CN101512674A - High pergormance coated material with improved metal dusting corrosion resistance - Google Patents

High pergormance coated material with improved metal dusting corrosion resistance Download PDF

Info

Publication number
CN101512674A
CN101512674A CN 200780032107 CN200780032107A CN101512674A CN 101512674 A CN101512674 A CN 101512674A CN 200780032107 CN200780032107 CN 200780032107 CN 200780032107 A CN200780032107 A CN 200780032107A CN 101512674 A CN101512674 A CN 101512674A
Authority
CN
China
Prior art keywords
coated metal
pqr
composition
coating
metal
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
CN 200780032107
Other languages
Chinese (zh)
Inventor
肯尼斯·E·巴格诺里
菲利普·G·安德森
特里克·A·拉马纳雷阿南
全昌旻
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.)
ExxonMobil Technology and Engineering Co
Original Assignee
ExxonMobil Research and Engineering Co
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 ExxonMobil Research and Engineering Co filed Critical ExxonMobil Research and Engineering Co
Publication of CN101512674A publication Critical patent/CN101512674A/en
Pending legal-status Critical Current

Links

Images

Classifications

    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
    • C01B3/00—Hydrogen; Gaseous mixtures containing hydrogen; Separation of hydrogen from mixtures containing it; Purification of hydrogen
    • C01B3/02—Production of hydrogen or of gaseous mixtures containing a substantial proportion of hydrogen
    • 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
    • C10G2/00—Production of liquid hydrocarbon mixtures of undefined composition from oxides of carbon
    • C10G2/30—Production of liquid hydrocarbon mixtures of undefined composition from oxides of carbon from carbon monoxide with hydrogen
    • C10G2/32—Production of liquid hydrocarbon mixtures of undefined composition from oxides of carbon from carbon monoxide with hydrogen with the use of catalysts
    • C10G2/34—Apparatus, reactors
    • C—CHEMISTRY; METALLURGY
    • C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
    • C23C—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; SURFACE TREATMENT OF METALLIC MATERIAL BY DIFFUSION INTO THE SURFACE, BY CHEMICAL CONVERSION OR SUBSTITUTION; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL
    • C23C10/00—Solid state diffusion of only metal elements or silicon into metallic material surfaces
    • C23C10/02—Pretreatment of the material to be coated
    • 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
    • C23C26/00—Coating not provided for in groups C23C2/00 - C23C24/00
    • C—CHEMISTRY; METALLURGY
    • C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
    • C23C—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; SURFACE TREATMENT OF METALLIC MATERIAL BY DIFFUSION INTO THE SURFACE, BY CHEMICAL CONVERSION OR SUBSTITUTION; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL
    • C23C28/00—Coating for obtaining at least two superposed coatings either by methods not provided for in a single one of groups C23C2/00 - C23C26/00 or by combinations of methods provided for in subclasses C23C and C25C or C25D
    • C23C28/30—Coatings combining at least one metallic layer and at least one inorganic non-metallic layer
    • C23C28/32—Coatings combining at least one metallic layer and at least one inorganic non-metallic layer including at least one pure metallic layer
    • C23C28/321—Coatings combining at least one metallic layer and at least one inorganic non-metallic layer including at least one pure metallic layer with at least one metal alloy layer
    • C—CHEMISTRY; METALLURGY
    • C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
    • C23C—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; SURFACE TREATMENT OF METALLIC MATERIAL BY DIFFUSION INTO THE SURFACE, BY CHEMICAL CONVERSION OR SUBSTITUTION; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL
    • C23C28/00—Coating for obtaining at least two superposed coatings either by methods not provided for in a single one of groups C23C2/00 - C23C26/00 or by combinations of methods provided for in subclasses C23C and C25C or C25D
    • C23C28/30—Coatings combining at least one metallic layer and at least one inorganic non-metallic layer
    • C23C28/34—Coatings combining at least one metallic layer and at least one inorganic non-metallic layer including at least one inorganic non-metallic material layer, e.g. metal carbide, nitride, boride, silicide layer and their mixtures, enamels, phosphates and sulphates
