EP3334521A1 - Reforming tube comprising an insert affording protection against corrosion - Google Patents

Reforming tube comprising an insert affording protection against corrosion

Info

Publication number
EP3334521A1
EP3334521A1 EP16750830.8A EP16750830A EP3334521A1 EP 3334521 A1 EP3334521 A1 EP 3334521A1 EP 16750830 A EP16750830 A EP 16750830A EP 3334521 A1 EP3334521 A1 EP 3334521A1
Authority
EP
European Patent Office
Prior art keywords
wall
reforming tube
tube according
ceramic
reforming
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.)
Pending
Application number
EP16750830.8A
Other languages
German (de)
French (fr)
Inventor
Nicolas Richet
Hans Werner Scholz
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
LAir Liquide SA pour lEtude et lExploitation des Procedes Georges Claude
Original Assignee
Air Liquide SA
LAir Liquide SA pour lEtude et lExploitation des Procedes Georges Claude
Priority date (The priority date 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 date listed.)
Filing date
Publication date
Application filed by Air Liquide SA, LAir Liquide SA pour lEtude et lExploitation des Procedes Georges Claude filed Critical Air Liquide SA
Publication of EP3334521A1 publication Critical patent/EP3334521A1/en
Pending legal-status Critical Current

Links

Classifications

    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J19/00—Chemical, physical or physico-chemical processes in general; Their relevant apparatus
    • B01J19/02—Apparatus characterised by being constructed of material selected for its chemically-resistant properties
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J19/00—Chemical, physical or physico-chemical processes in general; Their relevant apparatus
    • B01J19/0053—Details of the reactor
    • B01J19/0066—Stirrers
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J19/00—Chemical, physical or physico-chemical processes in general; Their relevant apparatus
    • B01J19/24—Stationary reactors without moving elements inside
    • B01J19/2415—Tubular reactors
    • F—MECHANICAL ENGINEERING; LIGHTING; HEATING; WEAPONS; BLASTING
    • F16—ENGINEERING ELEMENTS AND UNITS; GENERAL MEASURES FOR PRODUCING AND MAINTAINING EFFECTIVE FUNCTIONING OF MACHINES OR INSTALLATIONS; THERMAL INSULATION IN GENERAL
    • F16L—PIPES; JOINTS OR FITTINGS FOR PIPES; SUPPORTS FOR PIPES, CABLES OR PROTECTIVE TUBING; MEANS FOR THERMAL INSULATION IN GENERAL
    • F16L58/00—Protection of pipes or pipe fittings against corrosion or incrustation
    • F16L58/02—Protection of pipes or pipe fittings against corrosion or incrustation by means of internal or external coatings
    • F16L58/04—Coatings characterised by the materials used
    • F16L58/08—Coatings characterised by the materials used by metal
    • F—MECHANICAL ENGINEERING; LIGHTING; HEATING; WEAPONS; BLASTING
    • F16—ENGINEERING ELEMENTS AND UNITS; GENERAL MEASURES FOR PRODUCING AND MAINTAINING EFFECTIVE FUNCTIONING OF MACHINES OR INSTALLATIONS; THERMAL INSULATION IN GENERAL
    • F16L—PIPES; JOINTS OR FITTINGS FOR PIPES; SUPPORTS FOR PIPES, CABLES OR PROTECTIVE TUBING; MEANS FOR THERMAL INSULATION IN GENERAL
    • F16L58/00—Protection of pipes or pipe fittings against corrosion or incrustation
    • F16L58/02—Protection of pipes or pipe fittings against corrosion or incrustation by means of internal or external coatings
    • F16L58/04—Coatings characterised by the materials used
    • F16L58/14—Coatings characterised by the materials used by ceramic or vitreous materials
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J2219/00—Chemical, physical or physico-chemical processes in general; Their relevant apparatus
    • B01J2219/02—Apparatus characterised by their chemically-resistant properties
    • B01J2219/0204—Apparatus characterised by their chemically-resistant properties comprising coatings on the surfaces in direct contact with the reactive components
    • B01J2219/0218—Apparatus characterised by their chemically-resistant properties comprising coatings on the surfaces in direct contact with the reactive components of ceramic
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J2219/00—Chemical, physical or physico-chemical processes in general; Their relevant apparatus
    • B01J2219/02—Apparatus characterised by their chemically-resistant properties
    • B01J2219/0204—Apparatus characterised by their chemically-resistant properties comprising coatings on the surfaces in direct contact with the reactive components
    • B01J2219/0236—Metal based

