EP3239311A1 - Hitzebeständiges rohr mit aluminiumsperrschicht - Google Patents

Hitzebeständiges rohr mit aluminiumsperrschicht Download PDF

Info

Publication number
EP3239311A1
EP3239311A1 EP15872985.5A EP15872985A EP3239311A1 EP 3239311 A1 EP3239311 A1 EP 3239311A1 EP 15872985 A EP15872985 A EP 15872985A EP 3239311 A1 EP3239311 A1 EP 3239311A1
Authority
EP
European Patent Office
Prior art keywords
barrier layer
diameter side
content
heat
alumina barrier
Prior art date
Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
Granted
Application number
EP15872985.5A
Other languages
English (en)
French (fr)
Other versions
EP3239311B1 (de
EP3239311A4 (de
Inventor
Kunihide Hashimoto
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
Kubota Corp
Original Assignee
Kubota Corp
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Application filed by Kubota Corp filed Critical Kubota Corp
Publication of EP3239311A1 publication Critical patent/EP3239311A1/de
Publication of EP3239311A4 publication Critical patent/EP3239311A4/de
Application granted granted Critical
Publication of EP3239311B1 publication Critical patent/EP3239311B1/de
Active legal-status Critical Current
Anticipated expiration legal-status Critical

Links

Images

Classifications

    • C—CHEMISTRY; METALLURGY
    • C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
    • C22C—ALLOYS
    • C22C19/00—Alloys based on nickel or cobalt
    • C22C19/03—Alloys based on nickel or cobalt based on nickel
    • C22C19/05—Alloys based on nickel or cobalt based on nickel with chromium
    • C—CHEMISTRY; METALLURGY
    • C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
    • C22C—ALLOYS
    • C22C30/00—Alloys containing less than 50% by weight of each constituent
    • C—CHEMISTRY; METALLURGY
    • C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
    • C22C—ALLOYS
    • C22C38/00—Ferrous alloys, e.g. steel alloys
    • C—CHEMISTRY; METALLURGY
    • C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
    • C22C—ALLOYS
    • C22C38/00—Ferrous alloys, e.g. steel alloys
    • C22C38/18—Ferrous alloys, e.g. steel alloys containing chromium
    • C22C38/40—Ferrous alloys, e.g. steel alloys containing chromium with nickel
    • C22C38/58—Ferrous alloys, e.g. steel alloys containing chromium with nickel with more than 1.5% by weight of manganese
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B22—CASTING; POWDER METALLURGY
    • B22D—CASTING OF METALS; CASTING OF OTHER SUBSTANCES BY THE SAME PROCESSES OR DEVICES
    • B22D13/00—Centrifugal casting; Casting by using centrifugal force
    • B22D13/02—Centrifugal casting; Casting by using centrifugal force of elongated solid or hollow bodies, e.g. pipes, in moulds rotating around their longitudinal axis
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B22—CASTING; POWDER METALLURGY
    • B22D—CASTING OF METALS; CASTING OF OTHER SUBSTANCES BY THE SAME PROCESSES OR DEVICES
    • B22D13/00—Centrifugal casting; Casting by using centrifugal force
    • B22D13/06—Centrifugal casting; Casting by using centrifugal force of solid or hollow bodies in moulds rotating around an axis arranged outside the mould
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B22—CASTING; POWDER METALLURGY
    • B22D—CASTING OF METALS; CASTING OF OTHER SUBSTANCES BY THE SAME PROCESSES OR DEVICES
    • B22D13/00—Centrifugal casting; Casting by using centrifugal force
    • B22D13/10—Accessories for centrifugal casting apparatus, e.g. moulds, linings therefor, means for feeding molten metal, cleansing moulds, removing castings

