EP0889146B1 - Hitzebeständiger chromierter Stahl, Verfahren zur seiner Herstellung und seine Verwendung in anti-Verkokungsanwendungen - Google Patents

Hitzebeständiger chromierter Stahl, Verfahren zur seiner Herstellung und seine Verwendung in anti-Verkokungsanwendungen Download PDF

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Publication number
EP0889146B1
EP0889146B1 EP98401567A EP98401567A EP0889146B1 EP 0889146 B1 EP0889146 B1 EP 0889146B1 EP 98401567 A EP98401567 A EP 98401567A EP 98401567 A EP98401567 A EP 98401567A EP 0889146 B1 EP0889146 B1 EP 0889146B1
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EP
European Patent Office
Prior art keywords
coking
reactors
coated
article according
steel
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.)
Expired - Lifetime
Application number
EP98401567A
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English (en)
French (fr)
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EP0889146A1 (de
Inventor
Francois Ropital
Paul Broutin
Marcel Francois
Alain Bertoli
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IFP Energies Nouvelles IFPEN
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IFP Energies Nouvelles IFPEN
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Classifications

    • C—CHEMISTRY; METALLURGY
    • C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
    • C23C—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; SURFACE TREATMENT OF METALLIC MATERIAL BY DIFFUSION INTO THE SURFACE, BY CHEMICAL CONVERSION OR SUBSTITUTION; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL
    • C23C28/00—Coating for obtaining at least two superposed coatings either by methods not provided for in a single one of groups C23C2/00 - C23C26/00 or by combinations of methods provided for in subclasses C23C and C25C or C25D
    • C23C28/02—Coating for obtaining at least two superposed coatings either by methods not provided for in a single one of groups C23C2/00 - C23C26/00 or by combinations of methods provided for in subclasses C23C and C25C or C25D only coatings only including layers of metallic material
    • C23C28/023—Coating for obtaining at least two superposed coatings either by methods not provided for in a single one of groups C23C2/00 - C23C26/00 or by combinations of methods provided for in subclasses C23C and C25C or C25D only coatings only including layers of metallic material only coatings of metal elements only
    • C—CHEMISTRY; METALLURGY
    • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10G—CRACKING HYDROCARBON OILS; PRODUCTION OF LIQUID HYDROCARBON MIXTURES, e.g. BY DESTRUCTIVE HYDROGENATION, OLIGOMERISATION, POLYMERISATION; RECOVERY OF HYDROCARBON OILS FROM OIL-SHALE, OIL-SAND, OR GASES; REFINING MIXTURES MAINLY CONSISTING OF HYDROCARBONS; REFORMING OF NAPHTHA; MINERAL WAXES
    • C10G9/00—Thermal non-catalytic cracking, in the absence of hydrogen, of hydrocarbon oils
    • C10G9/14—Thermal non-catalytic cracking, in the absence of hydrogen, of hydrocarbon oils in pipes or coils with or without auxiliary means, e.g. digesters, soaking drums, expansion means
    • C10G9/18—Apparatus
    • C10G9/20—Tube furnaces
    • C10G9/203—Tube furnaces chemical composition of the tubes
    • C—CHEMISTRY; METALLURGY
    • C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
    • C23C—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; SURFACE TREATMENT OF METALLIC MATERIAL BY DIFFUSION INTO THE SURFACE, BY CHEMICAL CONVERSION OR SUBSTITUTION; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL
    • C23C10/00—Solid state diffusion of only metal elements or silicon into metallic material surfaces
    • C23C10/28—Solid state diffusion of only metal elements or silicon into metallic material surfaces using solids, e.g. powders, pastes
    • C23C10/34—Embedding in a powder mixture, i.e. pack cementation
    • C23C10/36—Embedding in a powder mixture, i.e. pack cementation only one element being diffused
    • C23C10/38—Chromising
    • C23C10/40—Chromising of ferrous surfaces
    • C23C10/42—Chromising of ferrous surfaces in the presence of volatile transport additives, e.g. halogenated substances
    • C—CHEMISTRY; METALLURGY
    • C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
    • C23C—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; SURFACE TREATMENT OF METALLIC MATERIAL BY DIFFUSION INTO THE SURFACE, BY CHEMICAL CONVERSION OR SUBSTITUTION; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL
    • C23C28/00—Coating for obtaining at least two superposed coatings either by methods not provided for in a single one of groups C23C2/00 - C23C26/00 or by combinations of methods provided for in subclasses C23C and C25C or C25D
    • C23C28/02—Coating for obtaining at least two superposed coatings either by methods not provided for in a single one of groups C23C2/00 - C23C26/00 or by combinations of methods provided for in subclasses C23C and C25C or C25D only coatings only including layers of metallic material
    • C23C28/028—Including graded layers in composition or in physical properties, e.g. density, porosity, grain size