    • C23C28/345—Coatings combining at least one metallic layer and at least one inorganic non-metallic layer including at least one inorganic non-metallic material layer, e.g. metal carbide, nitride, boride, silicide layer and their mixtures, enamels, phosphates and sulphates with at least one oxide layer
    • C—CHEMISTRY; METALLURGY
    • C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
    • C23C—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; SURFACE TREATMENT OF METALLIC MATERIAL BY DIFFUSION INTO THE SURFACE, BY CHEMICAL CONVERSION OR SUBSTITUTION; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL
    • C23C28/00—Coating for obtaining at least two superposed coatings either by methods not provided for in a single one of groups C23C2/00 - C23C26/00 or by combinations of methods provided for in subclasses C23C and C25C or C25D
    • C23C28/30—Coatings combining at least one metallic layer and at least one inorganic non-metallic layer
    • C23C28/34—Coatings combining at least one metallic layer and at least one inorganic non-metallic layer including at least one inorganic non-metallic material layer, e.g. metal carbide, nitride, boride, silicide layer and their mixtures, enamels, phosphates and sulphates
    • C23C28/345—Coatings combining at least one metallic layer and at least one inorganic non-metallic layer including at least one inorganic non-metallic material layer, e.g. metal carbide, nitride, boride, silicide layer and their mixtures, enamels, phosphates and sulphates with at least one oxide layer
    • C23C28/3455—Coatings combining at least one metallic layer and at least one inorganic non-metallic layer including at least one inorganic non-metallic material layer, e.g. metal carbide, nitride, boride, silicide layer and their mixtures, enamels, phosphates and sulphates with at least one oxide layer with a refractory ceramic layer, e.g. refractory metal oxide, ZrO2, rare earth oxides or a thermal barrier system comprising at least one refractory oxide layer
    • 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

Landscapes

  • Chemical & Material Sciences (AREA)
  • Engineering & Computer Science (AREA)
  • Organic Chemistry (AREA)
  • Mechanical Engineering (AREA)
  • Inorganic Chemistry (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Metallurgy (AREA)
  • Materials Engineering (AREA)
  • General Engineering & Computer Science (AREA)
  • Ceramic Engineering (AREA)
  • Oil, Petroleum & Natural Gas (AREA)
  • General Chemical & Material Sciences (AREA)
  • Combustion & Propulsion (AREA)
  • Other Surface Treatments For Metallic Materials (AREA)
  • Coating By Spraying Or Casting (AREA)

Abstract

High performance coated metal compositions resistant to metal dusting corrosion and methods of providing such compositions are provided by the present invention. The coated metal compositions are represented by the structure (PQR), wherein P is an oxide layer at the surface of (PQR), Q is a coating metal layer interposed between P and R, and R is a base metal. P includes alumina, chromia, silica, mullite or mixtures thereof. Q includes Ni and Al. R is selected from the group consisting of carbon steels, low chromium steels, ferritic stainless steels, austenetic stainless steels, duplex stainless steels, Inconel alloys, Incoloy alloys, Fe-Ni based alloys, Ni-based alloys and Co-based alloys. Advantages exhibited by the disclosed coated metal compositions include improved metal dusting corrosion resistance at high temperatures in carbon-supersaturated environments having relatively low oxygen partial pressures. The coated metal compositions are suitable for use in syngas generation process equipment.

Description

Has the corrosive high performance coated material of improved metal dusting resistantization
Invention field
The present invention relates to the field that synthesis gas produces institute's materials used in the technology.More particularly, the present invention relates to be exposed to material in corrosive reactants and the carbon supersaturated environments.More particularly, the present invention relates to coated material composition and method, they are used to control the metal dusting corrosion of the reactor system, gas/gas heat exchangers system and synthesis gas process pipe arrangement and the pipe-line equipment that are exposed to high-carbon activity and relative low oxygen activity.