Definitions

  • the present invention relates to a heat-resistant tube having an alumina barrier layer, and more specifically to a heat-resistant tube having an alumina barrier layer with a stable structure on the tube inner surface.
  • An austenite-based heat-resistant alloy having excellent high-temperature strength is used in heat-resistant tubes to be exposed to a high-temperature atmosphere, such as reaction tubes for production of ethylene or propylene and decomposition tubes used for thermal decomposition of hydrocarbons.
  • austenite-based heat-resistant alloy While this type of austenite-based heat-resistant alloy is used in a high-temperature atmosphere, a portion of components (e.g., Cr, Si, Al, and Fe) contained in the base material is oxidized, and thus a metal oxide layer is formed on the surface. This oxide layer serves as a barrier and suppresses further oxidation of the base material.
  • components e.g., Cr, Si, Al, and Fe
  • the metal oxide layer made of Cr-oxides (mainly constituted by Cr 2 O 3 (chromia))
  • Cr 2 O 3 Cr 2 O 3
  • a function for preventing the entry of oxygen and carbon is insufficient due to the oxides having a low denseness, thus causing the internal oxidation of the base material in a high-temperature atmosphere and the thickening of the oxide layer.
  • the thickened oxide layer is likely to be removed during repeated cycles of heating and cooling. Even in a case where the oxide layer is not removed, since the function for preventing the entry of oxygen and carbon from an outside atmosphere is insufficient, there is a disadvantageous situation in which oxygen and carbon pass through the oxide layer and cause the internal oxidation or carburization of the base material.
  • Al is a ferrite-forming element, and therefore, an increase in the Al content causes a problem in that the mechanical characteristics of the heat-resistant tube, such as creep rupture strength and tensile ductility, deteriorate and a problem in that weldability deteriorates.
  • a heat-resistant tube according to the present invention is a heat-resistant tube having an alumina barrier layer to be used for thermal decomposition of hydrocarbons, the alumina barrier layer including an Al oxide and being provided on an inner surface of a tube body, wherein, in the tube body, an Al content on an inner diameter side is larger than that on an outer diameter side.
  • outer diameter side refers to an outer circumferential side of the cross-sectional thickness of a heat-resistant tube shown in FIG. 1
  • inner diameter side refers to an inner circumferential side thereof.
  • a portion near the center of the cross-sectional thickness is taken as the center in a thickness direction (middle diameter side).
  • the Al content on the inner diameter side is larger than that on the outer diameter side by a factor of 2 or more.
  • the Al content on the inner diameter side is larger by 1.3 mass% or more than that on the outer diameter side.
  • the Al content on the inner diameter side of the tube body is larger than that on the outer diameter side thereof, and therefore, an alumina barrier layer can be favorably formed on the inner surface of the tube body by heating. Accordingly, the tube inner surface to be brought into contact with a high-temperature hydrocarbon gas during thermal decomposition of hydrocarbon can be provided with excellent oxidation resistance, carburization resistance, nitridation resistance, corrosion resistance, and the like.
  • the Al content on the outer diameter side of the tube body is small, and therefore, the deterioration of mechanical characteristics such as creep rupture strength and tensile ductility due to the contained Al can be prevented. Moreover, reducing the Al content on the outer diameter side of the tube body makes it possible to prevent the deterioration of weldability on the outer diameter side of the tube.
  • the heat-resistant tube having an alumina barrier layer of the present invention includes the tube body in which an oxide layer including alumina (Al 2 O 3 ) as a main component is provided on the tube inner surface, and is provided with improved oxidation resistance, carburization resistance, and the like and excellent mechanical characteristics such as the creep rupture strength, it is preferable to apply the heat-resistant tube to a heating furnace to be used in a high-temperature environment.
  • an oxide layer including alumina (Al 2 O 3 ) as a main component is provided on the tube inner surface, and is provided with improved oxidation resistance, carburization resistance, and the like and excellent mechanical characteristics such as the creep rupture strength
  • the Al content on the inner diameter side of the tube body is increased, and therefore, the alumina barrier layer can be favorably regenerated by action of the contained Al even if a portion of the alumina barrier layer inside the tube is removed during the operation or the like.
  • a heat-resistant tube of the present invention is used as a reaction tube for manufacturing ethylene, a decomposition tube for thermal decomposition of hydrocarbons, and the like, and is to be provided in a heating furnace for manufacturing hydrocarbons such as ethylene, for example.
  • an alumina barrier layer 14 that contains an Al-oxide including alumina as a main component is formed on the inner surface of a tube body 12.
  • the heat-resistant tube 10 may have an inner diameter of 30 to 300 mm, a length of 1000 to 6000 mm, and a thickness of 5 to 30 mm, for example. It will be appreciated that there is no limitation to these dimensions.
  • the heat-resistant tube 10 can be manufactured using a centrifugal casting apparatus 20 as shown in FIG. 2 .
  • the centrifugal casting apparatus 20 may have a configuration in which a tubular metal framework 22 that is rotated at a high speed by casting machine rollers 21 is provided, and a molten alloy 23 is poured into the metal framework 22 from a ladle 24 via a casting pail 25.
  • the heat-resistant tube 10 of the present invention is characterized in that the Al content on the inner diameter side (see FIG. 1 ) of the tube body 12 is larger than that on the outer diameter side (see FIG. 1 ).
  • the Al content in the molten alloy poured into the metal framework from the casting pail is changed over time in order to increase the Al content on the inner diameter side of the tube body compared with that on the outer diameter side, thus making it possible to manufacture the heat-resistant tube of the present invention.
  • the pouring time is divided into the early stage, the middle stage, and the last stage, and the Al content in the molten alloy at the middle stage and/or the last stage of casting is increased compared with that at the early stage of casting, thus making it possible to manufacture the heat-resistant tube of the present invention.
  • the early stage, the middle stage, and the last stage of casting can be set by dividing the pouring time into substantially equal three stages, for example. It will be appreciated that the pouring time may be divided into the first half and the latter half of casting, and the Al content in the molten alloy at the latter half may be increased.
  • the Al content in the molten alloy in the casting pail can be adjusted by preparing a ladle containing a molten alloy including a small amount of Al or no Al and a ladle containing a molten alloy including a large amount of Al.
  • molten Al may be directly added to the ladle or the casting pail using a dipper, or a lump of Al or an Al alloy may be charged into the ladle.
  • the Al content on the inner diameter side of the tube body casted through centrifugal casting can also be increased by pouring the molten alloy including a large amount of Al at only the middle stage, not at the middle and last stages or only the last stage.
