EP1529853A2 - Acier pour la chimie - Dispositifs - Composants - Google Patents

Acier pour la chimie - Dispositifs - Composants Download PDF

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Publication number
EP1529853A2
EP1529853A2 EP04450192A EP04450192A EP1529853A2 EP 1529853 A2 EP1529853 A2 EP 1529853A2 EP 04450192 A EP04450192 A EP 04450192A EP 04450192 A EP04450192 A EP 04450192A EP 1529853 A2 EP1529853 A2 EP 1529853A2
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EP
European Patent Office
Prior art keywords
max
component
elements
iron
strength
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
EP04450192A
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German (de)
English (en)
Other versions
EP1529853B1 (fr
EP1529853A3 (fr
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
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Publication date
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Application filed by BHDT GmbH, Boehler Edelstahl GmbH filed Critical BHDT GmbH
Publication of EP1529853A2 publication Critical patent/EP1529853A2/fr
Publication of EP1529853A3 publication Critical patent/EP1529853A3/fr
Application granted granted Critical
Publication of EP1529853B1 publication Critical patent/EP1529853B1/fr
Revoked legal-status Critical Current
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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 an iron-based alloy for use as a material for high-pressure components with elevated working temperature, in particular tempered steel for components such as tube heat exchangers in high-pressure polyethylene plants, containing the main alloying elements in% by weight of: Carbon (C) 0.22 to 0.29 Chrome (Cr) 1.1 to 1.5 Molybdenum (Mo) 0.3 to 0.6 Nickel (Ni) 3.3 to 3.7 possibly Vanadin (V) 0.05 to 0.15 Remainder iron (Fe) furthermore sulfide and oxide forming - as well as accompanying and impurity elements. Furthermore, the invention relates to a component with increased working temperature, in particular tube heat exchanger for polyethylene - high pressure systems formed from an iron-based alloy mentioned above.
  • 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.
  • An increase of the 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, whereby a ratio of 0.2% yield strength (FIG. Rp 0.2 ) 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.
  • a disadvantage with thick-walled pipes is reaching the so-called leak Rupture criteria, which in the high pressure technique for safety reasons always must be fulfilled.
  • a parameter for unstable break include the critical fracture toughness such as Klc or Jlc or the critical crack length ac
  • Material-specific characteristics are mainly due to the toughness of the material dependent.
  • the invention seeks to remedy these shortcomings and sets itself the task of a Iron-based alloy of the type mentioned for use for High pressure components with increased strength at high strain and To indicate toughness values of the material.
  • Another object of the invention is to provide a component, in particular Tube heat exchanger for high-pressure polyethylene plants with improved Use characteristics and / or similar safety criteria formed from an aforementioned iron base material with high strength and at the same time favorable elongation and toughness values.
  • the mode of action of the alloy according to the invention is intended present elements are set forth, the Main alloying elements related to a thermal remuneration are functionally kinetically matched.
  • 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 may 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 to a great extent 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 publication.
  • Molybdenum has a deleterious effect on temper embrittlement, is a stronger carbide former as chromium and iron and should be consistent with Cr with a content of at least 0.3 wt .-% in the steel present to a corresponding hardness-increasing effect exercise while tempering the part.
  • Advantageously fine Mo carbides and Mixed carbides are annealed to a Mo content of 0.6% by weight excreted what the ductility of the material at high hardness of the same promotes.
  • Nickel essentially affects the hardenability of the material and acts toughness promoting. Lower contents than 3.3% by weight are less effective, whereas higher nickel concentrations than 3.7% by weight are too strong Austenite stabilizing effect, whereby a narrow nickel content range of Alloy is justified.
  • Vanadium with contents of 0.05 to 0.15 wt .-% can be provided in the material be.
  • V as a very strong carbide former acts as a fine micro-alloying element material hardness increase due to extremely fine secondary carbide precipitations when tempering after curing in the temperature range between 450 ° C and 560 ° C. Higher contents than 0.15 wt .-% V, the hardenability undesirable influence and reduce the material toughness.
  • the iron-based alloy according to the invention has besides the Main alloying elements as the remainder of Iron and Companion as well Impurity elements.
  • Mn, Co, Cu and W are the elements Mn, Co, Cu and W incorporated in the solid solution.
  • Manganese affects the hardenability of the steel, binds off the residual sulfur content and is advantageously provided in a concentration range of 0.15 to 0.5 wt .-% in the steel. Lower levels can cause too low a sulfur activity, which increases the risk of breakage and the property profile are adversely affected.
  • Co, Cu and W are elements which can be incorporated in certain concentrations in the mixed crystal, however, they have an extremely disadvantageous effect on the ratio in concentrations above 0.31% by weight rp 0.2 , R m
  • the value for the 0.2% proof stress increases of the material in the case of sum quantities (Co, Cu and W) of greater than 0.31, resulting in a ratio with disadvantage of over 0.95.