Definitions

  • the present invention relates to a reforming tube comprising means for avoiding in its cavity the phenomenon of corrosion called "metal dusting".
  • metal dusting is meant a catastrophic disintegration of metals (Fe, Ni, Co) observed in the fuel atmospheres of chemical and petrochemical processes.
  • the aluminization of the alloy involves reacting the aluminum vapor with the alloy to form an outer layer rich in aluminum.
  • the chemical composition of the coating may vary. For example if we consider a Cr-Ni based alloy, the outer layer will contain Al, Ni and Cr.
  • Composite tubes are another way to reduce corrosion. This solution is based on the assembly of two materials with dissimilar properties. Usually a material will have a high resistance to corrosion under the process conditions while
  • FIRE REPLACEM ENT (RULE 26) that the other will have high mechanical properties. Both materials, usually alloys, are welded together using different manufacturing processes. This leads to two layers of materials having different thicknesses according to the process specifications. The main difficulty is to produce complex shapes and the problem of thermal expansion resulting in stresses that could increase the rate of corrosion or reduce the mechanical strength.
  • the first limitation of existing solutions vis-à-vis the phenomenon of corrosion called "metal dusting" is the size of the parts to be protected.
  • metal dusting the phenomenon of corrosion
  • these tubes are about 13 m long and it is difficult to find companies that have the appropriate equipment to achieve a homogeneous coating (thickness and chemical composition) .
  • the configuration of the parts to be protected can also reduce the choice in terms of coating techniques and chemical composition of the coating.
  • a solution of the present invention is a reforming tube 1 comprising:
  • the reforming tube according to the present invention may have one or more of the following characteristics:
  • the refractory material 5 matches the shape of the inner wall and the shape of the protective part
  • the refractory material 5 is chosen from: ceramic fiber fabrics, ceramic fiber paper, refractory ceramic fibers, and polycrystalline ceramic fibers.
  • said tube comprises a seam 6 between the upper end of the protection piece and the inner wall
  • said tube comprises a joint 7 between the lower end of the protection piece and the inner wall
  • At least one joint 6 or 7 is a weld, a solder or a joint made with glass or ceramic glass;
  • the protective part 4 comprises an inert material with respect to corrosion by metal dusting
  • the material of the protective part is chosen from alloys based on nickel and chromium; examples that may be mentioned are commercial alloys 601, 617, 690 and 693;
  • the material of the protective part 4 is made of ceramic or has a ceramic coating;
  • the corrosion protection piece 4 comprises a material having a low resistance to corrosion and coated with a material having a very good corrosion resistance or a ceramic coating;
  • the ceramic may be chosen from Al 2 O 3, MgAl 2 O 4, ZrO 2, Y 2 O 3 -ZrO 2, MgO, MgO-ZrO 2, Al 2 O 3 -ZrO 2, SiC, and SiN 4.
  • the solution proposed is to insert a protected ceramic or metal part.
  • the constituent material of this protective part is selected according to its resistance to corrosion and its chemical and physical compatibility with the alloy of the tube.
  • the protective piece does not stick to the alloy of the tube which makes a big difference with the solutions of the prior art.
  • the degree of freedom between the tube and the protective part makes it possible to reduce the mechanical stresses that could be induced by the thermal expansion of the parts exposed to high temperatures (400-1000 ° C).
  • this space between the inner wall of the tube and the protective part could lead to a flow of synthesis gas. Also, it is necessary to avoid the access of synthesis gas in this space.
  • the present invention proposes as a main solution to the problem of access of the synthesis gas in said space, the use of a refractory material filling said space between the inner wall and the protective part.
  • the refractory material adjusts to the shape of the inner wall of the tube.
  • the refractory material must be selected according to its ability to withstand a synthesis gas atmosphere (H2, CO, CH4, H2O) at high temperature (800 to 1000 ° C) and to deform when subjected to a limited load in order to fit the shape of the inner wall of the tube and the shape of the wall of the protective part.
  • the reforming tube according to the invention will preferably be used for the production of hydrogen from synthesis gas.
  • the solution proposed in the context of the invention solves the following problems: - corrosion protection possible for large areas of the reforming tube.
  • large surface is meant parts whose dimensions make it difficult or impossible to apply a protective coating;