  • the reason for this is that the molten alloy poured at the middle stage is mixed with the molten alloy poured at the last stage by convection of the molten alloy.
  • the tube body is made of a heat-resistant alloy containing at least Cr in an amount of 15 to 50%, Ni in an amount of 18 to 70%, and Al in an amount of 1 to 6%.
  • the tube body is made of a heat-resistant alloy containing C in an amount of 0.05 to 0.7%, Si in an amount of more than 0% to 2.5% or less, Mn in an amount of more than 0% to 5% or less, Cr in an amount of 15 to 50%, Ni in an amount of 18 to 70%, Al in an amount of 1 to 6%, a rare earth element in an amount of 0.005 to 0.4%, and W in an amount of 0.5 to 10% and/or Mo in an amount of 0.1 to 5%, and
  • the above heat-resistant alloy contains at least one selected from the group consisting of Nb in an amount of 0.1 to 3%, Ti in an amount of 0.01 to 0.6%, and Zr in an amount of 0.01 to 1%.
  • At least one rare earth element selected from La, Y, and Ce can be used.
  • the above heat-resistant alloy contains B in an amount of 0.001 to 0.5%.
  • the above heat-resistant alloy contains N in an amount of 0.005 to 0.2%.
  • the above heat-resistant alloy contains Ca in an amount of 0.001 to 0.5%.
  • the Cr content is set to 15% or more for the purpose of contribution to the improvement of high-temperature strength and cyclic oxidation resistance. However, if the content is too large, high-temperature creep rupture strength deteriorates, and therefore, the upper limit is set to 50%. It should be noted that the Cr content of 20 to 45% is more desirable.
  • Ni is an element that is necessary to secure cyclic oxidation resistance and the stability of a metal structure. If the Ni content is small, the Fe content relatively becomes large. As a result, a Cr-Fe-Mn-oxide is likely to be formed on the surface of the cast body, thus inhibiting the formation of the alumina barrier layer. Therefore, the Ni content is set to at least 18%. Even if the Ni content exceeds 70%, it is impossible to obtain the efficacy corresponding to the increasing amount, and therefore, the upper limit is set to 70%. It should be noted that the Ni content of 20 to 50% is more desirable.
  • the Al content refers to an average content in the entire tube body. That is, in the present invention, the Al content on the inner diameter side of the tube body in the heat-resistant tube is increased compared with that on the outer diameter side as described above, and therefore, when the Al content is 3%, for example, the Al content on the inner diameter side is larger than 3%, whereas the Al content on the outer diameter side is smaller than 3%.
  • the reason for adding Al is to form an alumina barrier layer having excellent oxidation resistance, carburization resistance, coking resistance, and the like on the inner surface of the tube body.
  • an increase in the Al content causes the deterioration of the mechanical characteristics such as creep rupture strength and a tensile characteristic, and the deterioration of weldability. Therefore, in the present invention, the Al content on the inner diameter side of the tube body is larger than that on the outer diameter side as described above.
  • the Al content is set to at least 1% in order to favorably form the alumina barrier layer on the inner diameter side of the tube body.
  • the Al content exceeds 6%, an effect of forming the alumina barrier layer on the inner diameter side of the tube body becomes substantially saturated, and therefore, the upper limit is set to 6% in the present invention. It should be noted that the Al content of 2.0 to 4.0% is more desirable.
  • the Al content on the inner diameter side is preferably set to be larger than that on the outer diameter side by a factor of 2 or more, desirably 2.5, and more preferably 4.0. Adjusting the Al content in this manner makes it possible to favorably form the alumina barrier layer on the inner surface of the tube body and to prevent the deterioration of the mechanical characteristics of the tube body.
  • Al content on the inner diameter side is preferably larger by 1.3 mass% or more, and more desirably larger by 2.0 mass% or more than that on the outer diameter side.
  • % refers to “mass%” unless otherwise stated. Adjusting the Al content in this manner makes it possible to favorably form the alumina barrier layer on the inner surface of the tube body and to prevent the deterioration of the mechanical characteristics of the tube body.
  • the Al content on the inner diameter side of the tube body is set to 1.5% or more, and the Al content on the outer diameter side thereof is set to 5% or less.
  • the Al content on the inner diameter side is smaller than the lower limit, a favorable alumina barrier layer is not formed, and when the Al content on the outer diameter side exceeds the upper limit, it is difficult to maintain the mechanical characteristics.
  • the C content is set to at least 0.05%.
  • a primary carbide of Cr 7 C 3 is likely to be extensively formed, and thus the movement of Al, which forms the alumina barrier layer, in the base material is suppressed.
  • Al is insufficiently supplied to the surface portion of a cast body and the alumina barrier layer locally splits, and thus the continuity of the alumina barrier layer is impaired.
  • a secondary carbide is excessively deposited to cause the deterioration of tensile ductility and toughness. Therefore, the upper limit is set to 0.7%. It should be noted that the C content of 0.2 to 0.6% is more desirable.
  • Si more than 0% to 2.5% or less
  • Si is contained for the purpose of using Si as a deoxidizer for molten alloy and enhancing the fluidity of the molten alloy. If the content is too large, high-temperature creep rupture strength deteriorates, or Si is oxidized to form an oxide layer having a low denseness, and therefore, the upper limit is set to 2.5%. It should be noted that the Si content of 2% or less is more desirable.
  • Mn more than 0% to 5% or less
  • Mn is contained for the purpose of using Mn as a deoxidizer for molten alloy and fixing S in the molten alloy. If the content is too large, high-temperature creep rupture strength deteriorates, and therefore, the upper limit is set to 5%. It should be noted that the Mn content of 1.6% or less is more desirable.
  • Rare earth element 0.005 to 0.4%
  • rare earth element means 17 elements including 15 elements of the lanthanide series ranging from La to Lu in the periodic table, and Y and Sc. It is preferable that at least one rare earth element selected from the group consisting of La, Y and Ce is contained in the heat-resistant alloy of the present invention. The rare earth element contributes to the formation of the alumina barrier layer and the enhancement of stability thereof.
  • the upper limit is set to 0.4%.
  • W and Mo form a solid solution in a matrix and strengthen an austenite phase in the matrix, thus improving creep rupture strength. At least one of W and Mo is contained in order to achieve this efficacy.
  • the W content is set to 0.5% or more, and the Mo content is set to 0.1% or more.
  • the W content is set to 10% or less
  • the Mo content is set to 5% or less. It should be noted that when both elements are contained, the total content is preferably set to 10% or less.
  • Nb, Ti, and Zr are elements that are likely to form carbides, and form less solid solutions in the matrix than W and Mo. Therefore, Nb, Ti, and Zr do not exhibit any particular action of forming the alumina barrier layer, but improve creep rupture strength. At least one of Ti, Zr and Nb may be contained as needed.
  • the Nb content is set to 0.1% or more, and the Ti content and the Zr content are set to 0.01% or more.
  • the upper limit of the Nb content is set to 1.8%, and the upper limits of the Ti content and the Zr content are set to 0.6%.
  • B Since B exhibits an action of strengthening the particle boundaries of the cast body, B may be contained as needed. It should be noted that if the B content is large, creep rupture strength deteriorates, and therefore, the B content is set to 0.5% or less even in the case where B is added.
