EP0718415A1 - Anti-coking steels - Google Patents

Anti-coking steels Download PDF

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Publication number
EP0718415A1
EP0718415A1 EP95402864A EP95402864A EP0718415A1 EP 0718415 A1 EP0718415 A1 EP 0718415A1 EP 95402864 A EP95402864 A EP 95402864A EP 95402864 A EP95402864 A EP 95402864A EP 0718415 A1 EP0718415 A1 EP 0718415A1
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Prior art keywords
steel
coking
steels
approximately
around
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German (de)
French (fr)
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EP0718415B1 (en
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Valérie Mousseaux
François Ropital
André Le Lido Casanova A2 Sugier
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IFP Energies Nouvelles IFPEN
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IFP Energies Nouvelles IFPEN
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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
    • 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
    • C10G9/16—Preventing or removing incrustation
    • 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
    • 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
    • C22C38/50—Ferrous alloys, e.g. steel alloys containing chromium with nickel with titanium or zirconium

Definitions

  • the present invention relates to steels intended to manufacture reactors, furnaces, pipes or certain of their elements used in particular in petrochemical processes, these steels having an improved resistance to coking.
  • the invention also relates to the manufacture of reactors, furnaces, pipes or some of their elements, using these steels.
  • coke The carbonaceous deposit that develops in furnaces during the conversion of hydrocarbons.
  • 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, significant blockages and therefore increases in pressure drops. 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 therefore in the yield.
  • Application JP 03-104843 is known, which describes an anti-coking refractory steel for an ethylene steam cracking furnace tube. But this steel contains more than 15% chromium and nickel, and less than 0.4% manganese. This steel is developed to limit the formation of coke between 750 ° C and 900 ° C for the steam cracking of naphtha, ethane or diesel.
  • the steels of the invention may also contain from 0.25 to about 0.5% by weight of titanium.
  • the invention also relates to a method for manufacturing plant elements intended for petrochemical processes taking place at temperatures between 350 and 1100 ° C., in which, to improve the resistance to coking of said elements, they are manufactured in all or part of it, using steel as defined above.
  • These steels can be used to manufacture installations using petrochemical processes, for example, catalytic or thermal cracking and dehydrogenation.
  • Another application may relate to a process of steam cracking of products such as naphtha, ethane or a gas oil, which leads to the formation of light unsaturated hydrocarbons, in particular ethylene, etc. at temperatures from 750 ° C. to 1100 ° C.
  • the steels according to the invention can be used to manufacture whole tubes or plates intended for the manufacture of furnaces or reactors.
  • the steels according to the present invention can be produced by the conventional foundry and molding methods, then shaped by the usual techniques for manufacturing sheets, grids, tubes, profiles, etc. semi-finished products can be used to build the main parts of reactors or only accessory or auxiliary parts.
  • steels according to the invention for covering the internal walls of furnaces, reactors or pipes, by at least one of the following techniques: co-centrifugation, plasma, electrolytic, "overlay”. These steels can then be used in powder form to coat the internal walls of the reactors, grids or tubes, in particular after installation of the installations.
  • the steels used in the examples have the compositions indicated below (% by weight): STEELS VS Yes Mn Or Cr S P Al Ti AS 0.06 0.5 1.1 10 17.5 0.015 ⁇ 0.04 0.07 0.5 F1 0.37 2.31 10.25 D1 0.04 1.9 1.8 12.5 19.3 0.001 0.02 0.06 0.005 D2 0.2 3.6 0.8 14.5 18.5 0.015 ⁇ 0.04 1.0 ⁇ 0.01 C1 0.06 5 1.2 10 17.5 0.015 ⁇ 0.04 0.07 0.5 C2 0.06 3.5 1.2 10 17.5 0.015 ⁇ 0.04 0.07 0.5 C3 0.05 3 1.2 12 17.5 0.015 ⁇ 0.04 0.06 0.35 C4 0.05 2.5 1.2 12 17.0 0.05 ⁇ 0.04 0.06 0.35
  • AS is a standard steel commonly used for the manufacture of reactors or reactor components. Steels F1, D1 and D2 are also presented for comparison.
  • the isobutane dehydrogenation reaction makes it possible to obtain isobutene.
  • a side reaction is the formation of coke.
  • the coke deposit consists mainly of coke of catalytic origin.
  • the steel F1 has a ferritic structure, the steels C1 and C2 an austeno-ferritic structure and the steels C3 and C4 an austenitic structure.
  • the chromium and nickel contents of steels C3 and C4 were adjusted using the equivalence coefficients of Guiraldenq and Pryce, in order to locate these steels in the austenitic single-phase domain of the Schaeffer diagram.
  • Alloys C1, C2, C3 and C4 have the ability to develop a stable and inert oxide layer vis-à-vis catalytic coking phenomena.
  • the presence of silicon in these alloys favors the formation of an outer and substantially continuous layer practically consisting solely of chromium oxide without Cr_Ni_Fe spinel oxides.
  • This chromium oxide layer is separated from the metal substrate by an oxide zone rich in silicon.
  • the atmosphere of the chemical reaction, for example the dehydrogenation of isobutane is then practically only in contact with a chromium oxide layer catalytically inert with respect to the coking phenomenon.
  • the microbalance makes it possible to continuously measure the gain in mass on the sample.
  • FIG. 1 shows a graph having the time in hours on the abscissa and the ordinate the mass of coke which forms on the sample during the reaction, mass given in grams per square meter (g / m 2 ).
  • Curve 1 relates to AS steel, curve 2 to F1 steel, curves 3 and 3b respectively to steels D1 and D2, all of curves 4 to steels C1, C2, C3 and C4.
  • Figure 2 shows the coking curves during several successive coking / decoking cycles.
  • the decoking was carried out in air at 600 ° C, for the time necessary to burn the deposited coke (5 to 10 minutes).
  • Curve 6 represents coking for AS steel in the first cycle
  • curve 5 represents coking for AS steel sample after 20 coking / decoking cycles.
  • Curves 7 represent the coking / decoking curves after 20 cycles for steels C3 and C4.
  • steels C3 and C4 After 20 coking / decoking cycles, steels C3 and C4 have the same resistance to coking. Their surface chromium oxide layer has not evolved and it has retained its very low original catalytic activity with regard to coking. On the other hand, for standard steel which contains practically no silicon, after 20 coking / decoking cycles, the carbon deposition rate after 6 hours of testing has been multiplied by four.
  • the protective layer of standard steel is not stable: during successive decoking, there is an enrichment of this layer with catalytic metallic element such as iron or nickel.
  • a second test was carried out with a steam cracking reaction of hexane at a temperature of about 850 ° C.
  • the protocol for preparing the steel samples and for testing is the same as for Example 1.
  • FIG. 3 shows the coking of a steel sample AS, represented by curve 8, clearly superior to curves 9 and 10 representing respectively the coking of samples of steels C4 and C3.
  • the C3 and C4 alloys which contain in particular silicon have a lower coking rate than that of standard steels.
  • Column 1 corresponds to the temperature of the sample, column 2 to the stress at the elastic limit, column 3 to the stress at break, column 4 to the elongation at break.
  • Column 5 corresponds to the breaking stress in the creep test after 10,000 hours, column 6 after the 100,000 hours, and column 7 to the stress for a 1% elongation in the creep test after 10,000 hours.