Landscapes

  • Chemical & Material Sciences (AREA)
  • Engineering & Computer Science (AREA)
  • General Engineering & Computer Science (AREA)
  • Organic Chemistry (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Mechanical Engineering (AREA)
  • Ceramic Engineering (AREA)
  • Physical Or Chemical Processes And Apparatus (AREA)
  • Hydrogen, Water And Hydrids (AREA)

Abstract

Reforming tube (1) comprising: a cavity (2) open at each end of the tube, an external wall, an internal wall (3), a corrosion-protection piece (4) inserted into the cavity to mirror at least part of the internal wall, a space comprised between the internal wall and the protective piece, and a refractory material (5) filling said space comprised between the internal wall and the protective piece.

Description

TUBE DE REFORMAGE COMPRENANT UN INSERT DE PROTECTION  REFORMING TUBE COMPRISING A PROTECTIVE INSERT
CONTRE LA CORROSION  AGAINST CORROSION
La présente invention a pour objet un tube de reformage comprenant un moyen permettant d'éviter dans sa cavité le phénomène de corrosion appelé « métal dusting ». Par « métal dusting » on entend une désintégration catastrophique des métaux (Fe, Ni, Co) observée dans les atmosphères carburantes de procédés chimiques et pétrochimiques. The present invention relates to a reforming tube comprising means for avoiding in its cavity the phenomenon of corrosion called "metal dusting". By "metal dusting" is meant a catastrophic disintegration of metals (Fe, Ni, Co) observed in the fuel atmospheres of chemical and petrochemical processes.
Cette corrosion rapide et locale peut conduire à des problèmes au sein du procédé de reformage notamment des problèmes de sécurité. This rapid and local corrosion can lead to problems within the reforming process including security problems.
Aujourd'hui les mécanismes de cette corrosion ne sont pas bien compris et il semble que de nombreux paramètres ont une influence : la composition chimique de l'alliage, la taille des grains, les contraintes résiduelles, la finition de la surface, la pression du procédé, la composition de l'atmosphère...Et il est difficile d'évaluer la contribution intrinsèque de chaque paramètre et leurs interactions.  Today the mechanisms of this corrosion are not well understood and it seems that many parameters have an influence: the chemical composition of the alloy, the size of the grains, the residual stresses, the finish of the surface, the pressure of the process, the composition of the atmosphere ... And it is difficult to evaluate the intrinsic contribution of each parameter and their interactions.
Depuis de nombreuses années, les chercheurs ont développé plusieurs barrières pour empêcher ce phénomène de corrosion appelé « métal dusting ».  For many years, researchers have developed several barriers to prevent this phenomenon of corrosion called "metal dusting".
Parmi les solutions développées la plus importante est l'aluminisation de l'alliage. Cela consiste à faire réagir la vapeur d'aluminium avec l'alliage pour former une couche extérieure riche en aluminium. Selon l'alliage, la composition chimique du revêtement peut varier. Par exemple si nous considérons un alliage à base de Cr-Ni, la couche extérieure contiendra Al, Ni et Cr.  Among the solutions developed the most important is the aluminization of the alloy. This involves reacting the aluminum vapor with the alloy to form an outer layer rich in aluminum. Depending on the alloy, the chemical composition of the coating may vary. For example if we consider a Cr-Ni based alloy, the outer layer will contain Al, Ni and Cr.
Plus récemment, les chercheurs ont développé une nouvelle formulation de revêtement avec l'objectif d'empêcher la formation de carbone de l'atmosphère. On sait aujourd'hui que par exemple le nickel peut catalyser la formation de carbone à partir d'une atmosphère de cémentation et qu'il s'agit de la première étape du mécanisme du phénomène de « métal dusting ». En utilisant une couche extérieure qui ne catalyse pas la formation de carbone, on prévient ainsi la formation de carbone et donc le phénomène de corrosion appelé « métal dusting ». Des revêtements comprenant de l'étain ont été développés et semblent présenter une bonne performance. More recently, researchers have developed a new coating formulation with the goal of preventing the formation of carbon from the atmosphere. It is now known that, for example, nickel can catalyze the formation of carbon from a carburizing atmosphere and is the first step in the mechanism of the "metal dusting" phenomenon. By using an outer layer which does not catalyze the formation of carbon, it prevents the formation of carbon and thus the phenomenon of corrosion called "metal dusting". Coatings comprising tin have been developed and appear to exhibit good performance.