  • N forms a solid solution in an alloy matrix and improves high-temperature tensile strength.
  • the N content is large, N binds to Al to form AlN, and tensile ductility deteriorates. Therefore, the N content is set to 0.2% or less.
  • the N content of 0.06 to 0.15% is preferable.
  • Ca serves as a desulfurizing element or a deoxidizing element. Therefore, Ca contributes to the improvement of the yields of Ti and Al. This effect can be obtained when Ca is added in an amount of 0.001% or more. However, if a large amount of Ca is added, weldability is impaired, and therefore, Ca is added in an amount of 0.5% or less.
  • the heat-resistant alloy constituting the tube body includes the above-described components and Fe as the balance.
  • P, S, and other impurities that are inevitably mixed in the alloy when melting the alloy may be present as long as the contents of such impurities are within a range that is usually allowable to this type of alloy material.
  • the Al content on the inner diameter side is larger than that on the outer diameter side.
  • An unsound layer that has protrusions and depressions or ununiformly includes impurities is present on the inner surface of the tube body obtained through centrifugal casting, and therefore, machining processing is performed on this unsound layer.
  • the machining processing preferably includes polishing processing that is performed such that the surface roughness (Ra) of the inner surface of the tube body is 0.05 to 2.5 ⁇ m. Setting the surface roughness (Ra) as mentioned above makes it possible to suppress the formation of Cr-oxides (e.g., Cr 2 O 3 ) on the inner surface of the tube body.
  • the alumina barrier layer is formed on the inner surface of the tube body by heating the tube body in an oxidizing atmosphere after the machining processing is performed on the inner surface. It should be noted that this heat processing can also be performed as an independent step or performed in a high-temperature atmosphere in which the tube body installed in a heating furnace is used.
  • the heat processing is performed in an oxidizing atmosphere.
  • the "oxidizing atmosphere” refers to an oxidizing environment in which an oxidizing gas containing oxygen in an amount of 20 vol% or more, steam, and CO 2 are mixed.
  • the heat processing is performed at a temperature of 900°C or higher, preferably 1000°C or higher, and more preferably 1050°C or higher, and heating time is one hour or more.
  • the inner surface of the tube body comes into contact with oxygen to oxidize Al, Cr, Ni, Si, and Fe that have diffused on the surface of the matrix, and an oxide layer is thus formed.
  • Al forms oxides prior to Cr, Ni, Si, and Fe.
  • the Al content on the inner diameter side of the tube body is large, and therefore, Al located near the inner surface of the tube body favorably binds to oxygen by being heated as described above to form, as the oxide layer, an alumina barrier layer including an Al-oxide (Al 2 O 3 ) as a main component.
  • Al-oxide Al 2 O 3
  • an alumina barrier layer is favorably formed on the inner surface due to the Al content on the inner diameter side being large, whereas the tube body forms a heat-resistant tube that is excellent in mechanical characteristics such as creep rupture strength and tensile ductility due to the Al content on the outer diameter side being small.
  • Al is a component that causes defective welding and reduces weldability.
  • the Al content on the outer diameter side is small, thus making it possible to suppress the deterioration of the weldability when the heat-resistant tube is installed in a heating furnace.
  • the heat-resistant tube of the present invention When the heat-resistant tube of the present invention is used in a high-temperature atmosphere, excellent oxidation resistance, carburization resistance, nitridation resistance, and corrosion resistance can be maintained for a long period of time due to the alumina barrier layer formed on the inner surface, and the mechanical characteristics are excellent. Furthermore, when the heat-resistant tube is installed in a heating furnace, weldability is also excellent. Accordingly, the lifetime of the heat-resistant tube can be improved significantly, and the operation efficiency can be enhanced to a level as high as possible.
  • Molten alloy was produced through atmospheric melting in a highfrequency induction melting furnace, and the centrifugal casting apparatus shown in FIG. 2 was used to form tube bodies having alloy compositions shown in Table 1 below (unit: %; it should be noted that an average content is used for Al) in the following conditions, followed by machining processing.
  • the tube bodies each had an inner diameter of 80 mm, an outer diameter of 100 mm, and a length of 250 mm prior to the machining processing. It should be noted that "-" shown in Table 1 means that the component is not contained in the tube body or is inevitably contained in the tube body.
  • Table 1 C Si Mn Cr Ni Mo W Al Nb Ti N Zr La Y B Ce Ca Inv. Ex.
  • Each of the tube bodies of inventive examples and comparative examples was produced by setting the total weight of molten alloy to be poured into a casting pail to 40 kg, preparing three types of molten alloy including an early-stage molten alloy, an middle-stage molten alloy, and the last-stage molten alloy in which the Al contents (Al inputs) were different or the same as shown in Table 2 below, and pouring the early-stage molten alloy, followed by pouring the middle-stage molten alloy and the last-stage molten alloy in this order. It should be noted that the reason why the composition of the manufactured tube body is inconsistent with the total weight of the alloy and the Al input is that a portion of Al adhered to a dipper or a melting pot and remained thereon.
  • the total time of the early stage, the middle stage, and the last stage was set to 14 to 16 seconds.
  • Zero second to fifth second was the early stage
  • fifth second to seventh second was the middle stage
  • seventh second and onward was the last stage.
  • the Al contents on the inner diameter side and the middle diameter side were larger than that on the outer diameter side in all of Inventive Examples 1 to 7.
  • the reason for this is that molten alloy containing a large amount of Al was used in the middle stage and/or the last stage of the casting in the inventive examples.
  • the Al contents on the inner diameter side and the middle diameter side were the same as that on the outer diameter side, or the Al content on the middle diameter side was smaller than that on the outer diameter side.
  • Al was poured at the early stage of the casting in the comparative examples, and Al was uniformly diffused in the molten alloy in the casting pail.
  • the tube bodies of Inventive Examples 1 to 7 and Comparative Examples 1 and 2 were heated in the atmosphere (containing oxygen in an amount of about 21%) at 950°C for 24 hours and then cooled in the furnace.
  • the alumina barrier layer formed on the inner surface of the tube body was removed in the following conditions in order to determine whether or not a favorable alumina barrier layer was formed again at a position where the alumina barrier layer had been removed.
  • the removing conditions were as follows: all the tube bodies were heated in the atmosphere (containing oxygen in an amount of about 21%) at 1200°C (which is higher than the operation temperature of a heating furnace for manufacturing ethylene) for 60 hours and then cooled in the furnace. As a result, while the tube body was being cooled, the alumina barrier layer was removed from the inner surface of the tube body due to the difference in heat shrinkage percentage between the tube body and the alumina barrier layer.
