EP3559321B1 - Verfahren zur chemischen wandbehandlung zur verringerung von koksbildung - Google Patents

Verfahren zur chemischen wandbehandlung zur verringerung von koksbildung Download PDF

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EP3559321B1
EP3559321B1 EP17821602.4A EP17821602A EP3559321B1 EP 3559321 B1 EP3559321 B1 EP 3559321B1 EP 17821602 A EP17821602 A EP 17821602A EP 3559321 B1 EP3559321 B1 EP 3559321B1
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Prior art keywords
carbides
treatment
treatment step
chemical
treatment method
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English (en)
French (fr)
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EP3559321A1 (de
Inventor
Christel AUGUSTIN
Sophie CAZOTTES
Nicolas VACHÉ
Philippe STEYER
Claude DURET THUAL
François Dupoiron
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Centre National de la Recherche Scientifique CNRS
Institut National des Sciences Appliquees de Lyon
TotalEnergies Raffinage Chimie SAS
Universite Claude Bernard Lyon 1
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Centre National de la Recherche Scientifique CNRS
Institut National des Sciences Appliquees de Lyon
Total Raffinage Chimie SAS
Universite Claude Bernard Lyon 1
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    • C—CHEMISTRY; METALLURGY
    • C25—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
    • C25F—PROCESSES FOR THE ELECTROLYTIC REMOVAL OF MATERIALS FROM OBJECTS; APPARATUS THEREFOR
    • C25F3/00—Electrolytic etching or polishing
    • C25F3/02—Etching
    • C25F3/06—Etching of iron or steel
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B24—GRINDING; POLISHING
    • B24C—ABRASIVE OR RELATED BLASTING WITH PARTICULATE MATERIAL
    • B24C1/00—Methods for use of abrasive blasting for producing particular effects; Use of auxiliary equipment in connection with such methods
    • B24C1/04—Methods for use of abrasive blasting for producing particular effects; Use of auxiliary equipment in connection with such methods for treating only selected parts of a surface, e.g. for carving stone or glass
    • 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
    • C23C8/00—Solid state diffusion of only non-metal elements into metallic material surfaces; Chemical surface treatment of metallic material by reaction of the surface with a reactive gas, leaving reaction products of surface material in the coating, e.g. conversion coatings, passivation of metals
    • C23C8/02—Pretreatment of the material to be coated

Definitions

  • the invention relates to a method of treating the surface of a metal wall having the effect of reducing the formation of coke on the surface of this wall. More specifically, the invention relates to a process for the surface removal of carbides from a metal alloy wall, in particular by chemical treatment. The invention also relates to the use of a metal wall treated by the treatment process in a hydrocarbon treatment process.
  • the walls of the reactors of certain units in the petrochemical or chemical industry are sometimes subjected to very severe operating conditions which can cause coking phenomena.
  • the manufacture of alkenes, monomers valued in the polymer industry is obtained by cracking hydrocarbons derived from petroleum at temperatures of the order of 800 to 900 ° C.
  • a mixture of hydrocarbons and water vapor is circulated at high speed in reactors, generally made up of metal tubes, often made of alloys rich in nickel and chromium.
  • the reactors are thus subjected to high temperatures and complex aggressive atmospheres and the formation of carbon (coke) is observed on the surface of the walls of the tubes, this formation being catalyzed by the iron and nickel present in the alloy. metal constituting the walls.
  • This coke deposit can result in clogging of the tubes, leading to a pressure drop, a degradation of the conductivity of the walls and a reduction in yields. It is then necessary to stop the unit in order to remove the coke formed, an operation which is detrimental to the productivity of the unit.
  • a protective oxide layer can in particular be obtained by using suitable alloys, for example rich in chromium or in aluminum, or by oxidation pretreatments.
  • a process is proposed for treating a wall made of Fe-Ni-Cr metal alloy of an industrial reactor reducing the formation of coke on said surface when it is subjected to operational conditions favorable to coking, l metal alloy comprising in particular within its structure carbides some of which may be flush with the surface.
  • the metal alloy contains at least 5% by mass of iron, at least 18% by mass of chromium, at least 25% by mass of nickel and at least 0.05% by mass of carbon.
  • operation conditions favorable to coking is understood to mean conditions liable to generate the formation of coke on the surface.