Abstract

Steel consists of in wt%: approx 0.05 C; 2.5-5 Si; 10-20Cr; 10-15 Ni; 0.5-1.5 Mn; max 0.8 Al; balance Fe. The steel may also contain 0.25-0.5 Ti.

Description

La présente invention concerne des aciers destinés à fabriquer des réacteurs, des fours, des conduites ou certains de leurs éléments utilisés notamment dans des procédés pétrochimiques, ces aciers ayant une résistance au cokage améliorée.The present invention relates to steels intended to manufacture reactors, furnaces, pipes or certain of their elements used in particular in petrochemical processes, these steels having an improved resistance to coking.

L'invention concerne également la fabrication de réacteurs, de fours, de conduites ou de certains de leurs éléments, au moyen de ces aciers.The invention also relates to the manufacture of reactors, furnaces, pipes or some of their elements, using these steels.

Le dépôt carboné qui se développe dans les fours lors de la conversion des hydrocarbures est généralement appelé coke. Ce dépôt de coke est néfaste dans les unités industrielles. En effet, la formation du coke sur les parois des tubes et des réacteurs entraîne notamment une diminution des échanges thermiques, des bouchages importants et donc des augmentations de pertes de charge. Pour conserver une température de réaction constante, il peut être nécessaire d'augmenter la température des parois, ce qui risque d'entraîner un endommagement de l'alliage constitutif de ces parois. On observe aussi une diminution de la sélectivité des installations et par conséquent du rendement.The carbonaceous deposit that develops in furnaces during the conversion of hydrocarbons 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, significant blockages and therefore increases in pressure drops. 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 therefore in the yield.