  • the impurity elements sulfur and phosphorus cause sinking Held to a mechanical improvement expected by the skilled person Characteristics of the material, however, should be extreme in terms of the required 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 .-% not exceed.
  • Oxygen in the steel is bonded by oxide-forming elements, wherein oxide inclusions are formed, which are the material properties, especially the toughness and elongation deteriorate. Also through Remelting processes can not completely eliminate the oxidation products Alloy are eliminated so that their oxygen content is 0.0038 maximum Wt .-% should be.
  • the grain boundary elements As, Bi, Sb, Sn, Zn and B with a sum content of less than 0.015 wt .-% in the alloy is also at high hardness values of the coated material the ductility of the same given sufficiently. A crossing of this However, cumulative concentration value promotes a deformation-free Brittle fracture tendency.
  • the strong nitride formers in the alloy according to the invention are low Have contents, but is a highest cumulative concentration of N + H of 0.01 wt .-%, with the advantage of 0.008 wt .-% required to a desired Be able to achieve property level of the material.
  • the material is hot worked by forging or rolling and a Degree of deformation greater than 4.1 times, can after a thermal Tempering of the part, in particular a rod or a pipe high Strength values and thereby significantly improved toughness properties at a Working temperature of 350 ° C can be achieved.
  • the alloy is prepared by means of pan metallurgical processes and / or using the ESU process and / or the Vacuum arc furnace process, because this production is also a Segregation in the block minimizes and thus the prerequisite for essentially creates the same material properties in the longitudinal and transverse direction of the part.
  • the further object of the invention is in a component, in particular
  • Tube heat exchanger for high-pressure polyethylene plants formed of an iron-based alloy having a composition as described above, achieved in that the component has a tensile strength Rm of the material of greater than 1100 N / mm 2 and a 0.2% yield strength at 320 ° C. of greater than 880 N / mm 2 ..
  • the wall thickness of the High pressure components are reduced because of the 0.2% yield strength at Room temperature and at an operating temperature of 320 ° C substantially spaced from the strength value and thus a high level of safety of the component is present against separation break.
  • Thinner wall thicknesses for example one Heat exchanger, also cause a higher specific heat transfer, so that the reactor with substantially reduced dimension the same performance or at the same size, the reactor has a higher performance. From Of particular importance is the "leak before crack" criterion.
  • the component in particular tube heat exchanger for high-pressure polyethylene plants
  • a tensile strength Rm of the material greater than 1170 N / mm 2
  • this has a 0.2% yield strength of greater than 1060 N / mm 2 and a 0.2% Yield point at 320 ° C of greater than 930 N / mm 2
  • a further reduction of the wall thickness of high-pressure components is possible, which can provide significant plant engineering, 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 component: Elongation A5 > 15/14% Elongation at break A4 > 17/16% Fracture necking Z > 55/45% Notched Toughness AV (RT) > 80/60 y Notched impact strength AV (-40 ° C) > 50/35 y
  • a separation fracture is achieved with a ratio of the material of 0.2 % Yield strength broken by tensile strength less than 0.94, preferably from less than 0.92.
  • the 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 invention is a choice or setting of the current stress intensity factor to fulfill the "leak before break" criterion.
  • Table 1 shows the chemical composition of two of the invention Materials.
  • the melts were treated by ladle metallurgy and each poured into electrodes.
  • the block of the batch H 75142 was in the Vacuum arc furnace remelted and in a long forging machine 5.85 times to a rod with a diameter of 200 mm ⁇ further deformed, off which rod tubes for a heat exchanger of a polyethylene reactor were manufactured.
  • the thermal treatment of the pipe material was carried out on 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 carried out the same way as the VLBO block.
  • Table 2 shows the measured mechanical values of the material of the Rod material indicated.
  • the indication "ZVF” stands for tensile test with fine strain measurement, that for " ZVW “stands for hot tensile test at 320 ° C.
  • the indication” KR “indicates a Notched impact strength test at room temperature, those with “KK” means Notched impact strength values at reduced temperature, in the given case - 23 ° C. In order to meet the high safety requirements, the Notched impact strength of the material tested by means of three samples.
  • the designation A5 stands for the used sample length and that 5x the Sample diameter.
  • Table 2 shows the inventive comparison of the measured values Improvement of material properties and in comparison with the state of The technical progress of the technical progress concerning the increase of the Property levels of materials for high pressure components, in particular Pipe heat exchangers for plants of the chemical industry.
  • Fig. 2 shows a dependence of 0.2% strain of the Sum concentration of the elements (Co + Cu + W), Fig.3 elongation at break values of the annealed material as a function of the sum concentration of containing elements (As + Bi + Sb + Sn + Zn + B).
EP04450192A 2003-11-07 2004-10-13 Utilisation d'un acier pour composants tubulaires et composants tubulaires pour échangeur thermique Revoked EP1529853B1 (fr)