  • the parameters influencing coking include, for example, the temperature, the nature of the liquid or gaseous fluids circulating inside the reactor and in contact with the surface, the fluid flow regime (turbulence).
  • the method comprises a chemical surface treatment step, during which at least part of the carbides initially present in the alloy, in particular at the surface, is removed by electrolytic dissolution.
  • Such a surface treatment step has the advantage of being easy to implement and relatively inexpensive.
  • the method according to the invention can advantageously be carried out to treat a wall of a reactor after the latter has been manufactured and before the reactor is put into service.
  • a step of oxidizing the wall can be envisaged, which makes it possible to further reduce the formation of coke.
  • the surface treatment seems to promote the formation of a homogeneous oxidized layer and thus reduce the formation of coke.
  • the invention is more particularly suitable for treating a wall of a steam cracking reactor (furnace), or of any other installation in which the formation of coke catalyzed by iron, nickel and optionally by other metal catalyst elements is observed. present in the metal alloy constituting the reactor.
  • the invention thus also relates to a process for treating hydrocarbons under conditions capable of causing the formation of coke, characterized in that the hydrocarbons are brought into contact with a surface of a wall made of a Fe-Ni-Cr metal alloy. , said surface of the metal wall being treated beforehand by a treatment method according to the invention so as to reduce the formation of a coke deposit.
  • the metal alloy is preferably a metal alloy containing at least 5% by mass of iron, at least 18% by mass of chromium, at least 25% by mass of nickel and at least 0.05% by mass of carbon .
  • the hydrocarbon treatment process can be a cracking process, in which the hydrocarbons are contacted with the wall mixed with water vapor.
  • a treatment is, for example, implemented in a steam cracking reactor.
  • the hydrocarbons can be brought into contact with the surface of the metal wall at a temperature of 800 to 900 ° C., in particular mixed with water vapor.
  • the treatment process according to the invention is intended for the treatment of Fe-Ni-Cr metal alloys, in particular containing carbides within their structure. These carbides may be flush with the surface, in other words be in contact with the gaseous medium surrounding the alloy, and / or may be located in close proximity to the surface, for example from a depth of 1 ⁇ m or more.
  • Such carbides are formed by precipitation during the manufacture of the wall. They may also appear partly in service.
  • the carbides which are particularly chemically stable, are formed from the carbon present in the metal alloy. These carbides can in particular be observed for a carbon content of the metal alloy of at least 0.05% by mass.
  • This type of metal alloy is particularly suitable for use at high temperature (“heat resistant alloys”).
  • the alloys treated are alloys having an Fe-Ni-Cr matrix, optionally austenitic, within which chromium carbides (Cr x C y ) precipitate, or even niobium carbides (NbC) when this element is present and / or carbonitrides when the alloy contains nitrogen, and / or other carbides optionally.
  • these alloys comprise carbon, in particular from 0.05 to 1% by mass of carbon, preferably from 0.08 to 0.6% by mass.
  • nickel or iron can be the predominant element.
  • the iron content is 100% complement of the content of other elements present in the alloy.
  • the metal alloy used can preferably be suitable for centrifugal molding.
  • it can comply with standard EN 10295 relating to refractory cast steels.
  • This technique consists in pouring the liquid metal in a mold animated by a rotational movement around its main axis.
  • the mold rotates at such a speed that it creates an average acceleration of the order of several hundred and up to 1000m / s 2 or more, in some cases.
  • the molds can be in sand or in metal shell, mounted on machines with horizontal, vertical or oblique axis. The parts obtained by centrifugation have very good physical and mechanical characteristics.
  • the treated wall can thus advantageously be produced by centrifugal molding.
  • this step is an electrochemical step, in particular an electrochemical step of selective dissolution.
  • the carbides initially present in the alloy are removed by electrolytic dissolution, in particular on the surface, namely the carbides flush with the surface and / or located in the immediate vicinity of the surface.
  • this step is advantageously carried out under conditions suitable for dissolving at least part of these carbides to a depth of at least 10 ⁇ m (from the treated surface), preferably of at least 20 ⁇ m, more preferably of at least 30 ⁇ m, or even at least 40 ⁇ m.