Definitions

  • the invention relates to steel objects having anti-coking properties, as well as the process used to obtain such objects by depositing a coating anti-coking on a matrix made of a steel, in general a refractory steel.
  • the process is used for the production of parts that must resist coking in various refining or petrochemical processes.
  • the coated parts of the invention can be used for various processes of the refining and petrochemicals involving temperatures above 350 ° C: steam reforming, dehydrogenation, visbreaking, among others. More specifically, the invention applies to the manufacture of tubular steam cracking ovens intended for a long-term service at temperatures of the order of 800 to 1100 ° C.
  • coke The carbonaceous deposit that develops in the ovens during the conversion of hydrocarbon is generally called coke.
  • This deposit of coke is harmful in industrial units. Indeed, the formation of coke on the walls of the tubes and reactors leads in particular to a reduction in heat exchanges, blockages significant and therefore increases in pressure drop. To keep a constant reaction temperature, it may be necessary to increase the temperature of the walls, which risks causing damage to the alloy constituting these walls. There is also a decrease in the selectivity of the installations and consequently of the performance.
  • the coke formation during thermal cracking of hydrocarbons is a phenomenon complex involving different mechanisms, at least one of which involves reactions catalyzed by the presence of oxides of metallic elements such as nickel, iron or cobalt on the wall of the devices used for the implementation of said processes.
  • metallic elements are generally contained in large quantities in the refractory superalloys used due in particular to the thermal levels encountered at the wall of these devices.
  • This catalytic mechanism is very preponderant: observations have shown that if this mechanism was inhibited, it was possible in the case steam cracking to increase by a factor of at least about 3 the cycle time between two stops for decoking the ovens necessary for the implementation of this process.
  • the deposited silicon carbide is a compound with a low coefficient of expansion, whereas the substrate employed usually has a coefficient much higher expansion, which leads over time and heating and cooling cycles a significant risk of loss of sealing, at least at certain points, of the coating of silicon carbide and consequently contact between the hydrocarbons and the superalloy which leads to an increase in the coking speed of the apparatus.
  • the substrate generally consists of a refractory steel, containing preferably from 0.20 to 0.80% (percent) by mass of carbon.
  • this steel has grains of austenitic structure at ambient temperature.
  • a specific family of steel considered in the invention is that Manaurite® (registered trademark of MANOIR INDUSTRIES).
  • Typical examples of steels which can be used in the invention have the main characteristics indicated in the following table (the compositions are in% by weight): VS mn Yes Or Cr Fe additions ASTM A297 HK Manaurite 20® 0.30 to 0.65 1-2 1-2.5 18-24 23-36 compl. Ti. Nb. W ASTM A297 HL 0.20 to 0.60 1-2 1-2 18-22 28-32 compl. ASTM A297 HN 0.20-0.50 1-2 1-2 23-27 19-23 compl. ASTM A297 HP 0,35-0.75 1-2 1-2,5 33-37 24-28 compl. Manaurite 36XS® 0.35 to 0.60 1-1.5 1-2 33-38 23-28 compl.
  • Nb W Manaurite XM® 0.35 to 0.60 1-1.5 1-2 33-38 23-28 compl.
  • Nb Ti, Zr Manaurite XT® 0.35-0.45 1-1.5 1-2 42-46 32-37 compl.
  • Nb Manaurite XTM® 0.40 to 0.45 1-2 1-2 43-48 34-37 compl.
  • Nb Ti
  • the invention is more particularly considered refractory steel objects coated by thermal chromium plating methods, such as chromisation by cementation, in particular by pack cementation or by gas phase carburizing.
  • pack-cementation is well known to those skilled in the art. He was described in numerous documents. For example in the United States patent US-A-5,589,220, the authors point out that pack-cementation is a derived process CVD (abbreviation for "Chemical Vapor Deposition”), which consists of heating, in closed or open enclosure containing the metal part to be coated, a "pack” at one high temperature for a fixed period, during which a deposit diffusion occurs on said metal part. The cementation "pack" in the closed or open enclosure is protected from oxidation by an inert atmosphere or reductive.
  • CVD abbreviation for "Chemical Vapor Deposition”