Background of invention
One of the abundantest fossil fuel are natural gases, and it mainly is a methane.Be high-value product (for example liquid hydrocarbon), chemicals (for example ethene) or produce in the high-temperature technology of electric energy comprising, run into usually and comprise the very active and relative environmental condition of hanging down oxygen activity of high-carbon methane conversion.In many other synthesis gas production processes, also may run into similar environment.In many synthesis gas production processes, be synthesis gas for example with methane conversion, coke is converted into synthesis gas, coal is converted into synthesis gas, heavy oil and pitch are converted into synthesis gas, all can run into environment with high-carbon activity and relative low oxygen activity.The pyroreaction modulator material of in this process, using, heat exchanger material, synthesis gas process pipe arrangement and pipeline material, in use deterioration owing to the corrosion of the very aggressive form that is called as metal dusting.Metal dusting is under the temperature of 350～10500 ℃ of scopes, and have low relatively by (about 10 -10～10 -20Under the individual atmospheric pressure) under the carbon supersaturation of partial pressure of oxygen (carbon activity〉1) environment, the high temperature corrosion of a kind of harmful form of Fe, Ni and Co base alloy experience.The corrosion characteristics of this form is that body phase metal is disintegrated and is powder or dust.Most of alloys of present commercially available acquisition are because this corrosion process and deterioration.
Original position forms chromium oxide (Cr in low oxygen partial pressure environment although many high temperature alloys are designed to 2O 3) skin covering of the surface, but under the situation that oxygen exists, (that is,〉1000 ℃) chromium oxide reaction at high temperature forms CrO 3, it is the alloy that steam and evaporation cause the chromium loss.The alloy of chromium loss can not form the protectiveness chromium oxide film, so carbon enters this alloy from the rich carbocyclic ring border (having the carbon activity greater than 1) of highly reducing.This causes the metal dusting corrosion.
Aluminium and silicon are that strong oxide forms thing, can join in the high temperature alloy to form aluminium oxide and silicon dioxide meter facial mask improvement corrosion resistance by original position.Yet these expectations of excessive adding are used for the element of excellent corrosion resistance, cause the poor mechanical strength under the high temperature that alloy uses usually.Therefore, the alloy that contains excess of aluminum and silicon can not be used for constructing the member of synthesis gas production process.
Disclosedly in the literature be used to control the metal dusting corroding method and comprise and use gaseous state inhibitor, for example H 2S.Pass through H 2S suppresses to have two shortcomings.One is H 2Most of catalyst poisonings that S often makes hydrocarbon conversion process use.Secondly, must from exit flow, remove H 2S, this has increased running cost in fact.
People's such as Ramanarayanan United States Patent (USP) 6,692,838 discloses the composition of metal dusting resistantization and has been used to prevent be exposed to the method for the metal surface metal dusting of carbon supersaturated environments.Said composition comprises (a) alloy and (b) oxide coating of the protectiveness on the alloy.This alloy comprises alloying metal and underlying metal, and wherein this alloying metal comprises the mixture of chromium and manganese, and this underlying metal comprises iron, nickel and cobalt.United States Patent (USP) 6,692,838 full content is introduced herein as a reference.
People's such as Ramanarayanan United States Patent (USP) 6,737,175 discloses the alloy composite of metal dusting resistantization, and the metal surface metal dusting corroding method that is used to suppress to be exposed to supersaturation carbocyclic ring border.This method comprises the structure cu-based alloy surface, or uses the acid bronze alloy coating surface.United States Patent (USP) 6,737,175 full content is introduced herein as a reference.
