WO2018168633A1 - Procédé d'évaluation de la corrosion d'un matériau métallique, et sonde - Google Patents

Procédé d'évaluation de la corrosion d'un matériau métallique, et sonde Download PDF

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Publication number
WO2018168633A1
WO2018168633A1 PCT/JP2018/008956 JP2018008956W WO2018168633A1 WO 2018168633 A1 WO2018168633 A1 WO 2018168633A1 JP 2018008956 W JP2018008956 W JP 2018008956W WO 2018168633 A1 WO2018168633 A1 WO 2018168633A1
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WO
WIPO (PCT)
Prior art keywords
metal material
probe
furnace
inclined surface
corrosion
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PCT/JP2018/008956
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English (en)
Japanese (ja)
Inventor
デディ エカ プリヤント
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株式会社Ihi
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Publication date
Application filed by 株式会社Ihi filed Critical 株式会社Ihi
Priority to JP2019505935A priority Critical patent/JP6856116B2/ja
Publication of WO2018168633A1 publication Critical patent/WO2018168633A1/fr

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    • G—PHYSICS
    • G01—MEASURING; TESTING
    • G01N—INVESTIGATING OR ANALYSING MATERIALS BY DETERMINING THEIR CHEMICAL OR PHYSICAL PROPERTIES
    • G01N33/00—Investigating or analysing materials by specific methods not covered by groups G01N1/00 - G01N31/00
    • G01N33/20—Metals
    • G01N33/208—Coatings, e.g. platings
    • G—PHYSICS
    • G01—MEASURING; TESTING
    • G01N—INVESTIGATING OR ANALYSING MATERIALS BY DETERMINING THEIR CHEMICAL OR PHYSICAL PROPERTIES
    • G01N17/00—Investigating resistance of materials to the weather, to corrosion, or to light