  • the electrolytic dissolution conditions can advantageously be adapted to dissolve one or more carbides chosen from chromium carbides, niobium carbides when the alloy contains niobium, carbonitrides when the alloy contains nitrogen or even other carbides, preferably chromium carbides.
  • the method according to the invention can comprise at least one other chemical treatment step, during which at least some of the carbides initially present in the alloy, in particular at the surface, and not dissolved during a previous step treatment chemical, is removed by electrolytic dissolution.
  • a chemical treatment step which is a step of electrolytic dissolution of chromium carbides and another chemical treatment step which is a step of electrolytic dissolution of niobium carbides when the alloy contains niobium, for example example in the quantities mentioned above.
  • a washing step can be provided between two successive chemical treatment steps under conditions suitable for removing traces of electrolytes from the treated surface. It may be one or more steps of rinsing the wall with water, preferably distilled water, optionally followed by one or more steps of rinsing with an alcohol, for example ethanol. This washing can be followed by drying under conditions allowing the rinsing fluid (s) to be removed from the wall to be treated.
  • the electrochemical dissolution of the chromium carbides is carried out followed by the electrochemical dissolution of the niobium carbides.
  • the chemical step is implemented by placing the wall to be treated at the anode of an electrolysis cell, the cathode being formed from a conductive part (for example metallic or graphite) and by applying an electric potential to the through the electrolysis cell.
  • a conductive part for example metallic or graphite
  • the chemical treatment step can be carried out in an electrolysis cell comprising an aqueous solution of an alkali metal hydroxide or an aqueous solution of sulfuric acid.
  • the electrolyte solution can thus comprise an aqueous solution of a soluble metal hydroxide.
  • This metal can be an alkali metal such as Na, K, Li, for example Na.
  • the electrolyte solution can comprise from 100 to 200 g / L of alkali metal hydroxide, preferably from 120 to 150 g / L.
  • the chloride content of the solution is less than 10 ppm by mass.
  • a procedure for dissolving niobium carbides is for example described in " Anode dissolution characteristics of titanium, niobium and chromium carbides ", 1971. V.Cihal, A. Desestret, M. Froment and GH Wagner .
  • the electrolytic solution can thus be an aqueous solution of sulfuric acid, the sulfuric acid concentration of which can be from 1 to 10 mol.L -1 , preferably from 2 to 9 mol.L -1 .
  • the invention is not however limited to these particular conditions: a person skilled in the art is able to determine other suitable concentrations of sulfuric acid, or even to use other suitable electrolytic solutions.
  • the difference in electric potential applied to the electrolysis cell can be 4 to 8 volts or 3 to volts, or even 3 to 5 volts. It may be preferable to avoid larger potential differences so as not to generate too much heat.
  • the current flow passing through the electrolysis cell is variable depending on the surface to be treated.
  • the current density can typically be from 5A / in 2 (7750A / m 2 ) to 10A / in 2 (15500A / m 2 ) of wall surface to be treated.
  • the duration of the treatment can be variable, for example from 4 to 50 hours or from 2 to 50 hours, for example from 2 to 30 hours, in depending on the amount of carbides and / or the wall depth that is to be treated.
  • the temperature of the electrolyte solution can vary from room temperature up to approximately 85 ° C. However, it is preferable that the temperature of the solution is kept below 60 ° C.
  • this step is preferably carried out after the chemical treatment step described above.
  • This surface treatment by impact is obtained by hammering the surface by spraying particles under conditions adapted to obtain a permanent plastic deformation of the surface, in particular under conditions adapted to obtain a covering of the carbides initially present on the surface by permanent plastic deformation of the surface.
  • the carbides initially present at the surface may be flush with the surface and / or be located in the immediate vicinity of the surface, in particular located at a depth of 1 ⁇ m and more from the surface.
  • this type of impact surface treatment is to compress the material below the impacted surface: this compressed material tends to regain its initial volume, resulting in strong residual compressive stresses. This makes it possible to significantly increase the life of an alloy part because almost all of the fatigue and stress corrosion failures are initiated on the surface of such parts.
  • the impacts caused by the projectiles will cover this surface with a uniform layer in compression.
  • the chemical treatment step generates the formation of cavities
  • the permanent plastic deformation obtained by the implementation of the mechanical treatment step makes it possible to fill these cavities at least in part.