  • FIGS. 3(a) and 3 (a') are SEM photographs of the tube bodies 12 of Inventive Example 7 and Comparative Example 1, respectively, after alumina barrier layer removing processing. These photographs show that an Al-oxide (Al 2 O 3 ) on the inner surface of the tube body 12 did not take a layered form, and only a portion of the Al-oxide remained on the inner surface of the tube body 12.
  • Al-oxide Al 2 O 3
  • the tube bodies on which the above alumina barrier layer removing processing had been performed were heated in the atmosphere (containing oxygen in an amount of about 21%) at 950°C for 24 hours and then cooled in the furnace.
  • the inner surface of the tube body was observed to check whether or not an alumina barrier layer was formed again thereon.
  • Table 4 (Layer regeneration) above shows the results.
  • A shows that an alumina barrier layer was regenerated on substantially the entire inner surface (90 area% or more) of the tube body
  • B means that an Al-oxide of 80 area% or more and less than 90 area% was formed, and an Al-oxide was not regenerated or Cr-oxides were formed on the remaining area
  • C means that an Al-oxide of less than 80 area% was regenerated, and an Al-oxide was not regenerated or Cr-oxides were formed on the remaining area.
  • Inventive Examples 2, 3, 5, and 7 were evaluated as "A" for layer regeneration, meaning that substantially the entire alumina barrier layer was regenerated. This was due to the Al contents on the inner diameter side of the tube bodies of these inventive examples being 4.0% or more. Al contained in a large amount on the inner diameter side bound to oxygen taken in through heat processing, and thus a favorable alumina barrier layer was regenerated.
  • Inventive Examples 1, 4, and 6 and Comparative Example 2 were inferior to the above inventive examples, and were evaluated as "B” for layer regeneration, meaning that an alumina barrier layer of 80 area% or more could be regenerated.
  • Comparative Example 1 was evaluated as "C” for layer regeneration due to the Al content on the inner diameter side of the tube body being small, meaning that an alumina barrier layer was regenerated insufficiently.
  • FIGS. 3(b) and 3 (b') are SEM photographs of the inner surfaces of the tube bodies 12 of Inventive Example 7 and Comparative Example 1, respectively, after alumina barrier layer regenerating processing.
  • the alumina barrier layer 14 constituted by an Al-oxide (Al 2 O 3 ) was observed on substantially the entire surface of the tube body 12, and the formation of Cr-oxides was not observed.
  • Al-oxide Al 2 O 3
  • Comparative Example 1 an Al oxide was partially regenerated, and Cr-oxides were also formed. It is thought that the Al content on the inner diameter side of the tube body of Comparative Example 1 was as small as 1%, and therefore, Cr, Ni, Si, Fe, and the like formed oxides while an Al oxide was formed.
  • alumina barrier layer regenerating processing Discussions of the above alumina barrier layer regenerating processing will be given. It is found that even when the alumina barrier layer is removed for one reason or another while each of the inventive examples is used in an ethylene manufacturing apparatus, the alumina barrier layer can be regenerated immediately, and oxidation resistance, carburization resistance, nitridation resistance, corrosion resistance, coking resistance, and the like can be provided.
  • Test pieces were produced from the tube bodies of Inventive Examples 1 to 7 and Comparative Examples 1 and 2, and tensile testing was performed thereon to measure tensile ductility.
  • the tube body was cut in the thickness direction, and the test piece was produced based on JIS Z 2201 (flat test piece).
  • the distance between marks in the thickness direction of the test piece is 5.65 ⁇ S (S: cross-sectional area).
  • the tensile testing was performed in conformity with JIS Z 2241 (metallic materials tensile testing method). It should be noted that the testing was performed at room temperature because a clear difference can be observed compared with a case where the testing is performed at a high temperature.
  • Table 4 shows that Inventive Examples 1, 2, 4, 6, and 7 and Comparative Example 1 had a tensile ductility of higher than 6% and thus were favorable. Inventive Examples 3 and 5 had a tensile ductility of higher than 3% and thus were also favorable. On the other hand, Comparative Example 2 had a tensile ductility of lower than 3%.
  • the inventive examples and comparative examples were evaluated comprehensively.
  • Comprehensive evaluation was determined as follows: in a case where an alumina barrier layer of 80 area% or larger was formed through the alumina barrier layer forming processing, the layer of 80 area% or more was regenerated (evaluation for layer regeneration was "A” or "B") through the alumina barrier layer regenerating processing, and the tensile ductility measured in the tensile testing was 3% or more, the comprehensive evaluation was "A", and in a case where at least one of the above criteria was not satisfied, the comprehensive evaluation was "B".
  • the comprehensive evaluation was "A" for all the inventive examples, and these results show that the inventive examples had a high ability to form and regenerate the alumina barrier layer and a high tensile ductility.
  • the reason why the ability to form and regenerate the alumina barrier layer could be enhanced is that the Al content on the inner diameter side of the tube body could be increased.
  • the reason why excellent mechanical characteristics could be provided is that the Al content on the outer diameter side of the tube body could be reduced.
  • the Al content on the inner diameter side of the tube body is preferably larger than that on the outer diameter side by a factor of 2 or more, and the Al content on the inner diameter side is preferably larger by 1.3 mass% or more than that on the outer diameter side.
  • Comparative Example 1 in which the Al content in the tube body was merely reduced, the mechanical characteristics could be secured, but the ability to form and regenerate the alumina barrier layer deteriorated, and therefore, the comprehensive evaluation was "B".
  • Comparative Example 2 in which the Al content in the tube body was merely increased, the ability to form and regenerate the alumina barrier layer could be enhanced, but the mechanical characteristics deteriorated, and therefore, the comprehensive evaluation was "B”.
  • Comparative Example 2 the Al content on the outer diameter side was large, and therefore, the weldability was not favorable. Accordingly, when comprehensively evaluated as heat-resistant tubes to be used in a high-temperature environment, these comparative examples were inferior to the inventive examples.
  • the alumina barrier layer is less likely to be removed even when subjected to repeated cycles of heating and cooling. Even if the alumina barrier layer is removed, the alumina barrier layer is regenerated immediately. Accordingly, even when used in a high-temperature atmosphere, the heat-resistant tube having an alumina barrier layer of the present invention can exhibit excellent oxidation resistance, carburization resistance, nitridation resistance, corrosion resistance, coking resistance, and the like for a long period of time, and is excellent in mechanical characteristics such as creep rupture strength and tensile ductility.
  • the Al content on the outer diameter side is small, and therefore, the heat-resistant tube also exhibits excellent weldability when installed in a heating furnace. Accordingly, the lifetime of the heat-resistant tube can be improved significantly, and the operation efficiency can be enhanced to a level as high as possible because a time and a frequency of maintenance such as a coking removing operation can be reduced.
EP15872985.5A 2014-12-26 2015-12-21 Hitzebeständiges rohr mit aluminiumsperrschicht Active EP3239311B1 (de)