Definitions

  • the present disclosure relates to a method for evaluating corrosion of a metal material and a probe used in the method.
  • corrosion may proceed depending on the form of impurities in the fuel, combustion gas, etc., which are not expected, and laboratory corrosion tests may not be sufficient.
  • Corrosion when a heat transfer tube made of various candidate materials is installed at a predetermined position in the actual steam furnace and a part of the actual steam is taken out of the heat transfer tube and flowed to raise the steam temperature.
  • a method for testing the sex is also employed. However, in this method, the corrosive environment is exactly the same as the actual machine, but the cost for testing is high.
  • the present disclosure is proposed in view of the above-described circumstances, and is used for a corrosion evaluation method for a metal material that can be tested in an environment similar to that of an actual pulverized coal boiler while suppressing costs.
  • An object is to provide a probe.
  • a probe in which a metal material of a specimen is installed on an inclined surface inclined at a predetermined angle with respect to a horizontal plane is inserted into the heating furnace, and the metal material is corroded in the furnace. And a step of removing the metal material installed on the inclined surface from the probe taken out from the furnace and evaluating the corrosion amount of the metal material.
  • the heating furnace is a vertical combustion furnace, and in the step of corroding the metal material, a probe may be inserted upward in the vertical direction from the lower side of the vertical combustion furnace.
  • the angle at which the inclined surface is inclined with respect to the horizontal plane may be in the range of 30 degrees to 60 degrees.
  • the step of corroding the metal material in the furnace may also include detecting the temperature of the metal material.
  • the step of corroding the metal material in the furnace may include maintaining the metal material at a predetermined temperature by cooling the back surface of the inclined surface with a coolant.
  • the step of evaluating the corrosion amount may include measuring a thickness of an oxide film formed on the metal material.
  • the step of evaluating the corrosion amount may include analyzing an element distribution in an oxide film formed on the metal material.
  • the probe used for the corrosion evaluation of the metal material in the heating furnace according to the present disclosure has a predetermined diameter at most and extends over a predetermined length, and is provided at the tip of the supporting portion, and is orthogonal to the longitudinal direction in which the supporting portion extends.
  • An inclined surface inclined at a predetermined angle with respect to the plane is formed, and a detection unit in which the metal material of the test specimen is installed on the inclined surface is included.
  • the heating furnace may be a vertical combustion furnace.
  • the angle at which the inclined surface is inclined with respect to the plane orthogonal to the longitudinal direction may be in the range of 30 degrees to 60 degrees.
  • a temperature sensor may be attached to the inclined surface.
  • the support portion may have a double tube structure for supplying a coolant that cools the inclined surface.
  • a groove for installing the metal material of the specimen may be formed on the inclined surface.
  • the cost can be reduced and the test can be performed in the same environment as the actual pulverized coal boiler. Moreover, the probe used for such a test can be provided.
  • a vertical combustion furnace called a drop tube furnace (DTF) in which the furnace extends in the vertical direction is used as a heating furnace assuming an actual pulverized coal boiler.
  • DTF drop tube furnace
  • FIG. 1A is a cross-sectional view schematically showing a vertical combustion furnace 100 and a probe 10 inserted in the vertical combustion furnace 100 used in the metal material corrosion evaluation method of the present embodiment.
  • a burner 103 is provided at the upper end of a ceramic tube 101 having a predetermined diameter and a predetermined length L extending in the vertical direction, an exhaust passage 104 is provided at the lower end, and the periphery is surrounded by a heater 102. It is configured.
  • the burner 103 for example, supplies a mixture of powdered fuel 121 and air having a predetermined flow rate sent from the micro feeder 120 into the furnace through a nozzle and burns them.
  • the microfeeder 120 rotates a disk carrying the powdered fuel 121 with a motor, and sends the powdered fuel 121 to the burner 103 at a predetermined flow rate along with the air.
  • the exhaust passage 104 extends downward from the lower end of the ceramic tube 101 so as to guide the combustion gas generated by the combustion of the ceramic tube 101 in the furnace. At the lower end of the exhaust passage 104, an opening is provided immediately below the ceramic tube 101, and the probe 10 is inserted vertically upward from this opening so that it can reach a desired position in the ceramic tube 101. It has become.
  • the probe 10 of the present embodiment has a detection unit 19 in which an inclined surface 11 inclined at an angle of, for example, 45 degrees with respect to the horizontal direction is formed, and a test piece metal material 21 is provided on the inclined surface 11 of the detection unit 19. Is installed.
  • a temperature sensor (not shown) is also provided on the inclined surface 11 of the detection unit 19.
  • the inclined surface 11 of the detection unit 19 is maintained at a predetermined temperature by supplying a coolant such as cooling water or air through the inside of the probe 10.
  • the probe 10 according to the present embodiment maintains the temperature of the metal material 21 at a desired temperature different from the temperature of the atmosphere in the ceramic tube 101 and provides an inclined surface 11 that is inclined with respect to a horizontal plane. The environment in which heat transfer materials are used in the heat transfer tube is reproduced.
  • FIG. 1B is a graph showing the temperature distribution in the vertical combustion furnace 100.
  • the horizontal axis of the graph represents temperature
  • the vertical axis represents the distance in the vertical direction from the opening at the lower end of the exhaust passage 104 of the vertical combustion furnace 100.
