EP1529853B1 - Verwendung eines Stahls für Rohrbauteile und Rohrbauteile für Rohr-Wärmetauscher - Google Patents

Verwendung eines Stahls für Rohrbauteile und Rohrbauteile für Rohr-Wärmetauscher Download PDF

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Publication number
EP1529853B1
EP1529853B1 EP04450192A EP04450192A EP1529853B1 EP 1529853 B1 EP1529853 B1 EP 1529853B1 EP 04450192 A EP04450192 A EP 04450192A EP 04450192 A EP04450192 A EP 04450192A EP 1529853 B1 EP1529853 B1 EP 1529853B1
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EP
European Patent Office
Prior art keywords
maximum
elements
minimum
yield strength
pipe component
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.)
Revoked
Application number
EP04450192A
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German (de)
English (en)
French (fr)
Other versions
EP1529853A3 (de
EP1529853A2 (de
Inventor
Johann Zand
Johannes Schedelmaier
Manfred Pölzl
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.)
BHDT GmbH
Voestalpine Boehler Edelstahl GmbH and Co KG
Original Assignee
BHDT GmbH
Boehler Edelstahl GmbH and Co KG
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Application filed by BHDT GmbH, Boehler Edelstahl GmbH and Co KG filed Critical BHDT GmbH
Publication of EP1529853A2 publication Critical patent/EP1529853A2/de
Publication of EP1529853A3 publication Critical patent/EP1529853A3/de
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    • 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
    • C22C38/44—Ferrous alloys, e.g. steel alloys containing chromium with nickel with molybdenum or tungsten
    • 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
    • C22C38/46—Ferrous alloys, e.g. steel alloys containing chromium with nickel with vanadium