  • an overlap of the carbides initially present on the surface is also observed - in other words a covering of the carbides flush with the surface and / or located in the immediate vicinity of the surface before the treatment. mechanical - which have not been dissolved by the chemical treatment step.
  • this modification of the surface limiting access to the carbides trapped inside the metal alloy also makes it possible to reduce the formation of coke.
  • such a surface treatment can be designated by the terms “microbanding” (use of balls), “sandblasting”, “corundum” (use of corundum particles), “shot blasting”.
  • the particles can be of various nature (mineral, metallic, etc.) of shapes (spherical or angular) and of various dimensions.
  • the particles can thus be chosen from particles of aluminum oxide (for example white or brown corundum), metal particles, balls of material inert under the operational conditions of use of the metal alloy wall, for example in glass or aluminum oxide, nesosilicate particles.
  • particles of aluminum oxide for example white or brown corundum
  • metal particles balls of material inert under the operational conditions of use of the metal alloy wall, for example in glass or aluminum oxide, nesosilicate particles.
  • the particles of nesosilicate have a general formula A m B n (SiO 4 ) t , where A is a transition metal or an alkaline earth and B is a transition metal or a rare earth.
  • A can be chosen from Mg, Ca and Mn and B can be chosen from Y, Ce, La.
  • the particles can have an average diameter of 100 to 500 ⁇ m.
  • glass beads with an average diameter of 100 to 200 ⁇ m, aluminum oxide particles with an average diameter of 250 to 500 ⁇ m can be used.
  • the particles can be projected by a gaseous fluid, for example air, argon or the like, under a pressure of 200 to 400kPa (2 to 4 bars), preferably of 250 to 350kPa (2.5 to 3 , 5 bars).
  • a gaseous fluid for example air, argon or the like
  • a pressure of 300 to 350 kPa can be used.
  • pressures of 270 to 320kPa can be used.
  • the projection distance can be 5 to 25cm, for example 10 to 20 cm.
  • the projection duration can be from 0.2 to 3 minutes, preferably from 0.5 to 2 minutes (in particular for an area of a few cm 2 ).
  • the step of surface treatment by impact can be implemented under suitable conditions to obtain a covering of the carbides and / or a closing of the cavities to a depth of at least 20 ⁇ m, preferably to a depth of at least less 30 ⁇ m.
  • This mechanical step is preferably carried out “cold”, in other words at ambient temperature, namely a temperature ranging from 18 to 35 ° C.
  • This step is carried out after the chemical treatment step, optionally after the mechanical surface treatment step. It is carried out under conditions which make it possible to form an oxide layer (s) on the treated surface of the wall, in particular a layer containing one or more chromium oxides.
  • the oxidation conditions can be those usually used to form an oxide layer (s) on this type of alloy and known from the prior art.
  • the oxidation can be carried out at a temperature of 800 to 1100 ° C., under a partial pressure of oxygen of 10 -6 atm to 0.2atm, for a period of 30min to 5h.
  • the figure 1 schematically represents an electrolytic cell 1. An electric potential difference is applied between two electrodes 2, 3 immersed in an electrolytic solution 4. The positive terminal is the anode 2, site of oxidation and the negative terminal is the cathode 3, seat of a reduction. A direct current generator 5 connected to the anode 2 and to the cathode 3 supplies the current.
  • the material to be dissolved must be located on the anode 2 (terminal +).
  • the distance between the two electrodes 2, 3 is for example around 1 cm.
  • a simple metal plate can be used for the cathode (the - terminal).
  • the electrolyte 4 will for example be a sodium hydroxide solution.
  • HP modified 25-35 type and 35-45 type metal alloy samples were tested. These alloys consist of an austenitic Fe-Ni-Cr matrix within which niobium (NbC) and chromium (Cr 7 C 3 ) carbides precipitate.
  • NbC niobium
  • Cr 7 C 3 chromium
  • Table 1 Typical chemical composition (% by mass) of the materials used Cr Or Fe VS Yes Mn Nb HP 25-35 25 35 26 0.5 1.4 1.6 0.5 HP 35-45 35 45 15 0.5 2.5 1.6 0.4
  • the samples used are plates of dimensions 8 x 30mm (samples C1 to C5) and 8 x 25mm (samples C6 to C9) and 2mm thick obtained by electroerosion in the heart of 5cm portions of new steam cracking tubes, of thickness initial 8mm.