Applications Claiming Priority (2)

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

Publications (3)

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

Family

ID=32686631

Family Applications (1)

Application Number Title Priority Date Filing Date
EP04450192A Revoked EP1529853B1 (fr) 2003-11-07 2004-10-13 Utilisation d'un acier pour composants tubulaires et composants tubulaires pour échangeur thermique

Country Status (6)

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

Cited By (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
EP3121199A1 (fr) 2015-07-23 2017-01-25 Basell Polyolefine GmbH Procédé de polymérisation haute pression de monomères éthyléniquement insaturés dans un réacteur tubulaire

Families Citing this family (3)

* 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
RU2629126C1 (ru) * 2016-05-10 2017-08-24 Публичное акционерное общество "Синарский трубный завод" (ПАО "СинТЗ") Труба бесшовная нефтяного сортамента высокопрочная в сероводородостойком исполнении

Citations (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JPS59129724A (ja) * 1983-01-14 1984-07-26 Nippon Steel Corp 厚肉超高張力鋼の製造方法
US5225156A (en) * 1989-02-01 1993-07-06 Metal Research Corporation Clean steel composition
EP0580062A1 (fr) * 1992-07-21 1994-01-26 Thyssen Stahl Aktiengesellschaft Procédé pour la fabrication des plaques de blindage épaisses
EP1127951A1 (fr) * 1999-06-16 2001-08-29 Nippon Steel Corporation Acier fortement nettoye

Family Cites Families (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JPH01179896A (ja) * 1988-01-06 1989-07-17 Hitachi Ltd 熱交換器
JP2712702B2 (ja) * 1990-02-06 1998-02-16 住友金属工業株式会社 圧力容器用鋼
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

Patent Citations (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JPS59129724A (ja) * 1983-01-14 1984-07-26 Nippon Steel Corp 厚肉超高張力鋼の製造方法
US5225156A (en) * 1989-02-01 1993-07-06 Metal Research Corporation Clean steel composition
EP0580062A1 (fr) * 1992-07-21 1994-01-26 Thyssen Stahl Aktiengesellschaft Procédé pour la fabrication des plaques de blindage épaisses
EP1127951A1 (fr) * 1999-06-16 2001-08-29 Nippon Steel Corporation Acier fortement nettoye

Non-Patent Citations (3)

* Cited by examiner, † Cited by third party
Title
L.E.K. HOLAPPA, A.S. HELLE: "Inclusion control in high performance steels" JOURNAL OF MATERIALS PROCESSING TECHNOLOGY, Nr. 53, 1995, Seiten 177-186, XP002427802 *
P.A. BRALSFORD, E. HYDES, G.A. HONEYMAN: "Residual contents in purchased scrap for use in basic electric arc technology" CLEAN STEEL: SUPERCLEAN STEEL, CONFERENCE PROCEEDINGS, 1996, Seiten 53-58, XP002427800 London *
R. VISWANATHAN: "Application of clean steel/superclean steel technology in the electric power industry - overview of EPRI research and products" CLEAN STEEL: SUPERCLEAN STEEL, CONFERENCE PROCEEDINGS, 1996, Seiten 1-31, XP002427801 London *

Cited By (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
EP3121199A1 (fr) 2015-07-23 2017-01-25 Basell Polyolefine GmbH Procédé de polymérisation haute pression de monomères éthyléniquement insaturés dans un réacteur tubulaire

Also Published As

Publication number Publication date
US20050169790A1 (en) 2005-08-04
ES2382633T3 (es) 2012-06-12
CA2486902C (fr) 2013-07-09
AT414341B (de) 2010-12-15
EP1529853B1 (fr) 2012-02-22
ATE546560T1 (de) 2012-03-15
NO20044796L (no) 2005-05-09
CA2486902A1 (fr) 2005-05-07
EP1529853A3 (fr) 2007-09-05
US7662246B2 (en) 2010-02-16
ATA17832003A (de) 2004-07-15

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