Definitions

  • the invention relates to the use of an iron-based alloy for tube components for tube heat exchangers in high-pressure polyethylene plants, comprising the main alloying elements in% by weight of: Carbon (C) 12:22 to 12:29 Chrome (Cr) 1.1 to 1.5 Molybdenum (Mo) 0.3 to 0.6 Nickel (Ni) optionally 3.3 to 3.7 Vanadin (V) 12:05 to 12:15 furthermore sulphide and oxide forming as well as accompanying and impurity elements remainder iron (Fe).
  • the invention relates to a pipe component for tube heat exchangers for high-pressure polyethylene plants formed using an iron-based alloy mentioned above.
  • the parts are austenitized and quenched and tempered by the austenitizing temperature at a high cooling rate and then tempered, with thermal annealing of the material Material often followed by a relaxation treatment at temperatures up to the tempering temperature.
  • An increase in the tensile strength of the material caused by tempering by means of hardening and tempering also has a significant effect on the other mechanical material properties at room temperature and at elevated working temperatures out.
  • An increase in tensile strength over a value of 1000 N / mm 2 to 1100 N / mm 2 and above disproportionately increases the 0.2% yield strength of the iron base material, resulting in a 0.2% yield strength (Rp 0.2 .)
  • Ratio characteristic of the safety of operation of high pressure equipment ) to tensile strength (Rm) is adversely affected.
  • the yield strength approaches tensile strength, significantly lowering the elongation at break and impact strength of the material and significantly reducing crack fracture toughness.
  • the aforesaid materials are only thermally tempered up to the strength at which the related elongation and toughness properties of the material are deemed sufficient or comply with regulations.
  • a technical technical disadvantage is thus a large wall thickness of the high-pressure components required, optionally influencing a reaction kinetics of the chemical substances and low cost of the reactor or the device given. If, for example, high-pressure heat exchangers are designed to set sufficiently high elongation and toughness values of the material with the requisite strength, the load must be dimensioned correspondingly to the wall thickness, with which a low specific heat transfer is connected, which requires large thick-walled reactors.
  • a disadvantage with thick-walled pipes is the achievement of the so-called "leak before break” criterion, which must always be met in high-pressure technology for safety reasons, in other words: If a crack grows in the pipe wall during operation of a reactor, it must first cover the outside surface
  • the values for unstable fracture include the critical fracture toughnesses such as Klc or Jlc or the critical crack length ac. These material-specific characteristics depend, above all, on the toughness of the material.
  • the invention seeks to remedy these shortcomings and sets itself the task of a
  • Another object of the invention is to provide a tube member for tube heat exchangers of high pressure polyethylene plants having improved performance characteristics and / or the like. Safety criteria formed using an aforementioned iron base alloy with high strength and at the same time favorable elongation and toughness values.
  • the mode of action of the elements present in the alloy according to the invention should be described in more detail, the main alloying elements being adjusted to one another in terms of kinetic energy with respect to a thermal tempering.
  • Carbon dissolves when heated in the austenite of the alloy in the solid solution and causes quenching a strain of the crystal lattice and thus hardening of the material.
  • C contents of at least 0.22% by weight are required in order to achieve a material hardness of at least 1100 N / mm 2 with a coating. If the carbon concentration exceeds 0.29% by weight, more stable carbides and reduced toughness values of the material can be present, so that a content range within narrow limits of 0.22 to 0.29% by weight C is provided.
  • chromium essentially binds Cr 23 C 6 , Cr 7 C 3 and Cr 3 C 2 carbides and greatly influences the hardening criteria of the material.
  • at least 1.1, but at most 1.5 wt .-% Cr are favorable for a desired carbide and Mischkarbid project.
  • Molybdenum has a reducing effect on embrittlement embrittlement, is a stronger carbide former than chromium and iron and should be present in the steel in accordance with Cr with a content of at least 0.3 wt .-% in order to exert a corresponding hardness-increasing effect in the annealing of the part.
  • Advantageously fine Mo carbides and mixed carbides are eliminated during tempering to a Mo content of 0.6 wt .-%, which promotes the same ductility of the material at high hardness.
  • Nickel essentially influences the hardenability of the material and has a ductile effect. Lower nickel contents than 3.3% by weight are less effective, whereas higher nickel concentrations than 3.7% by weight have too high an austenite stabilizing effect, thereby justifying a narrow nickel content range of the alloy.
  • Vanadium with contents of 0.05 to 0.15 wt .-% may be provided in the material.
  • V as a very strong carbide former acts as a micro-alloying element, fine-grained by an extremely fine secondary carbide precipitate, which raises the material hardness during tempering after hardening in the temperature range between 450 ° C and 560 ° C. Higher contents than 0.15% by weight V may undesirably affect the hardenability and reduce the material toughness.
  • the iron-based alloy which is used according to the invention for tube parts for heat exchangers in high-pressure polyethylene plant n, has in addition to the main alloying elements as the remainder iron and accompanying and impurity elements.