  • the cementation "pack” consists of a piece or a substrate of metal or of alloy to be coated, surrounded by the elements to be deposited (in the form of a metal or a master alloy), a halide activating salt and a pulverulent filler.
  • a inert gas such as argon or hydrogen as the gaseous environment of "pack”.
  • a reaction step takes place which results in the deposition of the desired element and in the formation, by diffusion in the solid state of a protective coating on the surface of the metal.
  • the surface reaction can be quite complex and involve adsorption, dissociation and / or diffusion of molecular species.
  • gas carburization consists of heating to a high temperature in an open enclosure containing the metal part during a fixed duration, during which a diffusion deposit occurs on said piece metallic by a chromium halide gas generated by the action of a halide and / or of its hydride on a bed of chromium or chromium alloy granules from 0.1 mm to 50 mm in diameter.
  • This metallizing gas is conveyed by a gas carrying the bed of granules to said piece by a specific distributor-diffuser.
  • the carrier gas is a gas such as argon or hydrogen as protective gaseous environment.
  • the process of metallizing gas supply to said metal part is governed by the rules of fluid dynamics and limits the formation of chromium deposits.
  • the mass concentration of chromium in the granules is at least fifty for hundred.
  • the parts to be coated are placed in boxes containing a cement made up chromium powders (30 to 40% by mass) and alumina (60 to 70% by mass) and a activating halide (0.1 to 2% by mass relative to all of the two powders) under an atmosphere, for example hydrogen or argon. Heat treatment isotherm is then carried out at a temperature of 900 to 1200 ° C.
  • the objects coated according to the invention can be used in general as building materials for tubular bundles of pyrolysis reactors of hydrocarbons, with or without the presence of water vapor, more particularly for steam reforming or steam cracking reactors. They can also be used as building materials for tube bundles for process furnaces petroleum or petrochemical, such as visbreaking. They can still be used in the coating of ferrules and / or internal of fixed bed reactors for treatments petrochemicals, such as for example dehydrogenation or reforming.
  • the coated objects according to the invention exhibit improved anti-coking properties.
  • the deposits obtained do not deteriorate during severe thermal cycles between room temperature and for example 1000 ° C., with heating and cooling rates of 500 ° C / h.
  • Manaurite XM® refractory steel having the following composition is treated by pack-hardening.
  • VS mn Yes Or Cr Fe additions Manaurite XM® 0.35 to 0.60 1-1.5 1-2 33-38 23-28 compl.
  • Chromium was deposited electrolytically. To do this, we have immersed a sample of Manaurite XM® refractory steel serving as cathode, in a chromate bath and the chromate ions were reduced to metallic chromium on the cathode. A chromed steel was obtained, designated hereafter by Manaurite XM® chromed by electrolysis.
  • a chromium-plated Manaurite XM® refractory steel sample is used as described in Example 1 and, for comparison.
  • Manaurite XM® chromized glass of Example 1 leads, at the end of the first coking, to a coking speed much lower than that observed with the Manaurite XM® before chromization (5 times weaker) or that observed with Manaurite XM® electrolytic or that the Manaurite XM® coated with a layer of titanium carbide.
  • the ManauriteXM® chromized in Example 1 also gives good results after second coking. For its part, a steel coated with titanium carbide and carbide silicon gives poor results from the second coking.
  • Thermal cycling resistance tests were carried out in order to simulate the thermal shocks that industrial steam cracking tubes can undergo. These tests have were carried out in a muffle furnace equipped with an air injection. The samples have undergone 15 thermal heating and cooling cycles, from room temperature to 1000 ° C (and vice versa), with a heating (or cooling) speed of 500 ° C per hour. During the first 15 cycles, the parts are examined after each cycle.
  • Example 1 The chromium-coated Manaurite XM® refractory steel as described in Example 1 was evaluated according to the previous protocol. After 145 cycles (which corresponds to cumulative thermal cycling on industrial plant for an estimated service life of 10 years), this steel has not degraded. During the first 15 cycles, the parts are examined after each cycle. Metallographic examinations confirm the integrity of the coating.