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
JP2014265938A JP6434306B2 (ja) 2014-12-26 2014-12-26 アルミナバリア層を有する耐熱管
PCT/JP2015/085655 WO2016104417A1 (ja) 2014-12-26 2015-12-21 アルミナバリア層を有する耐熱管

Publications (3)

Publication Number Publication Date
EP3239311A1 true EP3239311A1 (de) 2017-11-01
EP3239311A4 EP3239311A4 (de) 2018-06-20
EP3239311B1 EP3239311B1 (de) 2020-03-25

Family

ID=56150436

Family Applications (1)

Application Number Title Priority Date Filing Date
EP15872985.5A Active EP3239311B1 (de) 2014-12-26 2015-12-21 Hitzebeständiges rohr mit aluminiumsperrschicht

Country Status (6)

Country Link
EP (1) EP3239311B1 (de)
JP (1) JP6434306B2 (de)
CA (1) CA2972228C (de)
ES (1) ES2786180T3 (de)
SA (1) SA517381759B1 (de)
WO (1) WO2016104417A1 (de)

Cited By (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
EP3578676A1 (de) * 2018-06-07 2019-12-11 Manoir Pitres Austenitische legierung mit hohem aluminiumgehalt und assoziiertes designverfahren
CN110923512A (zh) * 2019-12-04 2020-03-27 上海旷彩环保科技发展有限公司 一种抗高温腐蚀的合金机芯、生产工艺及电磁加热回转窑
US11059134B2 (en) 2016-11-09 2021-07-13 Kubota Corporation Alloy for overlay welding and reaction tube
US11162151B2 (en) 2016-11-09 2021-11-02 Kubota Corporation Tube body that is to be used in high-temperature atmosphere and method for forming metal oxide layer on inner surface of tube body
US11612967B2 (en) 2016-11-09 2023-03-28 Kubota Corporation Alloy for overlay welding and reaction tube

Families Citing this family (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US11649517B2 (en) * 2016-10-21 2023-05-16 Korea Advanced Institute Of Science And Technology High-strength Fe—Cr—Ni—Al multiplex stainless steel and manufacturing method therefor
JP6339284B1 (ja) * 2017-11-06 2018-06-06 株式会社クボタ 鋼材と接触して使用される鉄鋼製品
CN111542639A (zh) * 2017-12-28 2020-08-14 日本制铁株式会社 奥氏体系耐热合金
JP7016283B2 (ja) * 2018-04-25 2022-02-04 株式会社クボタ 耐高温腐食性を有する耐熱合金、溶接用粉末及び外周面に肉盛溶接層を具える配管
CN109967713A (zh) * 2019-04-08 2019-07-05 四川鑫鼎新材料有限公司 一种核屏蔽复合管及其制备方法

Family Cites Families (8)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JPH01153887A (ja) * 1987-12-10 1989-06-16 Kubota Ltd 二層遠心鋳造管
JPH05195161A (ja) * 1992-01-13 1993-08-03 Kubota Corp 耐浸炭性にすぐれた二層耐熱鋼管
AU2001267204A1 (en) * 2000-06-08 2001-12-17 Surface Engineered Products Corporation Coating system for high temperature stainless steel
DE10302989B4 (de) * 2003-01-25 2005-03-03 Schmidt + Clemens Gmbh & Co. Kg Verwendung einer Hitze- und korrosionsbeständigen Nickel-Chrom-Stahllegierung
DK1717330T3 (en) * 2004-02-12 2018-09-24 Nippon Steel & Sumitomo Metal Corp METAL PIPES FOR USE IN CARBON GASA MOSPHERE
KR20110107370A (ko) * 2009-02-16 2011-09-30 수미도모 메탈 인더스트리즈, 리미티드 금속관의 제조 방법
BR112013009481A2 (pt) * 2010-10-21 2016-07-26 Exxonmobil Res & Eng Co tubo bimetálico formado de alumina para fornos de processos de refinaria e métodos de fabricação e uso do mesmo
JP6068158B2 (ja) * 2012-03-30 2017-01-25 株式会社クボタ アルミナバリア層を有する鋳造製品

Cited By (8)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US11059134B2 (en) 2016-11-09 2021-07-13 Kubota Corporation Alloy for overlay welding and reaction tube
US11162151B2 (en) 2016-11-09 2021-11-02 Kubota Corporation Tube body that is to be used in high-temperature atmosphere and method for forming metal oxide layer on inner surface of tube body
US11612967B2 (en) 2016-11-09 2023-03-28 Kubota Corporation Alloy for overlay welding and reaction tube
EP3578676A1 (de) * 2018-06-07 2019-12-11 Manoir Pitres Austenitische legierung mit hohem aluminiumgehalt und assoziiertes designverfahren
FR3082209A1 (fr) * 2018-06-07 2019-12-13 Manoir Pitres Alliage austenitique avec haute teneur en aluminium et procede de conception associe
US11408057B2 (en) 2018-06-07 2022-08-09 Manoir Pitres Austenitic alloy with high aluminum content and associated design process
CN110923512A (zh) * 2019-12-04 2020-03-27 上海旷彩环保科技发展有限公司 一种抗高温腐蚀的合金机芯、生产工艺及电磁加热回转窑
CN110923512B (zh) * 2019-12-04 2020-12-04 上海江竑环保科技有限公司 一种抗高温腐蚀的合金机芯、生产工艺及电磁加热回转窑