  • One group of these companion and impurity elements are the elements Mn, Co, Cu and W incorporated in the solid solution.
  • Co, Cu and W are elements which can be incorporated in certain proportions in the mixed crystal, however, they have an extremely disadvantageous effect on the ratio Rp 0.2 in concentrations above 0.31% by weight . rm
  • the impurity elements sulfur and phosphorus lead with sinking levels to an improvement of the mechanical properties of the material expected by a person skilled in the art, however, in view of the required extremely high property profile of the tempered material values of 0.003 wt .-% S and 0.005 wt .-% P at a cumulative concentration of 0.006 wt .-% does not exceed.
  • Dissolved oxygen in the steel is set by oxide-forming elements to form oxide inclusions, which deteriorate the material properties, in particular the toughness and elongation. Even by remelting processes, the oxidation products can not be completely eliminated from the alloy, so that their oxygen content MAX should be 0.0038 wt .-%.
  • the grain boundary elements As, Bi, Sb, Sn, Zn and B are present in the alloy with a sum content of less than 0.015% by weight, the ductility of the same is sufficiently high even with high hardness values of the tempered material given. Exceeding this sum concentration value, however, promotes a deformation-free separation tendency.
  • the strong nitride formers in the alloy according to the invention have low contents, however, a highest cumulative concentration of N + H of 0.01% by weight, advantageously 0.008% by weight, is required in order to achieve a desired property level of the material.
  • the material is hot-formed by forging or rolling and has a degree of deformation greater than 4.1 times, after a thermal
  • Toughening a pipe high strength and thereby significantly improved toughness properties can be achieved at a working temperature of 350 ° C.
  • the alloy is produced by means of ladle metallurgical processes and / or using the ESU process and / or the vacuum arc furnace process, because this production also minimizes segregation in the block and thus the prerequisite for substantially equal material properties in longitudinal and Transverse direction of the part creates.
  • the further object of the invention is achieved in a pipe component for heat exchangers of high-pressure polyethylene plants according to claim 4.
  • Pipe components can be reduced because the 0.2% yield strength at room temperature and at a working temperature of 320 ° C is significantly spaced from the strength value and thus there is a high level of safety of the pipe component against breakage.
  • Of particular importance is the "leak before break " criterion.
  • the tube component as a tube heat exchanger in polyethylene high-pressure systems, is tempered to a tensile strength Rm of the material greater than 1170 N / mm 2 , this has a 0.2% yield strength greater than 1060 N / mm 2 and a 0.2% yield strength at 320 ° C greater than 9 2 0 N / mm 2 , a further reduction of the wall thickness of high-pressure components is possible, which can provide significant plant-related, but also reaction kinetic advantages.
  • the mechanical property values of this aforementioned higher-strength material are measured in the direction of the longitudinal extent and transversely to the longitudinal extent of the pipe component: Elongation A5 > 15/14% Elongation at break A4 > 17/16% Fracture necking Z > 55/45% Notched Toughness AV (RT) > 80 / 60y Notched impact strength AV (-40 ° C)> 50 / 35years
  • the tube component with a crack fracture toughness J 1C of the material of greater than 150 kJ / m 2, measured according to ASTM -E 813, is preferred.
  • An essential part of the pipe component of the invention is a choice or adjustment of the current stress intensity factor to fulfill the "leak before break" criterion at high internal pressure.
  • Tab. 1 shows the chemical composition of two materials used according to the invention.
  • the melts were ladle metallurgically treated and cast into electrodes, respectively.
  • the block of batch H 75142 was remelted in a vacuum arc furnace and further deformed in a long forging machine 5.85 times to a rod with a diameter of 200 mm ⁇ , from which rod tubes for a heat exchanger of a polyethylene reactor were made.
  • the thermal treatment of the pipe material was carried out to a strength Rm of about Rm 1250 MPa.
  • the block of batch G 53227 was prepared by the ESU method.
  • the further processing to heat exchanger tubes was the same as in the VLBO block.
  • Table 2 shows the measured mechanical characteristics of the material of the rod material.
  • the indication “ZVF” stands for tensile test with fine strain measurement, that "ZVW” stands for hot tensile test at 320 ° C.
  • the indication “KR” indicates an impact test at room temperature, that with “KK” means impact resistance values at a low temperature, in this case -23 ° C. In order to meet the high safety requirements, the notched impact strength of the material was tested by means of three samples.
  • the designation A5 stands for the sample length used, namely 5 times the sample diameter.
  • Tab. 2 shows the comparison of the measured values the improvement of the material properties according to the invention and in comparison with the prior art, the technical progress concerning the increase of the property level of materials for high pressure components, especially tube heat exchangers for plants of the chemical industry.
  • Fig. 2 a dependence of the 0.2% strain on the sum concentration of the elements (Co + Cu + W)
  • Fig. 3 Ultimate elongation values of the tempered material as a function of the sum concentration of the elements contained (As + Bi + Sb + Sn + Zn + B).

