there is a difference in the equivalent time of conversion.
The invention has the further improvement that in the step 3), the sample cutting adopts a cutting mode with small damage to an oxide layer by electric spark cutting, and the damaged part caused by cutting the pipe on site is removed.
The further improvement of the invention is that in the step 3), the oxide layer is protected before the metallographic specimen is prepared by the sample, and the protection comprises cold embedding, hot embedding and metal layer electroplating.
The invention is further improved in that in the step 3), the measurement of the average thickness of the oxide layer is carried out by selecting not less than 5 complete fields of view of the oxide layer.
The invention is further improved in that in the step 4), the time interval between two temperature recording points is not less than 30 seconds and not more than 1 hour, so that the change condition of the historical operating temperature of the sample can be fully reflected by the temperature data, and the data amount is not too large.
A further improvement of the present invention is that, in step 4), the Arrhenius formula for calculating the equivalent operating time is:
wherein T isEquivalence ofTarget Oxidation kinetics Curve temperature, tEquivalence ofIs the equivalent time at the target temperature, tiTime interval for temperature recording, TiThe value recorded for the ith temperature, Q is the diffusion activation energy of the material and R is the gas constant.
The invention further improves that in the step 1), a plurality of samples with the number not less than 3 are obtained by taking samples with different temperature levels at the same time or taking samples for multiple times at the same position.
The invention has at least the following beneficial technical effects:
the method for obtaining the steam oxidation kinetic data of the power station material in the actual working condition utilizes the relation between the oxidation time and the temperature of the heat-resistant material of the power station to generally meet the rule of an Arrhenius formula, converts the running time at the actual running temperature into the equivalent time at the temperature to be calculated by utilizing the Arrhenius formula, obtains the steam oxidation kinetic data of the power station boiler material in the actual running working condition, and has important significance for the service life evaluation of key parts of a unit, the service life of the unit and the like. Compared with the prior art, the solution of the invention can obtain oxidation dynamics data of a large amount of materials under the actual operation working condition with very low cost, saves manpower and material resources, is more in line with the actual unit than laboratory data because the data is real data under the actual working condition, and is more reliable for unit material selection and part service life evaluation and unit service life extension.
Drawings
FIG. 1 is a schematic view of a sampling site.
Fig. 2 is a schematic diagram of temperature recording.
Fig. 3 is a metallographic photograph of the oxide layer.
Figure 4 is a graphical representation of oxidation kinetics data.
Detailed Description
Exemplary embodiments of the present disclosure will be described in more detail below with reference to the accompanying drawings. While exemplary embodiments of the present disclosure are shown in the drawings, it should be understood that the present disclosure may be embodied in various forms and should not be limited to the embodiments set forth herein. Rather, these embodiments are provided so that this disclosure will be thorough and complete, and will fully convey the scope of the disclosure to those skilled in the art. It should be noted that the embodiments and features of the embodiments may be combined with each other without conflict. The present invention will be described in detail below with reference to the embodiments with reference to the attached drawings.
Example 1
The sample is a T92 steel connection tube of a final-stage reheater header of a certain unit, the position is in a furnace top hot chamber, no heat exchange is caused in the normal operation process of the unit, a monitoring thermocouple is installed, a tube is cut and sampled at the position shown in figure 1, the distance from the ceiling exceeds 0.5 m, the influence of heat conduction of a tube section in a furnace is avoided, the distance from a fillet weld of the header exceeds 0.5 m, the sampling does not influence the header, the influence of heat conduction of the wall of a thick-wall tube of the header is avoided, and the actual temperature of the sampling position is consistent with the temperature record of the thermocouple. In total, 2 samples were taken during two blow-outs, the temperature profile of one sample being shown in FIG. 2, and the equivalent time at 620 ℃ being calculated for each temperature profile by the Arrhenius equation.
After sampling, cutting the sample to a proper size by using electric sparks, protecting the edge and an oxide layer of the sample by adopting hot inlaying, then pre-grinding by using sand paper with different particle sizes and polishing by using diamond polishing paste, observing by using a metallographic microscope, taking a typical picture as shown in figure 3, taking pictures of not less than 5 fields of view, measuring and calculating the average thickness.
The oxidation kinetics curve was obtained using the 620 ℃ equivalent time of each sample as the abscissa and the average thickness of the tube as the ordinate, see fig. 4.
Although the invention has been described in detail hereinabove with respect to a general description and specific embodiments thereof, it will be apparent to those skilled in the art that modifications or improvements may be made thereto based on the invention. Accordingly, such modifications and improvements are intended to be within the scope of the invention as claimed.