Also Published As

Publication number Publication date
JP6434306B2 (ja) 2018-12-05
WO2016104417A1 (ja) 2016-06-30
CA2972228A1 (en) 2016-06-30
JP2016125088A (ja) 2016-07-11
ES2786180T3 (es) 2020-10-09
EP3239311B1 (de) 2020-03-25
SA517381759B1 (ar) 2021-07-12
CA2972228C (en) 2022-08-02
EP3239311A4 (de) 2018-06-20

Similar Documents

Publication Publication Date Title
EP3239311B1 (de) Hitzebeständiges rohr mit aluminiumsperrschicht
JP5451751B2 (ja) アルミナバリア層を有する鋳造製品
US10144058B2 (en) Method for manufacturing round billet of Ni-containing high alloy having improved internal quality
CA3049514C (en) Heat-resistant alloy, and reaction tube
RU2690059C1 (ru) Стальной материал и стальная труба для нефтяных скважин
JP2016223017A (ja) アルミナバリア層を有するエチレン製造用反応管
US20190291219A1 (en) Alloy for overlay welding and reaction tube
EP3118341B1 (de) Ferritischer edelstahl
EP3124645B1 (de) Giessprodukt mit aluminiumoxidsperrschicht
JP2012214833A (ja) 冷間工具鋼
CA3030503C (en) Aluminum-containing steel product with excellent oxidation resistance and weldability for use in contact with steel material
US11612967B2 (en) Alloy for overlay welding and reaction tube
JP5977054B2 (ja) アルミナバリア層を有する鋳造製品の製造方法
JP5399000B2 (ja) 真空浸炭熱処理用耐熱鋳鋼ジグ材
US11674212B2 (en) Cast product having alumina barrier layer
KR102551616B1 (ko) 열간 압연용 롤 외층재 및 열간 압연용 복합 롤
JPH07258780A (ja) 耐浸炭性に優れた耐熱合金
JP2004091812A (ja) 製造性に優れるマルテンサイト系ステンレス熱延鋼帯
JP2002173720A (ja) 熱間加工性に優れたＮｉ基合金
JPH0987787A (ja) 耐酸化性、耐浸炭性、高温クリープ破断強度及び時効後の延性にすぐれる耐熱合金
JP2004263221A (ja) 耐ヒートクラック性および耐クリープ変形性に優れる耐熱合金
JPH09291374A (ja) 鉄系鋳造品の被覆材料およびそれによる被覆層を備えた鉄系鋳造品およびその被覆層の形成方法
JPS63121634A (ja) 搬送部材

Legal Events

Date Code Title Description
STAA Information on the status of an ep patent application or granted ep patent

Free format text: STATUS: THE INTERNATIONAL PUBLICATION HAS BEEN MADE

PUAI Public reference made under article 153(3) epc to a published international application that has entered the european phase

Free format text: ORIGINAL CODE: 0009012

STAA Information on the status of an ep patent application or granted ep patent

Free format text: STATUS: REQUEST FOR EXAMINATION WAS MADE

17P Request for examination filed

Effective date: 20170609

AK Designated contracting states

Kind code of ref document: A1

Designated state(s): AL AT BE BG CH CY CZ DE DK EE ES FI FR GB GR HR HU IE IS IT LI LT LU LV MC MK MT NL NO PL PT RO RS SE SI SK SM TR

AX Request for extension of the european patent

Extension state: BA ME

DAV Request for validation of the european patent (deleted)
DAX Request for extension of the european patent (deleted)
A4 Supplementary search report drawn up and despatched

Effective date: 20180517

RIC1 Information provided on ipc code assigned before grant

Ipc: C22C 30/00 20060101ALI20180511BHEP

Ipc: B22D 13/02 20060101ALI20180511BHEP

Ipc: C22C 19/05 20060101AFI20180511BHEP

Ipc: C22C 38/00 20060101ALI20180511BHEP

Ipc: C22C 38/58 20060101ALI20180511BHEP

Ipc: B22D 13/06 20060101ALI20180511BHEP

Ipc: B22D 13/10 20060101ALI20180511BHEP

GRAJ Information related to disapproval of communication of intention to grant by the applicant or resumption of examination proceedings by the epo deleted

Free format text: ORIGINAL CODE: EPIDOSDIGR1

GRAP Despatch of communication of intention to grant a patent

Free format text: ORIGINAL CODE: EPIDOSNIGR1

GRAP Despatch of communication of intention to grant a patent

Free format text: ORIGINAL CODE: EPIDOSNIGR1

STAA Information on the status of an ep patent application or granted ep patent

Free format text: STATUS: GRANT OF PATENT IS INTENDED

GRAJ Information related to disapproval of communication of intention to grant by the applicant or resumption of examination proceedings by the epo deleted

Free format text: ORIGINAL CODE: EPIDOSDIGR1

GRAP Despatch of communication of intention to grant a patent

Free format text: ORIGINAL CODE: EPIDOSNIGR1

INTG Intention to grant announced

Effective date: 20190926

INTG Intention to grant announced

Effective date: 20191016

GRAS Grant fee paid

Free format text: ORIGINAL CODE: EPIDOSNIGR3

GRAA (expected) grant

Free format text: ORIGINAL CODE: 0009210

STAA Information on the status of an ep patent application or granted ep patent

Free format text: STATUS: THE PATENT HAS BEEN GRANTED

AK Designated contracting states

Kind code of ref document: B1

Designated state(s): AL AT BE BG CH CY CZ DE DK EE ES FI FR GB GR HR HU IE IS IT LI LT LU LV MC MK MT NL NO PL PT RO RS SE SI SK SM TR