The U.S. Patent application 11/126,007 that people such as Chun submitted on May 10th, 2005 also discloses alloy composite and the method that is used to prevent be exposed to the metal surface metal dusting of carbon supersaturated environments.This alloy composite comprises alloy (PQR) and at the lip-deep multilayer of alloy (PQR) (at least three layers) oxide-film, wherein this alloy (PQR) comprises the metal (P) that is selected from Fe, Ni, Co and composition thereof, comprise Cr, Mn and comprise the alloying metal (Q) of Al, Si or Al/Si, and alloying element (R).This multilayer oxide-film in the oversaturated metal dusting environment of carbon in alloy composite between the operating period original position form.The full content of U.S. Patent application 11/126,007 is introduced herein as a reference.
The alloy and the surface-coated material that need a kind of energy metal dusting resistant corrosion newly.More specifically, need a kind of advanced person's coated material composition, wherein this metallizing is at low oxygen partial pressure (about 10 -10～about 10 -20Individual atmospheric pressure) and the environment of carbon supersaturation (carbon activity〉1) down can the metal dusting resistant corrosion, and comprise high temperature strength and other performances that needs are provided to coating material, for example the underlying metal of creep strength and toughness.So advanced coated material composition should be able to form the outer protection oxide skin(coating), to stop carbon diffusion by the diffusion impervious layer that enters as carbon.
Summary of the invention
According to of the present invention open, the coated material composition of favourable high-performance metal dusting resistant corrosion comprises: (PQR), wherein P is at (PQR) lip-deep oxide skin(coating), Q is the metallizing layer that inserts between P and R, R is a foundation metal layer, wherein P comprises aluminium oxide, chromium oxide, silica, mullite or its mixture, Q comprises Ni and Al, and at least a Cr that is selected from, Si, Mn, Fe, Co, B, C, N, P, Ga, Ge, As, In, Sn, Sb, Pb, Sc, La, Y, Ce, Ti, Zr, Hf, V, Nb, Ta, Mo, W, Ru, Rh, Ir, Pd, Pt, Cu, Ag, the element of Au and composition thereof, R is selected from carbon steel, low-chrome steel, ferritic stainless steel, austenitic stainless steel, two phase stainless steel, because of Cornell alloy (Inconelalloy), Yin Keluoyi alloy (Incoloy alloy), Fe-Ni base alloy, Ni base alloy and Co base alloy.
The present invention openly relates to the metal surface metal dusting corroding method that a kind of favourable preventing is exposed to the carbon supersaturated environments on the other hand, this method comprises high performance coated metal composition (PQR), wherein P is at (PQR) lip-deep oxide skin(coating), Q is the metallizing layer that inserts between P and R, R is a foundation metal layer, wherein P comprises aluminium oxide, chromium oxide, silica, mullite or its mixture, Q comprises Ni and Al, and at least a Cr that is selected from, Si, Mn, Fe, Co, B, C, N, P, Ga, Ge, As, In, Sn, Sb, Pb, Sc, La, Y, Ce, Ti, Zr, Hf, V, Nb, Ta, Mo, W, Ru, Rh, Ir, Pd, Pt, Cu, Ag, the element of Au and composition thereof, R is selected from carbon steel, low-chrome steel, ferritic stainless steel, austenitic stainless steel, two phase stainless steel, because of the Cornell alloy, the Yin Keluoyi alloy, Fe-Ni base alloy, Ni base alloy and Co base alloy; Wherein this method comprises the step that (PQR) is provided to the metal surface.
Produced many advantages and use/application therefore by the favourable high performance coated material composition that comprises (PQR), wherein P is at (PQR) lip-deep oxide skin(coating), and Q is the metallizing layer between P and R, and R is a foundation metal layer disclosed herein.
For example, in illustrative embodiments disclosed by the invention, comprise the high performance coated material composition of (PQR), at high temperature with the carbon supersaturated environments with relative low oxygen partial pressure in, present improved metal dusting resistant corrosivity.
Disclose in the other illustrative embodiments in the present invention, comprise that the high performance coated material composition of (PQR) presents the ability of the oxide-film that forms Thermodynamically stable, poor growth, adhesion inertia, with the diffusion barrier that enters as carbon.
Disclose in the other illustrative embodiments in the present invention, comprise that the high performance coated material composition of (PQR) can not make most of catalyst poisonings of using in hydrocarbon conversion process.