Claims (8)
1. The method for acquiring steam oxidation kinetic data of the power station material in the actual working condition is characterized by comprising the following steps of:
1) selecting a sampling position according to the installation position of the boiler temperature measuring point, the temperature level under the operation condition and the field condition;
2) cutting a pipe at a preset sampling position for sampling in the unit maintenance process;
3) cutting the sample to a proper size, preparing a metallographic specimen, and observing and measuring the average thickness of an oxide layer by using a microscope;
4) obtaining the temperature record of the time from the beginning of the sample operation to the tube cutting through the operation monitoring system, and converting the equivalent time at the required calculated temperature by using an Arrhenius formula;
5) the equivalent time of the plurality of samples is plotted as abscissa and the average thickness of the oxide layer is plotted as ordinate, and the oxidation kinetics curve at the calculated temperature is obtained.
2. The method for obtaining steam oxidation kinetic data of power station materials in actual working conditions according to claim 1, characterized in that, in step 1), the selection of sampling positions follows the following principle:
the furnace is provided with a part with stronger heat exchange, and the distance from the sampling position to the temperature measuring point is not more than 0.5 m;
the distance from the sampling position to a temperature measuring point is not more than 1 meter, the distance to the ceiling is not less than 0.5 meter, and the distance to the header is not less than 0.5 meter;
the sampling location includes a pipe with a relatively high temperature level, resulting in longer equivalent time data;
if conditions allow for multiple tube samples to be taken simultaneously, there is a significant difference in temperature level at each sampling location, so that there is a difference in the equivalent time of conversion.
3. The method for obtaining the steam oxidation kinetic data of the power station material in the actual working condition according to the claim 1, characterized in that in the step 3), the sample cutting adopts a cutting mode with small damage to an oxide layer by electric spark cutting, and a damaged part caused by cutting a pipe on site is removed.
4. The method for obtaining steam oxidation kinetic data of power station materials in practical conditions according to claim 1, characterized in that in step 3), the oxide layer is protected before the metallographic sample is prepared by the sample, and the protection comprises cold setting, hot setting and metal layer plating.
5. The method for obtaining steam oxidation kinetic data of a power station material in real working conditions according to claim 1, characterized in that in step 3), the measurement of the average thickness of the oxide layer is performed with a complete field of view of not less than 5 oxide layers.
6. The method for obtaining steam oxidation kinetic data of a power station material in an actual working condition according to claim 1, characterized in that in the step 4), the time interval between two temperature recording points is not less than 30 seconds and not more than 1 hour, so that the temperature data can sufficiently reflect the change condition of the historical operating temperature of the sample, and the data amount is not too large.
7. The method for obtaining steam oxidation kinetic data of power station materials in actual conditions according to claim 1, characterized in that, in the step 4), the Arrhenius formula for calculating the equivalent operation time is as follows:
wherein T isEquivalence ofTarget Oxidation kinetics Curve temperature, tEquivalence ofIs the equivalent time at the target temperature, tiTime interval for temperature recording, TiThe value recorded for the ith temperature, Q is the diffusion activation energy of the material and R is the gas constant.
8. The method for obtaining steam oxidation kinetic data of a power station material in practical conditions according to claim 1, characterized in that in step 1), a plurality of samples with the number not less than 3 are obtained by taking samples with different temperature levels at the same time or by taking samples at the same position for a plurality of times.
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| CN202110412686.5A CN113155719B (en) | 2021-04-16 | 2021-04-16 | Method for obtaining steam oxidation kinetic data of power station material in actual working condition |
| PCT/CN2021/115549 WO2022217810A1 (en) | 2021-04-16 | 2021-08-31 | Method for obtaining steam oxidation kinetics data of power station material under actual operation condition |
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| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN114137178A (en) * | 2021-11-23 | 2022-03-04 | 华能国际电力股份有限公司 | Steam oxidation resistance testing method for high-temperature alloy welded joint |
| WO2022217810A1 (en) * | 2021-04-16 | 2022-10-20 | 西安热工研究院有限公司 | Method for obtaining steam oxidation kinetics data of power station material under actual operation condition |