Les tubes composites sont une autre solution pour réduire la corrosion. Cette solution est basée sur l'assemblage de deux matériaux ayant des propriétés dissemblables. Habituellement un matériau présentera une résistance élevée à la corrosion dans les conditions du procédé tandis  Composite tubes are another way to reduce corrosion. This solution is based on the assembly of two materials with dissimilar properties. Usually a material will have a high resistance to corrosion under the process conditions while
FEU ILLE DE REMPLACEM ENT (RÈGLE 26) que l'autre présentera des propriétés mécaniques élevées. Les deux matériaux, habituellement des alliages, sont soudées ensemble en utilisant différents procédés de fabrication. Cela conduit à deux couches de matériaux ayant différentes épaisseurs selon les spécifications du procédé. La principale difficulté est de produire des formes complexes et le problème de la dilation thermique entraînant des contraintes qui pourraient augmenter la vitesse de corrosion ou réduire la résistance mécanique. FIRE REPLACEM ENT (RULE 26) that the other will have high mechanical properties. Both materials, usually alloys, are welded together using different manufacturing processes. This leads to two layers of materials having different thicknesses according to the process specifications. The main difficulty is to produce complex shapes and the problem of thermal expansion resulting in stresses that could increase the rate of corrosion or reduce the mechanical strength.
Partant de là, la première limitation des solutions existantes vis-à-vis du phénomène de corrosion appelé « métal dusting » est la dimension des pièces à protéger. Par exemple, si l'on considère les tubes utilisés pour le reformage du méthane, ces tubes font environ 13 m de long et il est difficile de trouver des entreprises qui possèdent l'équipement adapté pour réaliser un revêtement homogène (épaisseur et composition chimique). En outre il est difficile de réaliser le revêtement sur les petites sections de tube, avant de les souder ensemble pour obtenir la longueur finale, en raison de la faible capacité de soudage des revêtements en aluminium sur les petites sections.  From there, the first limitation of existing solutions vis-à-vis the phenomenon of corrosion called "metal dusting" is the size of the parts to be protected. For example, if we consider the tubes used for methane reforming, these tubes are about 13 m long and it is difficult to find companies that have the appropriate equipment to achieve a homogeneous coating (thickness and chemical composition) . In addition, it is difficult to coat the small sections of pipe before welding them together to obtain the final length, because of the low welding capacity of the aluminum coatings on the small sections.
La configuration des pièces à protéger peut aussi réduire le choix en termes de techniques de revêtement et composition chimique du revêtement. The configuration of the parts to be protected can also reduce the choice in terms of coating techniques and chemical composition of the coating.
Un autre des problèmes rencontrés est la différence de comportement de dilatation entre l'alliage du tube de reformage et le revêtement qui pourrait conduire à des fissures.  Another problem encountered is the difference in expansion behavior between the alloy of the reforming tube and the coating which could lead to cracks.
Dès lors, il s'agit de trouver un tube de reformage présentant un nouveau moyen amélioré permettant d'éviter dans sa cavité le phénomène de corrosion appelé « métal dusting ». Therefore, it is a question of finding a reforming tube presenting a new improved means for avoiding in its cavity the phenomenon of corrosion called "metal dusting".
Une solution de la présente invention est un tube de reformage 1 comprenant: A solution of the present invention is a reforming tube 1 comprising:
- une cavité 2 débouchant de part et d'autre du tube,  a cavity 2 opening on either side of the tube,
- une paroi externe,  an outer wall,
- une paroi interne 3,  an inner wall 3,
- une pièce de protection 4 contre la corrosion insérée dans la cavité en miroir d'au moins une partie de la paroi interne, a corrosion protection piece 4 inserted in the mirror cavity of at least a portion of the internal wall,
- un espace compris entre la paroi interne et la pièce de protection, et  a space between the inner wall and the protection part, and
- un matériau réfractaire 5 comblant ledit espace compris entre la paroi interne et la pièce de protection.  - A refractory material 5 filling said space between the inner wall and the protective part.