  • the temperature in the furnace reaches its maximum immediately below the flame formed by the burner 103 provided at the upper end of the ceramic tube 101, and decreases as it moves downward and away from the flame.
  • the probe 10 is inserted vertically upward from the opening at the lower end of the exhaust passage 104, and the detection unit 19 of the probe 10 is held at an appropriate position in the furnace, so that the metal material 21 can be formed in an atmosphere at a desired temperature. Corrosion can proceed.
  • FIG. 2A is an enlarged cross-sectional view schematically illustrating the probe 10 inserted into the ceramic tube 101 of the vertical combustion furnace 100.
  • the probe 10 can be inserted into the ceramic tube 101, and has an outer diameter D2 that is substantially smaller than the inner diameter D1 of the ceramic tube so as not to inhibit the flow of combustion gas in the ceramic tube 101.
  • the probe 10 includes a support portion 18 having a predetermined length extending in a predetermined direction (vertical direction in the drawing) and a detection portion 19 provided at the tip of the support portion 18.
  • the detector 19 has an inclined surface 11 that is inclined at an angle of 45 with respect to a plane orthogonal to the longitudinal direction in which the support 18 extends.
  • a groove (not shown) for installing the metal material 21 of the test body is formed on the inclined surface 11.
  • a temperature sensor (not shown) is attached to the surface of the inclined surface 11.
  • the support portion 18 extends in the longitudinal direction so that the detection portion 19 of the probe 10 reaches the desired position in the ceramic tube 101 through the opening at the lower end of the exhaust passage 104.
  • the support portion 18 has a double tube structure including the outer tube 15 and the inner tube 16 so that the coolant 200 such as cooling water or air can be supplied to the inclined surface 11 of the detection unit 19 from the back side. .
  • the refrigerant 200 is sent toward the detection unit 19 through the inner flow path 201 inside the inner tube 16 of the double tube, and the refrigerant 200 used for cooling the detection unit 19 is outside the inner tube 26 of the double tube. Is discharged through the outer flow path 202 inside the outer tube 16.
  • the probe 10 having such a configuration may be manufactured using, for example, stainless steel.
  • FIG. 2B is an enlarged cross-sectional view of the tip of the probe 10.
  • the surface of the metal material 21 of the test body is the same as or substantially the same as the inclined surface at the tip of the probe 10.
  • FIG. 3 is a flowchart showing a series of steps of the metal material corrosion evaluation method of the present embodiment.
  • step S1 as shown in FIGS. 1A and 2, in the vertical combustion furnace 100 in which the fuel supplied from the burner 103 is combusted in the furnace, the probe 10 is opened from the opening at the lower end of the exhaust passage 104. Is inserted into the furnace vertically upward. And the detection part 19 in which the metal material 21 of the test body was installed in the inclined surface 11 in the probe 10 is held at a predetermined position in the furnace. For example, the detection unit 19 of the probe 10 is held in an atmosphere at a desired temperature in the furnace.
  • the heater 102 may be used for heating the vertical combustion furnace 100. For example, when combustion is necessary, switching from heating by the heater 102 to combustion by the burner 103, or using the heater 102 and the burner 103 in combination. May be.
  • the detection unit 19 of the probe 10 is maintained in an atmosphere of a predetermined temperature by combustion of fuel by the burner 103 or heating by the heater 102.
  • the temperature of the metal material 21 installed in the detection unit 19 is kept at a predetermined temperature lower than the atmosphere by cooling with the refrigerant 200 through the inclined surface 11.
  • the temperature of the metal material 21 is monitored by a temperature sensor such as a thermocouple provided on the inclined surface 11 of the detection unit 19 of the probe 10.
  • combustion gas and ash are generated by the combustion of the fuel, and the ash 25 falls on the surface of the metal material 21 of the test body installed on the inclined surface 11 of the detection unit 19 of the probe 10. Since the inclined surface 11 of the detection unit 19 is inclined at an angle of, for example, 45 degrees with respect to the horizontal direction, the surface of the metal material 21 installed on the inclined surface 11 is also inclined at the same angle. A part of the ash that has fallen on the surface of the material 21 slides down from the surface of the metal material 21, and a part of the ash remains on the surface of the metal material 21. Ashes gradually accumulate on the surface of the metal material 21, and the surface of the metal material 21 is corroded to gradually form an oxide film.
  • the burner of the vertical combustion furnace 100 is finished.
  • the fuel supply to 103 is stopped and combustion is stopped, and heating by the heater 102 is also stopped, and the vertical combustion furnace 100 and the probe 10 are cooled.
  • the probe 10 is taken out from the vertical combustion furnace 100 and the metal material 21 installed on the inclined surface 11 of the detection unit 19 of the probe 10 is removed.
  • step S2 the metal material 21 that has undergone corrosion in step S1 is evaluated.
  • the thickness of the oxide film formed on the surface of the metal material 21 may be measured by a scanning electron microscope (SEM). Further, for example, elements constituting the oxide film may be analyzed by an energy dispersive spectrometer (EDS).
  • SEM scanning electron microscope
  • EDS energy dispersive spectrometer
  • the vertical combustion furnace 100 is used to burn the fuel, and the probe 10 in which the metal material 21 of the test specimen is installed in the furnace is inserted to the position of the atmosphere at a predetermined temperature. .
  • combustion gas and ash are obtained by burning fuel, and the ash is adhered to the surface of the metal material 21.
  • the surface temperature of the metal material 21 is adjusted by the flow rate of the refrigerant 200 supplied through the probe 10.
  • the actual combustion gas and ash are used, and the temperature of the combustion gas and the surface temperature of the metal material 21 are different, so that the metal material 21 is quantitatively measured under conditions close to the actual boiler environment. Corrosion can be evaluated.