Il s'avère donc nécessaire d'arrêter périodiquement les installations afin de procéder à un décokage. Il est donc intéressant économiquement de développer des matériaux ou des revêtements susceptibles de diminuer la formation du coke.It is therefore necessary to periodically stop the installations in order to carry out decoking. It is therefore economically advantageous to develop materials or coatings capable of reducing the formation of coke.

On connaît la demande JP 03-104843 qui décrit un acier réfractaire anti-cokage pour tube de four de vapocraquage à l'éthylène. Mais cet acier comporte plus de 15 % de chrome et de nickel, et moins de 0,4 % de manganèse. Cet acier est développé pour limiter la formation du coke entre 750°C et 900°C pour le vapocraquage d'un naphta, d'éthane ou d'un gasoil.Application JP 03-104843 is known, which describes an anti-coking refractory steel for an ethylene steam cracking furnace tube. But this steel contains more than 15% chromium and nickel, and less than 0.4% manganese. This steel is developed to limit the formation of coke between 750 ° C and 900 ° C for the steam cracking of naphtha, ethane or diesel.

Ainsi, la présente invention concerne des aciers de composition déterminée pour obtenir une bonne résistance au cokage. Ces aciers ont la composition pondérale suivante :

  • environ 0,05 % de carbone,
  • de 2,5 % à 5 % de silicium,
  • de 10 % à 20 % de chrome,
  • de 10 à 15 % de nickel,
  • de 0,5% à 1,5 % de manganèse,
  • au plus 0,8 % d'aluminium,
  • le complément à 100 % étant essentiellement du fer.
Thus, the present invention relates to steels of composition determined to obtain good resistance to coking. These steels have the following weight composition:
  • about 0.05% carbon,
  • from 2.5% to 5% of silicon,
  • from 10% to 20% chromium,
  • from 10 to 15% nickel,
  • from 0.5% to 1.5% manganese,
  • at most 0.8% aluminum,
  • the complement to 100% being essentially iron.

Les aciers de l'invention peuvent contenir en outre de 0,25 à environ 0,5 % en poids de titane.The steels of the invention may also contain from 0.25 to about 0.5% by weight of titanium.

Selon une variante de l'invention, les aciers peuvent avoir la composition pondérale suivante :

  • environ 0,06 % de carbone,
  • environ 3,5% à 5 % de silicium,
  • environ 17,5 % de chrome,
  • environ 10 % de nickel,
  • environ 1,2 % de manganèse,
  • environ 0,5 % de titane,
  • environ 0,07 % l'aluminium,
  • le complément à 100 % étant essentiellement du fer.
According to a variant of the invention, the steels can have the following weight composition:
  • about 0.06% carbon,
  • about 3.5% to 5% of silicon,
  • about 17.5% chromium,
  • about 10% nickel,
  • about 1.2% manganese,
  • about 0.5% titanium,
  • about 0.07% aluminum,
  • the complement to 100% being essentially iron.

Ils peuvent alors présenter une structure austéno-ferritique.They can then have an austenitic-ferritic structure.

Selon une autre variante de l'invention, les aciers peuvent avoir la composition pondérale suivante :

  • environ 0,05 % de carbone,
  • d'environ 2,5 % à 3 % de silicium,
  • d'environ 17 à 17,5 % de chrome,
  • environ 12 % de nickel,
  • environ 1,2 % de manganèse,
  • environ 0,35 % de titane,
  • et environ 0,06 % d'aluminium,
  • le complément à 100 % étant essentiellement du fer.
According to another variant of the invention, the steels can have the following weight composition:
  • about 0.05% carbon,
  • from about 2.5% to 3% of silicon,
  • about 17 to 17.5% chromium,
  • about 12% nickel,
  • about 1.2% manganese,
  • about 0.35% titanium,
  • and about 0.06% aluminum,
  • the complement to 100% being essentially iron.

Ils peuvent alors présenter une structure austénitique.They can then have an austenitic structure.

L'invention concerne également un procédé de fabrication d'éléments d'installations destinées à des procédés pétrochimiques se déroulant à des températures comprises entre 350 et 1100°C, dans lequel, pour améliorer la résistance au cokage desdits éléments, on les fabrique, dans leur totalité ou en partie, en utilisant un acier tel que défini plus haut.The invention also relates to a method for manufacturing plant elements intended for petrochemical processes taking place at temperatures between 350 and 1100 ° C., in which, to improve the resistance to coking of said elements, they are manufactured in all or part of it, using steel as defined above.