FEU ILLE DE REMPLACEMENT (RÈGLE 26) Selon le cas le tube de reformage selon la présente invention peut présenter une ou plusieurs des caractéristiques suivantes : FIRE REPLACEMENT ISLAND (RULE 26) Depending on the case, the reforming tube according to the present invention may have one or more of the following characteristics:
- le matériau réfractaire 5 épouse la forme de la paroi interne et la forme de la pièce de protection ;  the refractory material 5 matches the shape of the inner wall and the shape of the protective part;
- le matériau réfractaire 5 est choisi parmi : tissus de fibre céramiques, papier de fibres céramiques, les fibres céramiques réfractaires, et les fibres céramiques polycristallines. the refractory material 5 is chosen from: ceramic fiber fabrics, ceramic fiber paper, refractory ceramic fibers, and polycrystalline ceramic fibers.
- ledit tube comprend une jointure 6 entre l'extrémité supérieure de la pièce de protection et la paroi interne ;  said tube comprises a seam 6 between the upper end of the protection piece and the inner wall;
- ledit tube comprend une jointure 7 entre l'extrémité inférieure de la pièce de protection et la paroi interne ;  said tube comprises a joint 7 between the lower end of the protection piece and the inner wall;
- au moins une jointure 6 ou 7 est une soudure, une brasure ou une jointure réalisée avec du verre ou du verre céramique ;  at least one joint 6 or 7 is a weld, a solder or a joint made with glass or ceramic glass;
- la pièce de protection 4 comprend un matériau inerte vis-à-vis de la corrosion par métal dusting  the protective part 4 comprises an inert material with respect to corrosion by metal dusting
- le matériau de la pièce de protection est choisi parmi les alliages à base de nickel et de chrome ; on pourra citer à titre d'exemple les alliages commerciaux 601, 617, 690 et 693; the material of the protective part is chosen from alloys based on nickel and chromium; examples that may be mentioned are commercial alloys 601, 617, 690 and 693;
- le matériau de la pièce de protection 4 est en céramique ou présente un revêtement en céramique ; De préférence la pièce de protection 4 contre la corrosion comprend un matériau présentant une faible résistance à la corrosion et revêtement en un matériau présentant une très bonne résistance à la corrosion ou un revêtement en céramique ;  the material of the protective part 4 is made of ceramic or has a ceramic coating; Preferably, the corrosion protection piece 4 comprises a material having a low resistance to corrosion and coated with a material having a very good corrosion resistance or a ceramic coating;
- la céramique peut-être choisie parmi AI203, MgAI204, Zr02, Y203-Zr02, MgO, MgO-Zr02, AI203-Zr02, SiC, et SÏ3N4.  the ceramic may be chosen from Al 2 O 3, MgAl 2 O 4, ZrO 2, Y 2 O 3 -ZrO 2, MgO, MgO-ZrO 2, Al 2 O 3 -ZrO 2, SiC, and SiN 4.
Autrement dit la solution proposée consiste à insérer une pièce céramique ou métallique protégée. Le matériau constitutif de cette pièce de protection est sélectionné en fonction de sa résistance à la corrosion et de sa compatibilité chimique et physique avec l'alliage du tube. La pièce de protection ne colle pas à l'alliage du tube ce qui fait une grande différence avec les solutions de l'art antérieur. Le degré de liberté entre le tube et la pièce de protection permet de réduire les contraintes mécaniques qui pourraient être induites par la dilatation thermique des parties exposées à des températures élevées (400-1000°C). Cependant, cet espace entre la paroi interne du tube et la pièce de protection pourrait conduire à un écoulement du gaz de synthèse. Aussi, il est nécessaire d'éviter l'accès du gaz de synthèse dans cet espace. In other words, the solution proposed is to insert a protected ceramic or metal part. The constituent material of this protective part is selected according to its resistance to corrosion and its chemical and physical compatibility with the alloy of the tube. The protective piece does not stick to the alloy of the tube which makes a big difference with the solutions of the prior art. The degree of freedom between the tube and the protective part makes it possible to reduce the mechanical stresses that could be induced by the thermal expansion of the parts exposed to high temperatures (400-1000 ° C). However, this space between the inner wall of the tube and the protective part could lead to a flow of synthesis gas. Also, it is necessary to avoid the access of synthesis gas in this space.