  • the cost is much lower than the evaluation with the actual machine.
  • the inclined surface 11 of the detection unit 19 at the tip of the probe 10 on which the metal material 21 of the test body is installed is inclined at an angle of 45 degrees with respect to a plane perpendicular to the longitudinal direction of the support unit 18.
  • the inclined surface 11 is inclined at an angle of 45 degrees with respect to the horizontal plane. Therefore, in the present embodiment, the ash with a high melting point is hard to fall off due to the inclination angle of 45 degrees of the inclined surface 11, and the ash with a low melting point is likely to adhere, and the growth and dropping of the attached ash can be reproduced. Therefore, the phenomenon of ash adhesion occurring in the actual boiler can be reproduced, and more accurate corrosion evaluation becomes possible.
  • the probe 10 can be reused.
  • the inclined surface 11 has a horizontal plane or an inclination angle of 45 degrees with the longitudinal direction of the support portion 18 of the probe 10.
  • the inclination angle of the inclined surface 11 is not limited to this angle. What is necessary is just to exist in the range of 30 to 60 degrees with respect to the longitudinal direction of the support part 18 of the probe 10.
  • the ceramic tube 101 had an inner diameter D1 of 30 mm, an outer diameter of 60 mm, and a length L of 2000 mm.
  • the probe 10 had an outer diameter D2 of 34 mm.
  • Combustion in the vertical combustion furnace 100 was performed for two types shown in Table 1. The air ratio of 1.5 supplied to the burner 103 and the air volume of 5 liters per minute were common.
  • a plate-like STBA 24 having dimensions of 24 mm ⁇ 24 mm in length and 3 mm in thickness was used.
  • step S1 in the case of coal-fired, the combustion process of step S1 was performed using fuel as charcoal. As shown in Table 1, hunter valley pulverized coal was used as the charcoal.
  • the ceramic tube 101 of the vertical combustion furnace 100 was previously heated to 1400 ° C. by the heater 102, and the temperature distribution in the furnace was measured while flowing air from the burner 103 toward the exhaust passage 104. As a result, a temperature distribution similar to the temperature distribution due to combustion of the burner 103 as shown in FIG. 1B was obtained.
  • the metal material 21 of the test body was installed on the inclined surface 11 of the detection unit 19 of the probe 10 and inserted through the opening at the lower end of the exhaust passage 104 to a position where the temperature of the atmosphere in the furnace was 800 ° C.
  • the flow rates of the cooling water and the air refrigerant 200 supplied to the probe 10 were controlled so that the surface temperature of the metal material 21 installed on the inclined surface 11 was maintained at 650 ° C. Thereafter, fuel charcoal was supplied from the micro-feeder 120 to the burner 103 together with air, combustion occurred, combustion gas and ash 25 were generated, and ash 25 adhered to the surface of the metal material 21. After exposing the probe 10 in the furnace for 40 hours, the vertical combustion furnace 100 and the probe 10 were slowly cooled. Then, the probe 10 was taken out from the furnace, and the metal material 21 was removed from the probe 10.
  • FIG. 4 is a graph showing changes over time in the constituent components of the combustion gas in the case of coal-fired. As can be seen from the graph, carbon dioxide (CO 2) and oxygen gas (O 2) have substantially constant concentrations after a predetermined time has elapsed since the start of combustion. Nitrogen oxide (NOx) and sulfur oxide (SOx) also have a substantially constant concentration as a predetermined time elapses from the start of combustion.
  • CO 2 carbon dioxide
  • O 2 oxygen gas
  • SOx sulfur oxide
  • FIG. 5 is a graph showing the time change of the temperature of the surface of the metal material 21 in the case of coal-fired. It can be seen that the temperature of the surface of the metal material 21 is maintained almost constant regardless of the passage of time.
  • step S1 the combustion process of step S1 was carried out in the case of biomass mixed firing.
  • 50% of sawdust in the case of biomass co-firing is fine powder obtained by mixing 50% of cedar sawdust on a calorie basis and Hunter Valley charcoal.
  • the probe 10 was exposed to the furnace, the probe 10 was taken out of the furnace, and the metal material 21 was removed from the probe 10.
  • step S1 the combustion process of step S1 was also performed for the case where no ash was deposited on the surface of the metal material 21 of the test specimen, and no ash was deposited by combustion.
  • the metal material 21 is covered with an appropriate cover so that the ash 25 does not fall on the surface of the metal material 21, and the fuel can be implemented using charcoal in the same manner as in the case of coal-fired.
  • step S2 the corrosion amount evaluation process in step S2 was performed. Corrosion amount was measured about each of the metal material implemented by coal combustion, biomass co-firing, and the absence of ash in the combustion process of step S1.
  • the corrosion amount is evaluated by the thickness of the oxide film, the metal material 21 is hardened with a resin, the cross section is cut, and then the average oxide film thickness is measured by analysis using SEM and EDX.
  • FIG. 6 is a photomicrograph showing a cross section of the metal material 21 observed by SEM and EDX.
  • (a) shows no ash
  • (b) shows coal-fired
  • (c) shows biomass-fired.
  • the left end shows a micrograph by SEM, and the second and subsequent cases when the distribution of elements of oxygen, iron, chromium, sulfur, potassium, and calcium is detected by EDX
  • the micrograph of is shown.
  • D in the figure schematically shows a typical structure of the oxide film seen in (a) and (c).
  • FIG. 7 is a graph showing the average thickness of the oxide film formed by the combustion process in step S1.
  • the average oxide film thickness can be measured using, for example, a micrograph by SEM or EDX as shown in FIG.
  • corrosion did not occur in the absence of ash, but the formation of an oxide film was observed during the coal-fired and biomass-mixed combustion, and the corrosion progressed.
  • the thickness of the oxide film was larger and the corrosion increased when the biomass was co-fired than when the coal was fired exclusively.
  • the present disclosure may be used for a corrosion evaluation method of a metal material constituting a pulverized coal boiler and a probe used in this method.