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  • Chemical & Material Sciences (AREA)
  • Engineering & Computer Science (AREA)
  • Materials Engineering (AREA)
  • Mechanical Engineering (AREA)
  • Metallurgy (AREA)
  • Organic Chemistry (AREA)
  • Heat Treatment Of Steel (AREA)
  • Heat Treatment Of Articles (AREA)
  • Rigid Pipes And Flexible Pipes (AREA)
  • Compositions Of Macromolecular Compounds (AREA)
EP04450192A 2003-11-07 2004-10-13 Verwendung eines Stahls für Rohrbauteile und Rohrbauteile für Rohr-Wärmetauscher Revoked EP1529853B1 (de)

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
AT0178303A AT414341B (de) 2003-11-07 2003-11-07 Stahl für chemie - anlagen - komponenten
AT17832003 2003-11-07

Publications (3)

Publication Number Publication Date
EP1529853A2 EP1529853A2 (de) 2005-05-11
EP1529853A3 EP1529853A3 (de) 2007-09-05
EP1529853B1 true EP1529853B1 (de) 2012-02-22

Family

ID=32686631

Family Applications (1)

Application Number Title Priority Date Filing Date
EP04450192A Revoked EP1529853B1 (de) 2003-11-07 2004-10-13 Verwendung eines Stahls für Rohrbauteile und Rohrbauteile für Rohr-Wärmetauscher

Country Status (6)

Country Link
US (1) US7662246B2 (es)
EP (1) EP1529853B1 (es)
AT (2) AT414341B (es)
CA (1) CA2486902C (es)
ES (1) ES2382633T3 (es)
NO (1) NO20044796L (es)

Families Citing this family (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US20130323075A1 (en) * 2012-06-04 2013-12-05 General Electric Company Nickel-chromium-molybdenum-vanadium alloy and turbine component
US9738334B2 (en) * 2013-05-07 2017-08-22 Arcelormittal Track shoe having increased service life useful in a track drive system
EP3121199B1 (en) 2015-07-23 2017-04-26 Basell Polyolefine GmbH High-pressure polymerization process of ethylenically unsaturated monomers in a tubular reactor
RU2629126C1 (ru) * 2016-05-10 2017-08-24 Публичное акционерное общество "Синарский трубный завод" (ПАО "СинТЗ") Труба бесшовная нефтяного сортамента высокопрочная в сероводородостойком исполнении

Family Cites Families (8)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JPH064889B2 (ja) * 1983-01-14 1994-01-19 新日本製鐵株式会社 厚肉超高張力鋼の製造方法
JPH01179896A (ja) * 1988-01-06 1989-07-17 Hitachi Ltd 熱交換器
US5225156A (en) * 1989-02-01 1993-07-06 Metal Research Corporation Clean steel composition
JP2712702B2 (ja) * 1990-02-06 1998-02-16 住友金属工業株式会社 圧力容器用鋼
DE4223895C1 (de) * 1992-07-21 1994-03-17 Thyssen Stahl Ag Verfahren zur Herstellung von dicken Panzerblechen
JPH08120400A (ja) * 1994-10-25 1996-05-14 Japan Steel Works Ltd:The 超高圧圧力容器用鋼およびその製造方法
JP3096959B2 (ja) * 1996-02-10 2000-10-10 住友金属工業株式会社 高温強度に優れた低Ｍｎ低Ｃｒフェライト耐熱鋼
EP1127951A1 (en) * 1999-06-16 2001-08-29 Nippon Steel Corporation Highly cleaned steel

Also Published As

Publication number Publication date
EP1529853A3 (de) 2007-09-05
ATE546560T1 (de) 2012-03-15
ES2382633T3 (es) 2012-06-12
CA2486902A1 (en) 2005-05-07
US20050169790A1 (en) 2005-08-04
AT414341B (de) 2010-12-15
CA2486902C (en) 2013-07-09
EP1529853A2 (de) 2005-05-11
US7662246B2 (en) 2010-02-16
ATA17832003A (de) 2004-07-15
NO20044796L (no) 2005-05-09

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