Ces aciers peuvent être utilisés pour fabriquer des installations mettant en oeuvre des procédés pétrochimiques, par exemple, le craquage catalytique ou thermique et la déshydrogénation.These steels can be used to manufacture installations using petrochemical processes, for example, catalytic or thermal cracking and dehydrogenation.

Par exemple, pendant la réaction de déshydrogénation de l'isobutane qui permet d'obtenir de l'isobutène entre 550°C et 700°C, une réaction secondaire produit la formation de coke. Cette formation de coke est catalytiquement activée par la présence de nickel, fer et de leurs oxydes.For example, during the dehydrogenation reaction of isobutane which makes it possible to obtain isobutene between 550 ° C. and 700 ° C., a secondary reaction produces the formation of coke. This coke formation is catalytically activated by the presence of nickel, iron and their oxides.

Une autre application peut concerner un procédé de vapocraquage de produits comme un naphta, l'éthane ou un gasoil, qui conduit à la formation d'hydrocarbures insaturés légers, notamment l'éthylène, etc... à des températures de 750°C à 1100°C.Another application may relate to a process of steam cracking of products such as naphtha, ethane or a gas oil, which leads to the formation of light unsaturated hydrocarbons, in particular ethylene, etc. at temperatures from 750 ° C. to 1100 ° C.

Les aciers selon l'invention peuvent être utilisés pour fabriquer en totalité des tubes ou des plaques destinés à la fabrication de fours ou de réacteurs.The steels according to the invention can be used to manufacture whole tubes or plates intended for the manufacture of furnaces or reactors.

Dans ce cas, les aciers selon la présente invention peuvent être élaborés par les méthodes classiques de fonderie et de moulage, puis mis en forme par les techniques usuelles pour fabriquer des tôles, des grilles, des tubes, des profilés, etc...Ces produits semi-finis peuvent être utilisés pour construire les parties principales des réacteurs ou seulement des parties accessoires ou auxiliaires.In this case, the steels according to the present invention can be produced by the conventional foundry and molding methods, then shaped by the usual techniques for manufacturing sheets, grids, tubes, profiles, etc. semi-finished products can be used to build the main parts of reactors or only accessory or auxiliary parts.

On peut également utiliser les aciers selon l'invention pour le recouvrement des parois internes de fours, réacteurs, ou conduites, par l'une au moins des techniques suivantes: co-centrifugation, plasma, électrolytique, "overlay". Ces aciers peuvent alors être utilisés sous forme de poudre pour effectuer des revêtements des parois internes des réacteurs, des grilles ou tubes, en particulier après montage des installations.It is also possible to use the steels according to the invention for covering the internal walls of furnaces, reactors or pipes, by at least one of the following techniques: co-centrifugation, plasma, electrolytic, "overlay". These steels can then be used in powder form to coat the internal walls of the reactors, grids or tubes, in particular after installation of the installations.

L'invention sera mieux comprise et ses avantages apparaîtront plus clairement à la lecture des exemples et des essais, nullement limitatifs, qui suivent, illustrés par les figures ci-annexées parmi lesquelles:

  • la figure 1 montre les courbes de cokage de différents aciers au cours d'une réaction de déshydrogénation de l'isobutane,
  • la figure 2 compare l'effet cumulé de cokage puis décokage pour les aciers selon l'invention en comparaison avec un acier standard pour la même réaction,
  • la figure 3 montre des courbes de cokage pour différents aciers pour une réaction de vapocraquage de l'hexane.
The invention will be better understood and its advantages will appear more clearly on reading the examples and tests, which are in no way limitative, which follow, illustrated by the appended figures among which:
  • FIG. 1 shows the coking curves of various steels during a dehydrogenation reaction of isobutane,
  • FIG. 2 compares the cumulative effect of coking and then decoking for the steels according to the invention in comparison with a standard steel for the same reaction,
  • Figure 3 shows coking curves for different steels for a steam cracking reaction of hexane.