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| CN117558351A (en) * | 2023-11-23 | 2024-02-13 | 中国人民解放军96901部队23分队 | Method for constructing oxidation kinetics curve of plutonium metal |
Citations (9)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2000292419A (en) * | 1999-04-06 | 2000-10-20 | Babcock Hitachi Kk | Method and device for evaluating remaining life of creep in heat transfer pipe |
| US20060025936A1 (en) * | 2004-07-30 | 2006-02-02 | Siemens Westinghouse Power Corporation | Method of estimating oxidation progression in coated turbine components |
| CN1971262A (en) * | 2006-12-07 | 2007-05-30 | 复旦大学 | An in-situ token method of dynamics rule of metal film oxidation reaction |
| CN106874641A (en) * | 2016-12-15 | 2017-06-20 | 中国航天空气动力技术研究院 | Silicon nitride passive oxidation model experiment method of calibration and oxidated layer thickness influence factor determine method |
| US20180340897A1 (en) * | 2017-05-24 | 2018-11-29 | Board Of Trustees Of The University Of Arkansas | Techniques for Using Oxide Thickness Measurements for Predicting Crack Formation and Growth History in High-Temperature Metallic Components |
| CN109870295A (en) * | 2019-02-20 | 2019-06-11 | 华电电力科学研究院有限公司 | A kind of online service life evaluation system of thermal power plant jet chimney and method |
| CN111161806A (en) * | 2019-12-30 | 2020-05-15 | 国电科学技术研究院有限公司 | Method for calculating oxide film thickness of martensite heat-resistant steel under supercritical high-temperature steam |
| CN112326658A (en) * | 2020-10-30 | 2021-02-05 | 西安热工研究院有限公司 | Method for confirming parameters during equivalent temperature calculation of boiler tube |
| CN112630136A (en) * | 2021-03-09 | 2021-04-09 | 中广核三角洲（太仓）检测技术有限公司 | Nuclear PEEK cable service life assessment method |
Family Cites Families (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN103063995B (en) * | 2011-10-21 | 2015-02-11 | 北京大学 | Method for predicating reliability service life of silicon on insulator (SOI) metal-oxide -semiconductor field effect transistor (MOSFET) device |
| CN110672232A (en) * | 2019-09-20 | 2020-01-10 | 润电能源科学技术有限公司 | Method and device for correcting tube wall temperature of boiler heating surface and storage medium |
| CN112630130A (en) * | 2020-11-04 | 2021-04-09 | 江苏省沙钢钢铁研究院有限公司 | Method for detecting iron oxide on surface of hot-rolled wire rod |
| CN112597627A (en) * | 2020-11-27 | 2021-04-02 | 马鞍山钢铁股份有限公司 | Calculation method for predicting thickness of oxide layer in spring steel heating process |
| CN113155719B (en) * | 2021-04-16 | 2023-01-31 | 西安热工研究院有限公司 | Method for obtaining steam oxidation kinetic data of power station material in actual working condition |
-
2021
- 2021-04-16 CN CN202110412686.5A patent/CN113155719B/en active Active
- 2021-08-31 WO PCT/CN2021/115549 patent/WO2022217810A1/en active Application Filing
Patent Citations (9)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2000292419A (en) * | 1999-04-06 | 2000-10-20 | Babcock Hitachi Kk | Method and device for evaluating remaining life of creep in heat transfer pipe |
| US20060025936A1 (en) * | 2004-07-30 | 2006-02-02 | Siemens Westinghouse Power Corporation | Method of estimating oxidation progression in coated turbine components |
| CN1971262A (en) * | 2006-12-07 | 2007-05-30 | 复旦大学 | An in-situ token method of dynamics rule of metal film oxidation reaction |
| CN106874641A (en) * | 2016-12-15 | 2017-06-20 | 中国航天空气动力技术研究院 | Silicon nitride passive oxidation model experiment method of calibration and oxidated layer thickness influence factor determine method |
| US20180340897A1 (en) * | 2017-05-24 | 2018-11-29 | Board Of Trustees Of The University Of Arkansas | Techniques for Using Oxide Thickness Measurements for Predicting Crack Formation and Growth History in High-Temperature Metallic Components |
| CN109870295A (en) * | 2019-02-20 | 2019-06-11 | 华电电力科学研究院有限公司 | A kind of online service life evaluation system of thermal power plant jet chimney and method |
| CN111161806A (en) * | 2019-12-30 | 2020-05-15 | 国电科学技术研究院有限公司 | Method for calculating oxide film thickness of martensite heat-resistant steel under supercritical high-temperature steam |
| CN112326658A (en) * | 2020-10-30 | 2021-02-05 | 西安热工研究院有限公司 | Method for confirming parameters during equivalent temperature calculation of boiler tube |
| CN112630136A (en) * | 2021-03-09 | 2021-04-09 | 中广核三角洲（太仓）检测技术有限公司 | Nuclear PEEK cable service life assessment method |
Non-Patent Citations (3)
| Title |
|---|
| CAMILLE BLIVET等: "Thermal oxidation of cross-linked PE and EPR used as insulation materials: Multi-scale correlation over a wide range of temperatures", 《POLYMER TESTING》 * |
| 包建文: "耐高温树脂基复合材料及其应用", 《耐高温树脂基复合材料及其应用》 * |
| 唐丽英 等: "Tempaloy A-3锅炉钢管在650℃的蒸汽氧化试验研究", 《热力发电》 * |
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO2022217810A1 (en) * | 2021-04-16 | 2022-10-20 | 西安热工研究院有限公司 | Method for obtaining steam oxidation kinetics data of power station material under actual operation condition |
| CN114137178A (en) * | 2021-11-23 | 2022-03-04 | 华能国际电力股份有限公司 | Steam oxidation resistance testing method for high-temperature alloy welded joint |
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| CN113155719B (en) | 2023-01-31 |
| WO2022217810A1 (en) | 2022-10-20 |
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