Disclose in the other illustrative embodiments in the present invention, comprise that the high performance coated material composition of (PQR) has produced surface oxide film or the improved adherence of layer, this has improved spalling resistance.
Disclose in the other illustrative embodiments in the present invention, comprise that the high performance coated material composition of (PQR) has produced the carbon laydown that reduces in the carbon supersaturated environments.
Disclose in the other illustrative embodiments in the present invention, when the high performance coated material composition that comprises (PQR) is exposed to the metal dusting environment of low oxygen partial pressure, form oxide skin(coating) (P) in its surface.
Disclose in the other illustrative embodiments in the present invention, in the oversaturated environment of carbon, use during this alloy, comprising that original position forms oxide skin(coating) (P) on the high performance coated material composition surface of (PQR).
Disclose in the other illustrative embodiments in the present invention, before using, by this alloy being exposed under the oversaturated low oxygen partial pressure environment of carbon or being exposed under the controlled low oxygen partial pressure environment, form oxide skin(coating) (P) on the high performance coated material composition surface of (PQR) comprising.
Disclose in the other illustrative embodiments in the present invention, have low porosity at the lip-deep metallizing layer of the high performance coated material composition that comprises (PQR) (Q).
Another advantage that comprises the high performance coated material composition of (PQR) is; if in the oversaturated environment of carbon, use during the said composition; protectiveness oxide layer (P) is broken; then protectiveness oxide layer (P) can form in this crack again to repair this oxide skin(coating), therefore protects not metal dusting of this alloy during use.
The high performance coated material composition of disclosed comprising (PQR) can be applicable in the synthesis gas process equipment, whenever this equipment all contacts with the carbon supersaturated environments during use, comprises that reactor, gas/gas heat exchangers and synthesis gas produce the pipe arrangement and the pipeline of technology.
In order to protect, can provide disclosed and comprise the high performance coated material composition of (PQR) in the following way to the surface: 1) construct this equipment from (PQR), 2) co-extrusion pressure Q and R to be forming the surface of this equipment, or 3) on R, apply Q is exposed to the metal dusting environment with formation equipment surface.
These and other advantage, feature and attribute disclosed by the invention and comprise high performance coated material composition and their the favourable application and/or the purposes of (PQR), from detailed description subsequently, especially when reading together, with apparent with subsidiary herein accompanying drawing.
The accompanying drawing summary
For helping to make and to use those of ordinary skill in its theme association area, referring to subsidiary accompanying drawing, wherein:
Fig. 1 describes the schematic diagram that the present invention is used to protect the high-performance surface-coated material of the synthesis gas generation process equipment on pipe arrangement or pipeline diverse location.
Fig. 2 has described at 650 ℃, 50CO-50H 2After reacting 160 hours in the admixture of gas, the quality owing to carbon laydown (tolerance of metal dusting corrosion) on the alloy of Linde B polishing increases block diagram.
Fig. 3 has described at 650 ℃, 50CO-50H 2After reacting 160 hours in the admixture of gas, cross section scanning electron microscopy (SEM) image of uncoated Inconel 601 alloys (prior art) erosional surface.
Fig. 4 has described at 650 ℃, 50CO-50H 2In the admixture of gas after the reaction 160 hours, be the section S EM image of Inconel 693 alloys (prior art) erosional surface that applies.
Fig. 5 has described at 1050 ℃, 50CO-50H 2After testing 300 hours in the admixture of gas, the EDXS line of Inconel 601 materials that high-performance NiAl of the present invention applies distributes.
Fig. 6 has described at 1050 ℃, 50CO-50H 2After testing 300 hours in the admixture of gas, the surface and the section S EM image of Inconel 601 materials that high-performance NiAl of the present invention applies.
Fig. 7 has described at 1050 ℃, 50CO-50H 2Before testing 300 hours in the admixture of gas, Inconel 601 materials that high-performance NiCr Al of the present invention applies distribute near the EDXS line on coated surface.