Les aciers utilisés dans les exemples ont les compositions indiquées ci-après (% poids) : ACIERS C Si Mn Ni Cr S P Al Ti AS 0,06 0,5 1,1 10 17,5 0,015 <0,04 0,07 0,5 F1 0,37 2,31 10,25 D1 0,04 1,9 1,8 12,5 19,3 0,001 0,02 0,06 0,005 D2 0,2 3,6 0,8 14,5 18,5 0,015 <0,04 1,0 <0,01 C1 0,06 5 1,2 10 17,5 0,015 <0,04 0,07 0,5 C2 0,06 3,5 1,2 10 17,5 0,015 <0,04 0,07 0,5 C3 0,05 3 1,2 12 17,5 0,015 <0,04 0,06 0,35 C4 0,05 2,5 1,2 12 17,0 0,05 <0,04 0,06 0,35 The steels used in the examples have the compositions indicated below (% by weight): STEELS VS Yes Mn Or Cr S P Al Ti AS 0.06 0.5 1.1 10 17.5 0.015 <0.04 0.07 0.5 F1 0.37 2.31 10.25 D1 0.04 1.9 1.8 12.5 19.3 0.001 0.02 0.06 0.005 D2 0.2 3.6 0.8 14.5 18.5 0.015 <0.04 1.0 <0.01 C1 0.06 5 1.2 10 17.5 0.015 <0.04 0.07 0.5 C2 0.06 3.5 1.2 10 17.5 0.015 <0.04 0.07 0.5 C3 0.05 3 1.2 12 17.5 0.015 <0.04 0.06 0.35 C4 0.05 2.5 1.2 12 17.0 0.05 <0.04 0.06 0.35

AS est un acier standard utilisé couramment pour la fabrication de réacteurs ou d'élément de réacteurs. Les aciers F1, D1 et D2 sont également présentés à titre comparatif.AS is a standard steel commonly used for the manufacture of reactors or reactor components. Steels F1, D1 and D2 are also presented for comparison.

Exemple 1:Example 1:

Différents alliages ont été testés dans un réacteur de déshydrogénation de l'isobutane. La réaction de déshydrogénation de l'isobutane permet d'obtenir de l'isobutène. Une réaction secondaire est la formation de coke. Aux températures utilisées pour la déshydrogénation de l'isobutane, le dépôt de coke est principalement constitué de coke d'origine catalytique.Different alloys have been tested in an isobutane dehydrogenation reactor. The isobutane dehydrogenation reaction makes it possible to obtain isobutene. A side reaction is the formation of coke. At the temperatures used for the dehydrogenation of isobutane, the coke deposit consists mainly of coke of catalytic origin.

L'acier F1 présente une structure ferritique, les aciers C1 et C2 une structure austéno-ferritique et les aciers C3 et C4 une structure austénitique. Les teneurs en chrome et nickel des aciers C3 et C4 ont été ajustées en utilisant les coefficients d'équivalence de Guiraldenq et Pryce, afin de situer ces aciers dans le domaine monophasé austénitique du diagramme de Schaeffer.The steel F1 has a ferritic structure, the steels C1 and C2 an austeno-ferritic structure and the steels C3 and C4 an austenitic structure. The chromium and nickel contents of steels C3 and C4 were adjusted using the equivalence coefficients of Guiraldenq and Pryce, in order to locate these steels in the austenitic single-phase domain of the Schaeffer diagram.

Les alliages C1, C2, C3 et C4 ont la faculté de développer une couche d'oxyde stable et inerte vis-à-vis des phénomènes de cokage catalytique. La présence de silicium dans ces alliages favorise la formation d'une couche externe et sensiblement continue pratiquement constituée uniquement d'oxyde de chrome sans oxydes spinelles Cr_Ni_Fe. Cette couche d'oxyde de chrome est séparée du substrat métallique par une zone d'oxyde riche en silicium. L'atmosphère de la réaction chimique, par exemple de déshydrogénation de l'isobutane, est alors pratiquement uniquement en contact avec une couche d'oxyde de chrome inerte catalytiquement vis-à-vis du phénomène de cokage.Alloys C1, C2, C3 and C4 have the ability to develop a stable and inert oxide layer vis-à-vis catalytic coking phenomena. The presence of silicon in these alloys favors the formation of an outer and substantially continuous layer practically consisting solely of chromium oxide without Cr_Ni_Fe spinel oxides. This chromium oxide layer is separated from the metal substrate by an oxide zone rich in silicon. The atmosphere of the chemical reaction, for example the dehydrogenation of isobutane, is then practically only in contact with a chromium oxide layer catalytically inert with respect to the coking phenomenon.