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  • Chemical & Material Sciences (AREA)
  • Organic Chemistry (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Engineering & Computer Science (AREA)
  • Materials Engineering (AREA)
  • Metallurgy (AREA)
  • Mechanical Engineering (AREA)
  • Oil, Petroleum & Natural Gas (AREA)
  • Physics & Mathematics (AREA)
  • Thermal Sciences (AREA)
  • General Chemical & Material Sciences (AREA)
  • Production Of Liquid Hydrocarbon Mixture For Refining Petroleum (AREA)
  • Chemical Vapour Deposition (AREA)

Claims (10)

  1. Stahlartikel mit Überzug, der über Antikokungseigenschaften verfügt, dadurch gekennzeichnet, dass er umfasst:
    a. ein Substrat aus feuerfestem Stahl, das wenigstens 0,2 Massen-% Kohlenstoff einschließt;
    b. eine Diffusionsbarriere oder -grenzschicht, die reich an Kohlenstoff ist;
    c. und eine äußere Schicht mit einem Gehalt von 90 bis 99 Massen-% Chrom
    und dadurch gekennzeichnet, dass sie aufgrund von "cementation" bzw. Aufkohlung oder Carburierung mit Überzug versehen worden ist.
  2. Stahlartikel nach Anspruch 1, dadurch gekennzeichnet, dass er durch "pack-cementation" bzw. Pulvercementierung oder durch Cementation in gasförmiger Phase mit Überzug versehen worden ist.
  3. Stahlartikel nach einem der Ansprüche 1 und 2, dadurch gekennzeichnet, dass der Kohlenstoffgehalt des Substrats bei 0,2 bis 0,8 Massen-% liegt.
  4. Stahlartikel nach einem der Ansprüche 1 bis 3, dadurch gekennzeichnet, dass das Substrat die folgende Zusammensetzung hat: C Mn Si Ni Cr Fe Zugaben 0,35-0,60 1-1,5 1-2 33-38 23-28 Kompl. Nb, Ti, Zr
  5. Verwendung eines Artikels nach einem der Ansprüche 1 bis 4, als Material zur Herstellung von Rohrbündeln für Kohlenwasserstoff-Pyrolyse-Reaktoren mit oder ohne Anwesenheit von Wasserdampf.
  6. Verwendung nach Anspruch 5, dadurch gekennzeichnet, dass die Reaktoren (Wasser)dampf-Reformierungs-Reaktoren sind.
  7. Verwendung nach Anspruch 5, dadurch gekennzeichnet, dass diese Reaktoren (Wasser)dampf-Crack-Reaktoren sind.
  8. Verwendung des Artikels nach einem der Ansprüche 1 bis 4 als Material zur Herstellung von Rohrbündeln für Öfen zur Behandlung von Erdöl- oder petrochemischen Produkten.
  9. Verwendung nach Anspruch 8, dadurch gekennzeichnet, dass die Behandlung eine Viscoreduktionsbehandlung ist.
  10. Verwendung eines Gegenstandes nach einem der Ansprüche 1 bis 4 als Material zur Bildung von (Mantel)schüssen und/oder Inneneinbauten von Reaktoren mit festem Bett für petrochemische Behandlungsvorgänge.
EP98401567A 1997-07-04 1998-06-25 Hitzebeständiger chromierter Stahl, Verfahren zur seiner Herstellung und seine Verwendung in anti-Verkokungsanwendungen Expired - Lifetime EP0889146B1 (de)