Fig. 8 has described at 1050 ℃, 50CO-50H 2After testing 300 hours in the admixture of gas, Inconel 601 materials that high-performance NiCr Al of the present invention applies are near the surface on coated surface and the image in cross section.
Fig. 9 has described at 1050 ℃, 50CO-50H 2Before testing 300 hours in the admixture of gas, 35/45 alloy that high-performance NiCr Al of the present invention applies distributes near the EDXS line on coated surface.
Figure 10 has described at 1050 ℃, 50CO-50H 2After testing 300 hours in the admixture of gas, 35/45 alloy that high-performance NiCr Al of the present invention applies is near the surface on coated surface and the image in cross section.
Figure 11 has described at 650 ℃, 50CO-50H 2After testing 160 hours in the admixture of gas, Inconel 601 materials (prior art) that NiCrAl applies are near the surface and the cross-sectional image on coated surface.
Embodiment
The present invention relates to form the high performance coated material of stable alumina surface film.The coated material composition difference with the prior art of high-performance metal dusting resistant of the present invention corrosion is to comprise oxide layer, be positioned at the metallizing on oxide layer one side, with the underlying metal that is positioned at the oxide skin(coating) side relative with metallizing.More specifically, metallizing difference with the prior art of the present invention is surface oxide film or the improved adhesion strength of layer, and this can improve spalling resistance.Metallizing difference with the prior art of the present invention also is the improved adhesion strength of this underlying metal, and this can improve the coating integrality.In addition, metallizing of the present invention has reduced carbon laydown with respect to prior art in the oversaturated environment of carbon.
With respect to the alloy composite of prior art as protection metal dusting coating on the metal surface that is exposed to the carbon supersaturated environments, high performance coated material composition of the present invention can provide tangible advantage.The advantageous property of disclosed high-performance coated alloy composition and/or characteristic be at least in part based on the structure of the pellumina that forms on coating metal surfaces, this especially comprises the tendency that the carbon laydown of improved metal dusting resistant corrosivity, minimizing, the catalyst poisoning used reduce, the improved adhesion strength of surface oxide film that original position forms, improved spalling resistance in hydrocarbon conversion process, before using and in using when being exposed to the carbon supersaturated environments improved formation easiness.
The coated material composition of the high performance metal dusting resistant corrosion of the present invention is represented by general formula (PQR).P is the oxide skin(coating) that comprises aluminium oxide, chromium oxide, silica, mullite and composition thereof.P forms the outer surface layer of this high performance coated material composition, and therefore this layer directly contacts with the oversaturated low oxygen partial pressure environment of carbon.With oxide skin(coating) P adjacency be metallizing Q, it comprises the element of Ni and Al and at least a Cr of being selected from, Si, Mn, Fe, Co, B, C, N, P, Ga, Ge, As, In, Sn, Sb, Pb, Sc, La, Y, Ce, Ti, Zr, Hf, V, Nb, Ta, Mo, W, Ru, Rh, Ir, Pd, Pt, Cu, Ag, Au and composition thereof.That be positioned at metallizing layer Q opposite side is underlying metal R, and it is selected from carbon steel, low-chrome steel, ferritic stainless steel, austenitic stainless steel, two phase stainless steel, because of Cornell alloy, Yin Keluoyi alloy, Fe-Ni base alloy, Ni base alloy and Co base alloy.
Outer oxide layer (P)
Use in the carbon supersaturated environments during the coating material, at metallizing Q, original position forms oxide skin(coating) P on the surface.As selection,,, form oxide skin(coating) P on the surface at metallizing Q by before coating material being exposed to the oversaturated low oxygen partial pressure environment use of carbon.As selection,,, form oxide skin(coating) P on the surface at metallizing Q by before coating material being exposed to controlled low oxygen partial pressure environment use.