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Abstract

La présente invention comprend : une étape d'insertion, dans un four de chauffage (100), d'une sonde (10) ayant un matériau métallique (21) à tester, ledit matériau métallique étant disposé sur une surface inclinée (11) inclinée à un angle prédéterminé par rapport au plan horizontal, et corroder le matériau métallique (21) dans le four ; et une étape pour extraire le matériau métallique (21) de la sonde retirée de l'intérieur du four, ledit matériau métallique ayant été disposé sur la surface inclinée (11), et évaluer la quantité de corrosion du matériau métallique (21).
PCT/JP2018/008956 2017-03-14 2018-03-08 Procédé d'évaluation de la corrosion d'un matériau métallique, et sonde WO2018168633A1 (fr)

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Cited By (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
DE102021120195A1 (de) 2021-08-03 2023-02-09 Chemin Gmbh Sonde, Kesselanordnung und Verfahren

Citations (8)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JPH08114534A (ja) * 1994-10-18 1996-05-07 Nuclear Fuel Ind Ltd 管状試料の金相試験用体形成方法
JPH08262009A (ja) * 1995-03-23 1996-10-11 Hitachi Ltd 高温部材の余寿命評価法
JP2001296237A (ja) * 2000-04-17 2001-10-26 Babcock Hitachi Kk 腐食センサと高感度腐食監視装置と方法
JP2011185710A (ja) * 2010-03-08 2011-09-22 National Institute For Materials Science バーナーリグ試験装置
JP2012112700A (ja) * 2010-11-22 2012-06-14 Sumitomo Heavy Ind Ltd 損耗の評価装置及び評価方法
WO2014061830A1 (fr) * 2012-12-25 2014-04-24 住友電気工業株式会社 Procédé pour mise en oeuvre d'un test d'évaluation pour moteur à combustion interne
US20160245738A1 (en) * 2014-12-17 2016-08-25 Instituto Mexicano Del Petróleo Methodology for three-dimensional morphological and quantitative determination of micro and nanocavities produced by chemical and microbiological corrosion in metallic materials
WO2017110617A1 (fr) * 2015-12-21 2017-06-29 三菱重工業株式会社 Dispositif de test de pénétration de sel fondu et procédé de test de pénétration de sel fondu

Patent Citations (8)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JPH08114534A (ja) * 1994-10-18 1996-05-07 Nuclear Fuel Ind Ltd 管状試料の金相試験用体形成方法
JPH08262009A (ja) * 1995-03-23 1996-10-11 Hitachi Ltd 高温部材の余寿命評価法
JP2001296237A (ja) * 2000-04-17 2001-10-26 Babcock Hitachi Kk 腐食センサと高感度腐食監視装置と方法
JP2011185710A (ja) * 2010-03-08 2011-09-22 National Institute For Materials Science バーナーリグ試験装置
JP2012112700A (ja) * 2010-11-22 2012-06-14 Sumitomo Heavy Ind Ltd 損耗の評価装置及び評価方法
WO2014061830A1 (fr) * 2012-12-25 2014-04-24 住友電気工業株式会社 Procédé pour mise en oeuvre d'un test d'évaluation pour moteur à combustion interne
US20160245738A1 (en) * 2014-12-17 2016-08-25 Instituto Mexicano Del Petróleo Methodology for three-dimensional morphological and quantitative determination of micro and nanocavities produced by chemical and microbiological corrosion in metallic materials
WO2017110617A1 (fr) * 2015-12-21 2017-06-29 三菱重工業株式会社 Dispositif de test de pénétration de sel fondu et procédé de test de pénétration de sel fondu

Cited By (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
DE102021120195A1 (de) 2021-08-03 2023-02-09 Chemin Gmbh Sonde, Kesselanordnung und Verfahren

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