  • the initial surface condition is a rough machined condition.
  • the tubes from which the tested samples were obtained were manufactured by centrifugal molding.
  • SEM Scanning electron microscope
  • Ionic cutting the transverse cuts are made by ionic cutting by defocused ion beam. This technique uses accelerated argon ions to tear off material, allowing a very fine and pollution-free surface polishing.
  • the samples are glued onto titanium masks using a “silver lacquer” made up of fine silver platelets suspended in a solvent.
  • Example 1 electrochemical treatment of the surface
  • the sample is subjected to a chemical treatment of electrolytic dissolution.
  • the sample to be tested is placed at the anode of an electrolysis cell as described in figure 1 , the cathode being a metallic plate of stainless steel or graphite, of similar or larger dimensions than the sample.
  • the anode and cathode are spaced a distance of about 1 cm, the plates being substantially parallel inside the electrolytic cell.
  • An electrolytic solution is prepared by dissolving, with mechanical stirring, 135 g of NaOH (in the form of pellets) in 1 L of distilled water, then the electrolysis cell is filled with the solution obtained.
  • the chloride content of the solution is less than 10 ppm by mass.
  • a potential difference is applied between the anode (sample) and the cathode.
  • the figures 2 and 3 are photographs of the C4 sample dissolved for 15h ( fig.2 ) and sample C5 dissolved 20h ( fig. 3 ).
  • the acceleration voltage applied for the measurement is 15kV
  • the magnification is 619x ( fig.2 ) and 629x ( fig.3 ) and the 10 ⁇ m scale.
  • sample C4 cavities are observed to a depth of about 40 ⁇ m, which seems to indicate the existence of interconnected carbide networks.
  • the cavities extend to a depth of 80 ⁇ m. Between 50 and 80 ⁇ m there are still chromium carbides, which seems to indicate that the carbide network is not completely interconnected.
  • Table 2 indicates for samples C6 to C9 the maximum depth to which a dissolution of chromium carbides was observed.
  • the figures 4 and 5 schematically represent observations typical of a section of an untreated sample ( fig. 4 ) and a chemically treated sample ( fig. 5 ).
  • the black parts correspond to chromium carbides
  • the gray parts correspond to niobium carbides.
  • Niobium carbides are observed in the cavities.
  • the solution could propagate by dissolving the chromium carbides resulting from the interconnected networks but preserving the niobium carbides (NbC).
  • NbC niobium carbides
  • the cavities are not completely empty.
  • SEM / EDX Energy Dispersive X-ray Spectrometry
  • Example 2 mechanical surface treatment / microbeading
  • a sample M1 is obtained.
  • Example 3 mechanical surface treatment / sandblasting (corundum)
  • Example 4 Chemical treatment + mechanical treatment / microbeading
  • Sample C4 of Example 1 is subjected to the same microbeading treatment as that described in Example 2. A sample CM4 is obtained.
  • Example 5 Chemical treatment + mechanical treatment / corundum
  • Sample C4 of Example 1 is subjected to the same microbeading treatment as that described in Example 3.
  • a sample CM5 is obtained.
  • the figure 6 schematically represents the typical observation of a section of a sample of alloy having undergone a chemical and mechanical treatment. It is noted that the chromium carbides are no longer in direct contact with the surface and that the cavities formed by the electrochemical dissolution have been at least partly closed for most of them.
  • the samples were observed by SEM.
  • the figures 7a and 7b are photographs (35x and 150x magnifications respectively) of the surface of the reference sample which has not undergone any particular treatment apart from the initial polishing. The formation of coke is observed on the surface.
  • the figures 8a and 8b are photographs of sample C4 having undergone the electrochemical treatment (35x and 150x magnifications respectively), the figures 9a and 9b are photographs of the CM5 sample (35x and 150x magnifications respectively).
  • the samples which have undergone a chemical treatment show less coke overall than the reference sample. Coke is still observed on about 10% of the surface of the sample.
  • Example 7 electrochemical treatment of the surface
  • the sample undergoes a chemical electrolytic dissolution treatment to remove niobium carbides.
  • the sample to be tested is placed at the anode of an electrolysis cell of the same type as that shown figure 1 and described in Example 1.