Oxide skin(coating) P is the oxide skin(coating) that comprises aluminium oxide, chromium oxide, silica, mullite and composition thereof, and can comprise the oxide impurity that some are formed by the element that constitutes metallizing Q and underlying metal R.Preferred oxide skin(coating) P is an aluminium oxide.The thickness range of oxide skin(coating) P be from least about 1nm to about 100 μ m, be preferably from least about 10nm to about 50 μ m, more preferably from least about 100nm to about 10 μ m.
By coating material being exposed to the metal dusting environment, form on coating metal surfaces that the present invention describes at the lip-deep oxide skin(coating) P of metallizing Q.The unrestricted example of metal dusting environment is the 50CO:50H of gaseous state 2Mixture.The metal dusting environment can also comprise other gas such as CH 4, NH 3, N 2, O 2, He, Ar and hydrocarbon, and can on metallizing Q, form the stable oxide skin(coating) P that comprises aluminium oxide, chromium oxide, silica, mullite and composition thereof.Therefore, alloy between the operating period or before, being exposed to like the metal dusting environmental classes under the reaction condition, form the protective oxide layer with it.The temperature range of metal dusting environmental optimization is about 350 ℃～about 1200 ℃, preferred about 550 ℃～about 1200 ℃.Typical open-assembly time scope about 1 hour～about 500 hours, preferred about 1 hour～about 300 hours, more preferably from about 1 hour～about 100 hours.
On coating metal surfaces,, also can on metallizing Q surface, form the oxide skin(coating) P that the present invention describes by coating material being exposed to controlled low oxygen partial pressure environment.The unrestricted example of controlled low oxygen partial pressure environment is the H of gaseous state 2O:H 2The CO of mixture and gaseous state 2: the CO mixture.The gas that the low oxygen partial pressure environment of control can also comprise other is CH for example 4, NH 3, N 2, O 2, He, Ar and hydrocarbon, and can on metallizing Q, form the stable oxide skin(coating) P that comprises aluminium oxide, chromium oxide, silica, mullite and composition thereof.Therefore, in the metal dusting environment, use before the alloy, form the protective oxide layer.This controlled low oxygen partial pressure environment preferred temperature range is about 350 ℃～about 1200 ℃, preferred about 550 ℃～about 1200 ℃.Typical open-assembly time scope about 1 hour～about 500 hours, preferred about 1 hour～about 300 hours, more preferably from about 1 hour～about 100 hours.
Metallizing layer (Q)
Metallizing Q comprises the element of Ni and Al and at least a Cr of being selected from, Si, Mn, Fe, Co, B, C, N, P, Ga, Ge, As, In, Sn, Sb, Pb, Sc, La, Y, Ce, Ti, Zr, Hf, V, Nb, Ta, Mo, W, Ru, Rh, Ir, Pd, Pt, Cu, Ag, Au and composition thereof.As being exposed to the alloy composite that protects the metal dusting coating on the carbon supersaturated environments metal surface, coated metal composition disclosed by the invention can provide tangible advantage with respect to prior art.As limiting examples, alloying element is Sc, La, Y and Ce for example, the improved adhesion strength of surface oxide film that provides original position to form, and this helps to strengthen spalling resistance.Alloying element such as Ga, Ge, As, In, Sn, Sb, Pb, Pd, Pt, Cu, Ag and Au provide the carbon laydown of minimizing, because these elements are on-catalytics for the surface carbon transfer reaction.
This metallizing layer Q comprises the aluminium of about 4wt%～about 70wt%, the aluminium of preferably about 4wt%～about 50wt%, the more preferably from about aluminium of 4wt%～about 30wt%.In a preferred embodiment, the iron that comprises in metallizing Q of metallizing layer Q lacks than the iron that comprises in underlying metal R.This metallizing Q comprises the iron less than about 12wt%, preferably less than the iron of about 10wt%, is more preferably less than the iron of about 8wt%.Comprise metallizing Q, in the oversaturated low oxygen partial pressure environment of carbon, cause the metal dusting resistant corrosivity of difference much larger than 12wt% iron.Ni as the metallizing layer component also can reduce the ashing corrosion rate, because its ashing corrosion rate is than the low about order of magnitude of pure iron.