Le protocole opératoire utilisé pour la réalisation des essais est le suivant:

  • Les échantillons d'acier sont découpés par électro-érosion puis polis au papier SiC # 180 pour assurer un état de surface standard et enlever la croûte d'oxyde qui a pu se former lors du découpage.
  • Un dégraissage dans un bain de CCl4, acétone puis éthanol est effectué.
  • Les échantillons sont ensuite suspendus au bras d'une thermobalance.
  • Le réacteur tubulaire est ensuite fermé. La montée en température est réalisée sous argon.
  • Le mélange réactionnel constitué d'isobutane, d'hydrogène et d'argon et environ 300 ppm d'oxygène est injecté dans le réacteur.
The operating protocol used for carrying out the tests is as follows:
  • The steel samples are cut by electro-erosion and then polished with SiC # 180 paper to ensure a standard surface finish and remove the oxide crust that may have formed during cutting.
  • Degreasing in a CCl 4 , acetone then ethanol bath is carried out.
  • The samples are then suspended from the arm of a thermobalance.
  • The tubular reactor is then closed. The temperature rise is carried out under argon.
  • The reaction mixture consisting of isobutane, hydrogen and argon and approximately 300 ppm of oxygen is injected into the reactor.

La microbalance permet de mesurer en continu la gain de masse sur l'échantillon.The microbalance makes it possible to continuously measure the gain in mass on the sample.

La figure 1 montre un graphique ayant en abscisses le temps en heures et en ordonnées la masse de coke qui se forme sur l'échantillon en cours de réaction, masse donnée en gramme par mètre carré (g/m2). La courbe 1 est relative à l'acier AS, la courbe 2 à l'acier F1, les courbes 3 et 3b respectivement aux aciers D1 et D2, l'ensemble des courbes 4 aux aciers C1, C2, C3 et C4.FIG. 1 shows a graph having the time in hours on the abscissa and the ordinate the mass of coke which forms on the sample during the reaction, mass given in grams per square meter (g / m 2 ). Curve 1 relates to AS steel, curve 2 to F1 steel, curves 3 and 3b respectively to steels D1 and D2, all of curves 4 to steels C1, C2, C3 and C4.

Il est clair que pour les aciers C1, C2, C3 et C4 selon l'invention le taux de cokage est réduit. Dans les mêmes conditions, les aciers F1, D1 et D2 montrent une moins bonne résistance au cokage.It is clear that for steels C1, C2, C3 and C4 according to the invention the coking rate is reduced. Under the same conditions, steels F1, D1 and D2 show poorer resistance to coking.

La figure 2 montre les courbes de cokage lors de plusieurs cycles de cokage/décokage successifs. Les décokages ont été réalisés sous air à 600°C, pendant le temps nécessaire pour brûler le coke déposé (de 5 à 10 minutes). La courbe 6 représente le cokage pour l'acier AS au premier cycle, la courbe 5 représente le cokage pour l'échantillon d'acier AS après 20 cycles de cokage/décokage.Figure 2 shows the coking curves during several successive coking / decoking cycles. The decoking was carried out in air at 600 ° C, for the time necessary to burn the deposited coke (5 to 10 minutes). Curve 6 represents coking for AS steel in the first cycle, curve 5 represents coking for AS steel sample after 20 coking / decoking cycles.

Les courbes 7 représentent les courbes de cokage/décokage après 20 cycles pour les aciers C3 et C4.Curves 7 represent the coking / decoking curves after 20 cycles for steels C3 and C4.

Après 20 cycles de cokage/décokage, les aciers C3 et C4 ont la même résistance vis-à-vis du cokage. Leur couche d'oxyde de chrome superficielle n'a pas évolué et elle a conservé sa très faible activité catalytique originelle vis-à-vis du cokage. Par contre, pour l'acier standard qui ne contient pratiquement pas de silicium, après 20 cycles de cokage/décokage, le taux de dépôt de carbone au bout de 6 heures d'essai a été multiplié par quatre. La couche protectrice de l'acier standard n'est pas stable: lors des décokages successifs, il se produit un enrichissement de cette couche en élément métallique catalytique comme le fer ou le nickel.After 20 coking / decoking cycles, steels C3 and C4 have the same resistance to coking. Their surface chromium oxide layer has not evolved and it has retained its very low original catalytic activity with regard to coking. On the other hand, for standard steel which contains practically no silicon, after 20 coking / decoking cycles, the carbon deposition rate after 6 hours of testing has been multiplied by four. The protective layer of standard steel is not stable: during successive decoking, there is an enrichment of this layer with catalytic metallic element such as iron or nickel.

Exemple 2:Example 2:

Un second test a été effectué avec une réaction de vapocraquage de l'hexane à une température d'environ 850°C. Le protocole de préparation des échantillons d'acier et de test est le même que pour l'exemple 1.A second test was carried out with a steam cracking reaction of hexane at a temperature of about 850 ° C. The protocol for preparing the steel samples and for testing is the same as for Example 1.