La présente invention propose comme solution principale au problème d'accès du gaz de synthèse dans ledit espace, l'utilisation d'un matériau réfractaire comblant ledit espace compris entre la paroi interne et la pièce de protection. De préférence le matériau réfractaire s'ajuste à la forme de la paroi interne du tube. Le matériau réfractaire doit être sélectionné en fonction de sa capacité à résister à une atmosphère de gaz de synthèse (H2, CO, CH4, H20), à haute température (800 à 1000°C) et à se déformer lorsqu'il est soumis à une charge limitée afin de pouvoir s'ajuster à la forme de la paroi interne du tube et à la forme de la paroi de la pièce de protection. Cette déformation (compression) du matériau réfractaire sous son propre poids et avec l'impact du flux de syngas sur la partie conique de la pièce 4 va réduire le débit d'écoulement de gaz de synthèse dans l'espace entre la paroi interne du tube et la pièce de protection. Notons que les fibres céramiques réfractaires sont de bons candidats pour cette application.  The present invention proposes as a main solution to the problem of access of the synthesis gas in said space, the use of a refractory material filling said space between the inner wall and the protective part. Preferably the refractory material adjusts to the shape of the inner wall of the tube. The refractory material must be selected according to its ability to withstand a synthesis gas atmosphere (H2, CO, CH4, H2O) at high temperature (800 to 1000 ° C) and to deform when subjected to a limited load in order to fit the shape of the inner wall of the tube and the shape of the wall of the protective part. This deformation (compression) of the refractory material under its own weight and with the impact of the flow of syngas on the conical part of the part 4 will reduce the flow rate of synthesis gas in the space between the inner wall of the tube and the protection piece. Note that refractory ceramic fibers are good candidates for this application.
A cette solution principale 2 solutions secondaires peuvent être ajoutées séparément ou en combinaison :  To this main solution 2 secondary solutions can be added separately or in combination:
- utilisation d'une jointure entre l'extrémité supérieure de la pièce de protection et la paroi interne ; et/ou  - use of a joint between the upper end of the protective part and the inner wall; and or
- utilisation d'une jointure entre l'extrémité inférieure de la pièce de protection et la paroi interne. - Use of a joint between the lower end of the protective part and the inner wall.
Ces 2 solutions secondaires permettent dans le cas où la solution principale réduit fortement mais laisse passer le flux gazeux d'obtenir dans l'espace compris entre la paroi interne et la pièce de protection un gaz de synthèse statique ce qui réduit considérablement le taux de corrosion.  These 2 secondary solutions allow in the case where the main solution strongly reduces but allows the gas flow to obtain in the space between the inner wall and the protective part a static synthesis gas which considerably reduces the rate of corrosion. .
Notons que le tube de reformage selon l'invention sera de préférence utilisé pour la production d'hydrogène à partir de gaz de synthèse.  Note that the reforming tube according to the invention will preferably be used for the production of hydrogen from synthesis gas.
La solution proposée dans le cadre de l'invention permet de résoudre les problèmes suivants : - protection contre la corrosion possible pour des grandes surfaces du tube de reformage. On entend par grande surface des pièces dont les dimensions rendent difficile ou impossible l'application d'un revêtement de protection; The solution proposed in the context of the invention solves the following problems: - corrosion protection possible for large areas of the reforming tube. By large surface is meant parts whose dimensions make it difficult or impossible to apply a protective coating;
- le choix des matériaux de la pièce de protection et la compatibilité avec l'alliage de base est beaucoup plus facile étant donné que la pièce de protection n'est pas en contact avec la paroi interne du tube de reformage ; et  the choice of the materials of the protective part and the compatibility with the base alloy is much easier since the protective part does not come into contact with the inner wall of the reforming tube; and
- les risques de fissuration au niveau de la pièce de protection sont également diminuées car les pièces ne sont pas solidaires et peuvent se déplacer les unes par rapport aux autres librement. Ceci permet de réduire au maximum les contraintes à l'interface entre les pièces.  - The risk of cracking at the protective part is also reduced because the parts are not integral and can move relative to each other freely. This minimizes the constraints at the interface between the parts.