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
FR9708511A FR2765594B1 (fr) 1997-07-04 1997-07-04 Acier refractaire chromise, son procede d'obtention et ses utilisations dans des applications anti-cokage
FR9708511 1997-07-04

Publications (2)

Publication Number Publication Date
EP0889146A1 EP0889146A1 (de) 1999-01-07
EP0889146B1 true EP0889146B1 (de) 2004-05-06

Family

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EP98401567A Expired - Lifetime EP0889146B1 (de) 1997-07-04 1998-06-25 Hitzebeständiger chromierter Stahl, Verfahren zur seiner Herstellung und seine Verwendung in anti-Verkokungsanwendungen

Country Status (6)

Country Link
US (1) US6348145B1 (de)
EP (1) EP0889146B1 (de)
JP (1) JP4206491B2 (de)
CA (1) CA2241349C (de)
DE (1) DE69823585T2 (de)
FR (1) FR2765594B1 (de)

Families Citing this family (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
GB2340911B (en) 1998-08-20 2000-11-15 Doncasters Plc Alloy pipes and methods of making same
US6644358B2 (en) 2001-07-27 2003-11-11 Manoir Industries, Inc. Centrifugally-cast tube and related method and apparatus for making same

Family Cites Families (15)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
GB1149163A (en) 1966-03-22 1969-04-16 Ici Ltd Protection against carburisation
US4350719A (en) * 1979-09-07 1982-09-21 Alloy Surfaces Company, Inc. Diffusion coating and products therefrom
BE810647A (fr) * 1974-02-05 1974-05-29 Procede de chromisation de la face interne d'un tube en metal ferreux et specialement en acier.
US4086107A (en) 1974-05-22 1978-04-25 Nippon Steel Corporation Heat treatment process of high-carbon chromium-nickel heat-resistant stainless steels
US4532109A (en) 1982-01-21 1985-07-30 Jgc Corporation Process for providing an apparatus for treating hydrocarbons or the like at high temperatures substantially without carbon deposition
US4863892A (en) * 1983-08-16 1989-09-05 Phillips Petroleum Company Antifoulants comprising tin, antimony and aluminum for thermal cracking processes
US4507196A (en) * 1983-08-16 1985-03-26 Phillips Petroleum Co Antifoulants for thermal cracking processes
US5169515A (en) 1989-06-30 1992-12-08 Shell Oil Company Process and article
JPH0735555B2 (ja) * 1989-09-19 1995-04-19 住友金属工業株式会社 耐コーキング性エチレン分解炉管用耐熱鍛伸鋼
JPH0426751A (ja) * 1990-05-18 1992-01-29 Mitsubishi Heavy Ind Ltd オーステナイト系ステンレス鋼の表面改質処理法
CA2113366C (en) 1993-01-15 2005-11-08 George A. Coffinberry Coated articles and method for the prevention of fuel thermal degradation deposits
US5575902A (en) * 1994-01-04 1996-11-19 Chevron Chemical Company Cracking processes
US5658452A (en) 1994-01-04 1997-08-19 Chevron Chemical Company Increasing production in hydrocarbon conversion processes
WO1997016507A1 (en) * 1995-10-31 1997-05-09 K.T.I. Group B.V. Process for reducing the formation of carbon deposits
US5873951A (en) 1996-08-23 1999-02-23 Alon, Inc. Diffusion coated ethylene furnace tubes

Also Published As

Publication number Publication date
DE69823585T2 (de) 2004-09-16
JPH1180926A (ja) 1999-03-26
EP0889146A1 (de) 1999-01-07
CA2241349C (fr) 2009-05-05
FR2765594A1 (fr) 1999-01-08
US6348145B1 (en) 2002-02-19
JP4206491B2 (ja) 2009-01-14
CA2241349A1 (fr) 1999-01-04
FR2765594B1 (fr) 1999-08-27
DE69823585D1 (de) 2004-06-09

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