  • a potential difference of the order of 0.8 V is applied between the anode (sample) and the cathode for 2 hours.
  • the sample is then rinsed with distilled water and then with ethanol, dried and stored in a case protected from scratches and air in a desiccator.
  • a second test was carried out under the same electrolysis conditions on a sample of the same dimensions and of the same alloy previously subjected to electrolytic dissolution of the chromium carbides. This is carried out with a current density of 5A.in -2 (0.775A.cm -2 ) for 2 hours in a solution of NaOH (135g in the form of pellets in 1L of water). The sample obtained is then rinsed with distilled water and then with ethanol and dried before being introduced into the sulfuric acid solution for dissolving the niobium carbides.
  • the successive electrolytic decomposition of chromium carbides and niobium carbides therefore dissolves the NbCs on the surface.
  • the electrolytic dissolution of M 23 C 6 / M 7 C 3 could come in part "loosen” the NbCs and increase the free surface in contact with the electrolyte of the second dissolution.

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Claims (15)

  1. Verfahren zur Behandlung einer Wand aus Fe-Ni-Cr-Metalllegierung eines Industriereaktors zur Verringerung von Koksbildung an der Wand, wenn sie Betriebsbedingungen ausgesetzt ist, die für die Verkokung günstig sind, wobei die Metalllegierung innerhalb ihrer Struktur Carbide umfasst, von denen einige bündig mit der Oberfläche sein können, wobei das Verfahren umfasst:
    - einen chemischen Oberflächenbehandlungsschritt, bei dem mindestens ein Teil der ursprünglich in der Legierung vorhandenen Carbide, insbesondere an der Oberfläche, durch elektrolytische Auflösung entfernt wird.
  2. Behandlungsverfahren nach Anspruch 1, wobei der chemische Behandlungsschritt unter Bedingungen durchgeführt wird, die zum Auflösen mindestens eines Teils der Carbide bis zu einer Tiefe von mindestens 10 µm, vorzugsweise mindestens 20 µm, geeignet sind.
  3. Behandlungsverfahren nach einem der Ansprüche 1 und 2, wobei der chemische Behandlungsschritt unter Bedingungen durchgeführt wird, die zum Auflösen mindestens eines Teils der Carbide geeignet sind, ausgewählt aus Chromcarbiden, Niobcarbid, wenn die Legierung Niob enthält, Carbonitriden, wenn die Legierung Stickstoff enthält.
  4. Behandlungsverfahren nach einem der Ansprüche 1 bis 3, wobei der chemische Behandlungsschritt in einer Elektrolysezelle durchgeführt wird, die eine wässrige Lösung umfasst, ausgewählt aus einer Lösung eines Alkalimetallhydroxids und einer wässrigen Schwefelsäurelösung.
  5. Behandlungsverfahren nach einem der Ansprüche 1 bis 4, umfassend mindestens einen weiteren chemischen Behandlungsschritt, bei dem mindestens ein Teil der anfänglich in der Legierung, insbesondere an der Oberfläche, vorhandenen und während eines vorherigen chemischen Behandlungsschritts nicht gelösten Carbide durch elektrolytische Auflösung entfernt wird.
  6. Verfahren nach einem der Ansprüche 1 bis 5, wobei:
    - ein chemischer Behandlungsschritt ein Schritt der elektrolytischen Auflösung von Chromcarbiden ist,
    - ein weiterer chemischer Behandlungsschritt ein Schritt der elektrolytischen Auflösung von Niobcarbiden ist, wobei die Metalllegierung Niob enthält.
  7. Behandlungsverfahren nach Anspruch 6, bei dem die elektrochemische Auflösung der Chromcarbide durchgeführt wird, gefolgt von der elektrochemischen Auflösung der Niobcarbide.
  8. Behandlungsverfahren nach einem der Ansprüche 1 bis 7, dadurch gekennzeichnet, dass es nach dem chemischen Oberflächenbehandlungsschritt ferner umfasst:
    - einen mechanischen Schritt der Oberflächenbehandlung durch Aufprall, bei dem die Oberfläche der Wand, die der chemischen Behandlung durch Sprühen von Partikeln unterzogen wurde, unter Bedingungen gehämmert wird, die geeignet sind, eine dauerhafte plastische Verformung der Oberfläche zu erhalten.