Claims

Revendications claims
1. Tube de reformage (1) comprenant: 1. Reforming tube (1) comprising:
- une cavité (2) débouchant de part et d'autre du tube, a cavity (2) emerging on either side of the tube,
- une paroi externe,  an outer wall,
- une paroi interne (3),  an inner wall (3),
- une pièce de protection (4) contre la corrosion insérée dans la cavité en miroir d'au moins une partie de la paroi interne,  a corrosion protection piece (4) inserted in the mirror cavity of at least a portion of the internal wall,
- un espace compris entre la paroi interne et la pièce de protection, et a space between the inner wall and the protection part, and
- un matériau réfractaire (5) comblant ledit espace compris entre la paroi interne et la pièce de protection.  - A refractory material (5) filling said space between the inner wall and the protective part.
2. Tube de reformage selon la revendication 1, caractérisé en ce que le matériau réfractaire (5) épouse la forme de la paroi interne et la forme de la pièce de protection. 2. Reforming tube according to claim 1, characterized in that the refractory material (5) matches the shape of the inner wall and the shape of the protective part.
3. Tube de reformage selon l'une des revendications 1 ou 2, caractérisé en ce que le matériau réfractaire (5) est choisi parmi les tissus de fibre céramiques, papier de fibres céramiques, les fibres céramiques réfractaires, et les fibres céramiques polycristallines. 3. Reforming tube according to one of claims 1 or 2, characterized in that the refractory material (5) is selected from ceramic fiber fabrics, ceramic fiber paper, refractory ceramic fibers, and polycrystalline ceramic fibers.
4. Tube de reformage selon l'une des revendications 1 à 3, caractérisé en ce que ledit tube comprend une jointure (6) entre l'extrémité supérieure de la pièce de protection et la paroi interne. 4. Reforming tube according to one of claims 1 to 3, characterized in that said tube comprises a seam (6) between the upper end of the protective part and the inner wall.
5. Tube de reformage selon l'une des revendications 1 à 4, caractérisé en ce que ledit tube comprend une jointure (7) entre l'extrémité inférieure de la pièce de protection et la paroi interne. 5. Reforming tube according to one of claims 1 to 4, characterized in that said tube comprises a seam (7) between the lower end of the protective part and the inner wall.
6. Tube de reformage selon l'une des revendications 5 ou 6, caractérisé en ce qu'au moins une jointure (6) ou (7) est une soudure, une brasure ou une jointure réalisée avec du verre ou du verre céramique. 6. reforming tube according to one of claims 5 or 6, characterized in that at least one joint (6) or (7) is a weld, a solder or a joint made with glass or ceramic glass.