REG Reference to a national code

Ref country code: GB

Ref legal event code: FG4D

REG Reference to a national code

Ref country code: AT

Ref legal event code: REF

Ref document number: 1248629

Country of ref document: AT

Kind code of ref document: T

Effective date: 20200415

Ref country code: IE

Ref legal event code: FG4D

REG Reference to a national code

Ref country code: DE

Ref legal event code: R096

Ref document number: 602015049607

Country of ref document: DE

PG25 Lapsed in a contracting state [announced via postgrant information from national office to epo]

Ref country code: RS

Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT

Effective date: 20200325

Ref country code: FI

Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT

Effective date: 20200325

Ref country code: NO

Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT

Effective date: 20200625

PG25 Lapsed in a contracting state [announced via postgrant information from national office to epo]

Ref country code: HR

Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT

Effective date: 20200325

Ref country code: LV

Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT

Effective date: 20200325

Ref country code: SE

Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT

Effective date: 20200325

Ref country code: BG

Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT

Effective date: 20200625

Ref country code: GR

Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT

Effective date: 20200626

REG Reference to a national code

Ref country code: NL

Ref legal event code: MP

Effective date: 20200325

REG Reference to a national code

Ref country code: LT

Ref legal event code: MG4D

PG25 Lapsed in a contracting state [announced via postgrant information from national office to epo]

Ref country code: NL

Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT

Effective date: 20200325

REG Reference to a national code

Ref country code: ES

Ref legal event code: FG2A

Ref document number: 2786180

Country of ref document: ES

Kind code of ref document: T3

Effective date: 20201009

PG25 Lapsed in a contracting state [announced via postgrant information from national office to epo]

Ref country code: SM

Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT

Effective date: 20200325

Ref country code: EE

Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT

Effective date: 20200325

Ref country code: CZ

Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT

Effective date: 20200325

Ref country code: IS

Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT

Effective date: 20200725

Ref country code: RO

Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT

Effective date: 20200325

Ref country code: SK

Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT

Effective date: 20200325

Ref country code: LT

Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT

Effective date: 20200325

Ref country code: PT

Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT

Effective date: 20200818

REG Reference to a national code

Ref country code: AT

Ref legal event code: MK05

Ref document number: 1248629

Country of ref document: AT

Kind code of ref document: T

Effective date: 20200325

REG Reference to a national code

Ref country code: DE

Ref legal event code: R097

Ref document number: 602015049607

Country of ref document: DE

PG25 Lapsed in a contracting state [announced via postgrant information from national office to epo]

Ref country code: DK

Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT

Effective date: 20200325

Ref country code: AT

Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT

Effective date: 20200325

Ref country code: IT

Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT

Effective date: 20200325

PLBE No opposition filed within time limit

Free format text: ORIGINAL CODE: 0009261

STAA Information on the status of an ep patent application or granted ep patent

Free format text: STATUS: NO OPPOSITION FILED WITHIN TIME LIMIT

PG25 Lapsed in a contracting state [announced via postgrant information from national office to epo]

Ref country code: PL

Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT

Effective date: 20200325

26N No opposition filed

Effective date: 20210112

PG25 Lapsed in a contracting state [announced via postgrant information from national office to epo]

Ref country code: SI

Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT

Effective date: 20200325

REG Reference to a national code

Ref country code: CH

Ref legal event code: PL

GBPC Gb: european patent ceased through non-payment of renewal fee

Effective date: 20201221

PG25 Lapsed in a contracting state [announced via postgrant information from national office to epo]

Ref country code: MC

Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT

Effective date: 20200325

REG Reference to a national code

Ref country code: BE

Ref legal event code: MM

Effective date: 20201231

PG25 Lapsed in a contracting state [announced via postgrant information from national office to epo]

Ref country code: LU

Free format text: LAPSE BECAUSE OF NON-PAYMENT OF DUE FEES

Effective date: 20201221

Ref country code: IE

Free format text: LAPSE BECAUSE OF NON-PAYMENT OF DUE FEES

Effective date: 20201221

PG25 Lapsed in a contracting state [announced via postgrant information from national office to epo]

Ref country code: GB

Free format text: LAPSE BECAUSE OF NON-PAYMENT OF DUE FEES

Effective date: 20201221

Ref country code: LI

Free format text: LAPSE BECAUSE OF NON-PAYMENT OF DUE FEES

Effective date: 20201231

Ref country code: CH

Free format text: LAPSE BECAUSE OF NON-PAYMENT OF DUE FEES

Effective date: 20201231

PG25 Lapsed in a contracting state [announced via postgrant information from national office to epo]

Ref country code: TR

Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT

Effective date: 20200325

Ref country code: MT

Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT

Effective date: 20200325

Ref country code: CY

Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT

Effective date: 20200325

PG25 Lapsed in a contracting state [announced via postgrant information from national office to epo]

Ref country code: MK

Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT

Effective date: 20200325

Ref country code: AL

Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT

Effective date: 20200325

PG25 Lapsed in a contracting state [announced via postgrant information from national office to epo]

Ref country code: BE

Free format text: LAPSE BECAUSE OF NON-PAYMENT OF DUE FEES

Effective date: 20201231

PGFP Annual fee paid to national office [announced via postgrant information from national office to epo]

Ref country code: ES

Payment date: 20230109

Year of fee payment: 8

REG Reference to a national code

Ref country code: DE

Ref legal event code: R082

Ref document number: 602015049607

Country of ref document: DE

Representative=s name: TER MEER STEINMEISTER & PARTNER PATENTANWAELTE, DE

PGFP Annual fee paid to national office [announced via postgrant information from national office to epo]

Ref country code: FR

Payment date: 20231108

Year of fee payment: 9

Ref country code: DE

Payment date: 20231031

Year of fee payment: 9

PGFP Annual fee paid to national office [announced via postgrant information from national office to epo]

Ref country code: ES

Payment date: 20240110

Year of fee payment: 9