  9. Behandlungsverfahren nach Anspruch 8, wobei die während des mechanischen Behandlungsschritts verwendeten Partikel ausgewählt sind aus Aluminiumoxidpartikeln, Metallpartikeln, unter den Betriebsbedingungen inerten Materialkugeln, Partikeln von Nesosilikaten.
  10. Behandlungsverfahren nach einem der Ansprüche 8 und 9, wobei die in dem mechanischen Behandlungsschritt verwendeten Partikel einen durchschnittlichen Durchmesser von 100 bis 500 µm aufweisen.
  11. Behandlungsverfahren nach einem der Ansprüche 8 bis 10, bei dem während des mechanischen Behandlungsschritts die Partikel durch eine gasförmige Flüssigkeit unter einem Druck von 200 bis 400 kPa gesprüht werden.
  12. Behandlungsverfahren nach einem der Ansprüche 1 bis 11, wobei die Metalllegierung mindestens 5 Massen-% Eisen, mindestens 18 Massen-% Chrom, mindestens 25 Massen-% Nickel, mindestens 0,05 Massen-% Kohlenstoff enthält.
  13. Behandlungsverfahren nach einem der Ansprüche 1 bis 12, dadurch gekennzeichnet, dass es nach dem chemischen Behandlungsschritt und gegebenenfalls nach dem mechanischen Oberflächenbehandlungsschritt bei seiner Implementierung umfasst:
    - einen Oxidationsschritt, der unter geeigneten Bedingungen durchgeführt wird, um (eine) Oxidschicht(en) auf der Oberfläche zu bilden, die der chemischen Behandlung und gegebenenfalls der mechanischen Behandlung unterzogen wurde, insbesondere eine Schicht, die ein oder mehrere Chromoxide enthält.
  14. Verfahren zur Behandlung von Kohlenwasserstoffen unter Bedingungen, die die Bildung von Koks verursachen können, dadurch gekennzeichnet, dass die Kohlenwasserstoffe mit einer Oberfläche einer Wand aus einer Fe-Ni-Cr-Metalllegierung in Kontakt gebracht werden, wobei diese Oberfläche der Metallwand zuvor durch ein Behandlungsverfahren gemäß einem der Ansprüche 1 bis 13 behandelt worden ist, um die Bildung einer Koksablagerung zu verringern.
  15. Verfahren zur Behandlung von Kohlenwasserstoffen nach dem vorhergehenden Anspruch, bei dem die Kohlenwasserstoffe bei einer Temperatur von 800 bis 900 °C mit der Oberfläche der Metallwand in Kontakt gebracht werden.
EP17821602.4A 2016-12-20 2017-12-19 Verfahren zur chemischen wandbehandlung zur verringerung von koksbildung Not-in-force EP3559321B1 (de)

Applications Claiming Priority (2)

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FR1662911A FR3060611A1 (fr) 2016-12-20 2016-12-20 Procede de traitement chimique d'une paroi reduisant la formation de coke
PCT/EP2017/083566 WO2018114963A1 (fr) 2016-12-20 2017-12-19 Procede de traitement chimique d'une paroi reduisant la formation de coke.

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SU441355A1 (ru) * 1972-11-30 1974-08-30 Уральский Филиал Всесоюзного Ордена Трудового Красного Знамени Теплотехнического Научно-Исследователького Института Имени Ф.Э.Дзержинского Электролит дл изолировани карбидов м 23 с 6
US4851093A (en) 1988-06-06 1989-07-25 United Technologies Corporation Selective decomposition of a chromium carbide coating from a chromium carbide coated nickel alloy substrate
JPH02240298A (ja) * 1989-03-10 1990-09-25 Komatsu Ltd 多孔質鋼
US5873950A (en) * 1996-06-13 1999-02-23 Inco Alloys International, Inc. Strengthenable ethylene pyrolysis alloy
WO2010108517A1 (en) * 2009-03-26 2010-09-30 Siemens Aktiengesellschaft Electropolishing method and electromagnetic flowmeter having electropolished electrodes

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EP3559321A1 (de) 2019-10-30
FR3060611A1 (fr) 2018-06-22
US20190390362A1 (en) 2019-12-26
WO2018114963A1 (fr) 2018-06-28
CA3047497A1 (fr) 2018-06-28

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