7. Tube de reformage selon l'une des revendications 1 à 6, caractérisé en ce que la pièce de protection (4) contre la corrosion comprend un matériau inerte vis-à-vis de la corrosion par métal dusting. 7. Reforming tube according to one of claims 1 to 6, characterized in that the protection piece (4) against corrosion comprises a material inert vis-à-vis corrosion metal dusting.
8. Tube de reformage selon la revendication 7, caractérisé en ce que le matériau de la pièce de protection (4) est choisi parmi les alliages à base de nickel et de chrome. 8. Reforming tube according to claim 7, characterized in that the material of the protective part (4) is selected from alloys based on nickel and chromium.
9. Tube de reformage selon la revendication 7, caractérisé en ce que le matériau de la pièce de protection (4) est en céramique ou présente un revêtement en céramique. 9. Reforming tube according to claim 7, characterized in that the material of the protective piece (4) is ceramic or has a ceramic coating.
10. Tube de reformage selon la revendication 9, caractérisé en ce que la céramique peut-être choisie parmi AI203, MgAI204, Zr02, Y203-Zr02, MgO, MgO-Zr02, AI203-Zr02, SiC, et SÏ3N4. 10. Reforming tube according to claim 9, characterized in that the ceramic may be selected from Al 2 O 3, MgAl 2 O 4, ZrO 2, Y 2 O 3 -ZrO 2, MgO, MgO-ZrO 2, Al 2 O 3 -ZrO 2, SiC, and SiN 4.
11. Utilisation d'un tube de reformage selon l'une des revendications 1 à 10 pour la production d'hydrogène à partir de gaz de synthèse. 11. Use of a reforming tube according to one of claims 1 to 10 for the production of hydrogen from synthesis gas.
EP16750830.8A 2015-08-12 2016-08-11 Reforming tube comprising an insert affording protection against corrosion Pending EP3334521A1 (en)

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
EP15180784.9A EP3130397A1 (en) 2015-08-12 2015-08-12 Reforming tube with protection part against corrosion
PCT/EP2016/069106 WO2017025587A1 (en) 2015-08-12 2016-08-11 Reforming tube comprising an insert affording protection against corrosion

Publications (1)

Publication Number Publication Date
EP3334521A1 true EP3334521A1 (en) 2018-06-20

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EP15180784.9A Withdrawn EP3130397A1 (en) 2015-08-12 2015-08-12 Reforming tube with protection part against corrosion
EP16750830.8A Pending EP3334521A1 (en) 2015-08-12 2016-08-11 Reforming tube comprising an insert affording protection against corrosion

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EP15180784.9A Withdrawn EP3130397A1 (en) 2015-08-12 2015-08-12 Reforming tube with protection part against corrosion

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US (1) US10421057B2 (en)
EP (2) EP3130397A1 (en)
CN (1) CN208906063U (en)
WO (1) WO2017025587A1 (en)

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US20180229206A1 (en) 2018-08-16
US10421057B2 (en) 2019-09-24
WO2017025587A1 (en) 2017-02-16
EP3130397A1 (en) 2017-02-15
CN208906063U (en) 2019-05-28

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