La figure 3 montre le cokage d'un échantillon d'acier AS, représenté par la courbe 8, nettement supérieure aux courbes 9 et 10 représentant respectivement le cokage des échantillons d'aciers C4 et C3.FIG. 3 shows the coking of a steel sample AS, represented by curve 8, clearly superior to curves 9 and 10 representing respectively the coking of samples of steels C4 and C3.

Pour ce second test, les alliages C3 et C4 qui contiennent notamment du silicium ont un taux de cokage inférieur à celui des aciers standards.For this second test, the C3 and C4 alloys which contain in particular silicon have a lower coking rate than that of standard steels.

Il faut noter les bonnes caractéristiques mécaniques en température des aciers C3 et C4 selon l'invention: -1- -2- -3- -4- -5- -6- -7- T Re Rm A trup trup t1% 10000 100000 10000 (°C) (MPa) (MPa) (%) (MPa) (MPa) (MPa) 600 140 370 40 210 150 140 700 130 320 44 75 30 50 800 120 300 50 15 7,5 8 The good mechanical temperature characteristics of the C3 and C4 steels according to the invention should be noted: -1- -2- -3- -4- -5- -6- -7- T Re Rm AT t rup t rup t 1% 10,000 100,000 10,000 (° C) (MPa) (MPa) (%) (MPa) (MPa) (MPa) 600 140 370 40 210 150 140 700 130 320 44 75 30 50 800 120 300 50 15 7.5 8

La colonne 1 correspond à la température de l'échantillon, la colonne 2 à la contrainte à la limite élastique, la colonne 3 à la contrainte à la rupture, la colonne 4 à l'allongement à la rupture. La colonne 5 correspond à la contrainte à la rupture en test de fluage après 10000 heures, la colonne 6 après 100000 heures, et la colonne 7 à la contrainte pour un allongement de 1% en test de fluage après 10000 heures.Column 1 corresponds to the temperature of the sample, column 2 to the stress at the elastic limit, column 3 to the stress at break, column 4 to the elongation at break. Column 5 corresponds to the breaking stress in the creep test after 10,000 hours, column 6 after the 100,000 hours, and column 7 to the stress for a 1% elongation in the creep test after 10,000 hours.

Claims (12)

Acier présentant une résistance au cokage améliorée caractérisé en ce qu'il présente essentiellement la composition pondérale suivante : • environ 0,05 % de carbone, • de 2,5 à 5 % de silicium, • de 10 à 20 % de chrome, • de 10 à 15 % de nickel, • de 0,5 à 1,5 % de manganèse, • au plus 0,8 % d'aluminium, • le complément à 100 % étant essentiellement du fer. Steel having improved resistance to coking, characterized in that it essentially has the following weight composition: • about 0.05% carbon, • from 2.5 to 5% of silicon, • from 10 to 20% chromium, • from 10 to 15% of nickel, • from 0.5 to 1.5% manganese, • at most 0.8% aluminum, • the 100% supplement being essentially iron. Acier selon la revendication 1, caractérisé en ce qu'il contient en outre de 0,25 à environ 0,5 % en poids de titane.Steel according to claim 1, characterized in that it additionally contains from 0.25 to approximately 0.5% by weight of titanium. Acier selon l'une des revendications 1 et 2 caractérisé en ce qu'il présente essentiellement la composition pondérale suivante : • environ 0,06 % de carbone, • environ 3,5 à 5 % de silicium, • environ 17,5 % de chrome, • environ 10 % de nickel, • environ 1,2 % de manganèse, • environ 0,5 % de titane, • et environ 0,07 % l'aluminium, • le complément à 100 % étant essentiellement du fer. Steel according to either of Claims 1 and 2, characterized in that it essentially has the following weight composition: • about 0.06% carbon, • approximately 3.5 to 5% of silicon, • approximately 17.5% chromium, • around 10% nickel, • around 1.2% manganese, • approximately 0.5% titanium, • and approximately 0.07% aluminum, • the 100% supplement being essentially iron. Acier selon la revendication 3 ayant une structure austéno-ferritique.Steel according to claim 3 having an austenitic-ferritic structure. Acier selon l'une des revendications 1 et 2, caractérisé en ce qu'il présente essentiellement la composition pondérale suivante : • environ 0,05 % de carbone, • d'environ 2,5 à 3 % de silicium, • d'environ 17 à 17,5 % de chrome, • environ 12 % de nickel, • environ 1,2 % de manganèse, • environ 0,35 % de titane, • et environ 0,06 % d'aluminium, • le complément à 100 % étant essentiellement du fer. Steel according to either of Claims 1 and 2, characterized in that it essentially has the following weight composition: • about 0.05% carbon, • about 2.5 to 3% silicon, • about 17 to 17.5% chromium, • around 12% nickel, • around 1.2% manganese, • approximately 0.35% titanium, • and around 0.06% aluminum, • the 100% supplement being essentially iron. Acier selon la revendication 5 ayant une structure austénitique.Steel according to claim 5 having an austenitic structure. Procédé de fabrication d'éléments d'unités destinées à des procédés pétrochimiques se déroulant à des températures comprises entre 350 et 1100°C, caractérisé en ce que, pour améliorer la résistance au cokage desdits éléments, on les fabrique, dans leur totalité ou en partie, en un acier selon l'une des revendications 1 à 6.Method for manufacturing elements of units intended for petrochemical processes taking place at temperatures between 350 and 1100 ° C, characterized in that, in order to improve the resistance to coking of said elements, they are manufactured, in their entirety or in part, made of a steel according to one of Claims 1 to 6. Procédé selon la revendication 7, caractérisé en ce qui lesdits éléments sont fabriqués en totalité en ledit acier.A method according to claim 7, characterized in that said elements are made entirely of said steel. Procédé selon l'une des revendications 7 et 8, caractérisé en ce que l'on effectue le recouvrement par ledit acier des parois internes des éléments desdites unités après leur montage.Method according to one of Claims 7 and 8, characterized in that the internal walls of the elements of the said units are covered by said steel after their assembly. Procédé selon la revendication 9, caractérisé en ce que ledit recouvrement est effectué par au moins une technique choisie parmi la co-centrifugation, la technique de plasma, le recouvrement électrolytique et la technique dite "overlay".Method according to Claim 9, characterized in that the said covering is carried out by at least one technique chosen from co-centrifugation, the plasma technique, the electrolytic covering and the so-called "overlay" technique. Procédé selon l'une des revendications 7 à 10, caractérisé en ce que l'unité est une unité de déshydrogénation de l'isobutane fonctionnant entre 550 -700°C.Method according to one of claims 7 to 10, characterized in that the unit is an isobutane dehydrogenation unit operating between 550 -700 ° C. Procédé selon l'une des revendications 7 à 10, caractérisé en ce que l'unité est un vapocraquage de naphta, d'éthane ou de gasoil fonctionnant entre 750 et 1100°C.Method according to one of claims 7 to 10, characterized in that the unit is a steam cracking of naphtha, ethane or gas oil operating between 750 and 1100 ° C.
EP95402864A 1994-12-20 1995-12-18 Anti-coking steels Expired - Lifetime EP0718415B1 (en)

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FR9415453A FR2728271A1 (en) 1994-12-20 1994-12-20 ANTI-COKAGE STEEL
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US6824883B1 (en) * 2000-09-12 2004-11-30 Nova Chemicals (International) S.A. Surface on a stainless steel matrix
FR2819526B1 (en) * 2001-01-15 2003-09-26 Inst Francais Du Petrole USE OF AUSTENITIC STAINLESS STEELS IN APPLICATIONS REQUIRING ANTI-COCKING PROPERTIES
FR2833020B1 (en) * 2001-11-30 2004-10-22 Inst Francais Du Petrole USE OF QUASI-CRYSTALLINE ALUMINUM ALLOYS IN REFINING AND PETROCHEMICAL APPLICATIONS
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KR101603455B1 (en) 2011-09-30 2016-03-14 유오피 엘엘씨 Process and apparatus for treating hydrocarbon streams
CN106399990B (en) * 2016-08-16 2019-09-20 深圳市诚达科技股份有限公司 A kind of anti-coking nano material and preparation method thereof based on stainless steel surface

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ATE205889T1 (en) 2001-10-15
CN1132265A (en) 1996-10-02
US5693155A (en) 1997-12-02
RU2146301C1 (en) 2000-03-10
KR100391747B1 (en) 2003-10-22
EP0718415B1 (en) 2001-09-19
NO955144D0 (en) 1995-12-18
JPH08218152A (en) 1996-08-27
CN1080323C (en) 2002-03-06
FR2728271B1 (en) 1997-02-21
FR2728271A1 (en) 1996-06-21
NO314807B1 (en) 2003-05-26

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