Metallizing of the present invention has low porosity, and this helps its improved anti-carbon deposition in the carbon supersaturated environments.Metallizing layer Q comprises the porosity less than about 8 volume %, preferably less than the porosity of about 3 volume %, is more preferably less than the porosity of about 2 volume %, and even is more preferably less than the porosity of 1 volume %.Porosity excessive in this metallizing layer is transferred to metallizing and underlying metal surface as passage with corrosive gas in the metal dusting environment.Carbon transmission cause in this metallizing layer carbon deposition and in the layering of metallizing at the interface of coating/underlying metal.Therefore, the metallizing layer of realizing comprising minimal amount of porosity is favourable.
The metallizing layer of low-porosity can form by cladding process such as CVD, MOCVD, PVD, slurry coating, solid state diffusion, built-up welding and plasma powder welding.This metallizing layer can after annealing, or lf, to realize highdensity coating.On the contrary, conventional hot spray process obtains the higher metallizing layer of porosity usually such as plasma, HVOF and detonation-gun.Conventional thermally sprayed coating is made by the following method, and that wherein will melt by collision or softening particle is applied on the matrix.This coating comprises lenticular or filmated grainiess usually, and this structure is by the little molten drop of rapid curing, and bump cold surface under high speed and flattening obtains.In fact can not guarantee that all particles are accurate same sizes, can not realize identical temperature and speed.Therefore, during thermal spray process, individual particle causes the cermet coating that comprises excessive porosity of heterogeneous texture to the variation of impact conditions.
Two preferred embodiments of high performance coated material composition of the present invention comprise coating metal Q, and it comprises or (1) Ni and Al, perhaps (2) Ni, Al and Cr.Coated metal composition, NiAl is the intermetallic phase that is called as the β phase.By the following method, such as CVD, MOCVD, PVD, slurry coating and solid state diffusion β-NiAl coating is applied to underlying metal R.The thickness range of β-NiAl is about 1～about 300 μ m, preferred about 1～about 200 μ m, more preferably from about 1～about 100 μ m.This coated metal composition NiAl comprises the aluminium of about 17wt%～about 39wt% and the nickel of about 61wt%～about 83wt%.Preferably, this coated metal composition NiAl comprises the aluminium of about 18wt% and the nickel of about 82wt%.This coated metal composition NiCrAl can be applied to underlying metal R by the welding of overlaying method such as plasma powder.The thickness range of NiCrAl is about 100 μ m～about 5mm, preferred about 100 μ m～about 4mm, more preferably from about 100 μ m～about 3mm.This coated metal composition NiCrAl comprises the aluminium of about 4wt%～about 10wt%, the nickel of the chromium of about 15wt%～about 30wt% and about 60wt%～about 81wt%.Preferably, metallizing Q comprises the aluminium of about 6wt%, the chromium of about 25wt% and the nickel of about 69wt%.
Underlying metal (R)
Underlying metal R is selected from carbon steel, low-chrome steel, ferritic stainless steel, austenitic stainless steel, two phase stainless steel, because of Cornell alloy, Yin Keluoyi alloy, Fe-Ni base alloy, Ni base alloy and Co base alloy.Underlying metal R also can be any alloy that is used to construct synthesis gas manufacturing process equipment that can commercially obtain.Be used for nonrestrictive underlying metal R of the present invention, be provided in the table 1.These underlying metals are suitable for making the favourable high performance coated material (PQR) of metal dusting resistant corrosion.
Table 1:
Underlying metal, R Alloy UNS No. Alloy composition (wt%)
Carbon steel 1018 G10180 The Fe of surplus, 0.6～0.9 Mn, 0.14～0.20 C
4130 G41300 The Fe of surplus, 0.35～0.60 Mn, 0.80～1.15 Cr, 0.27～0.34 C
Low-chrome steel T11 K11562 The Mo of the Cr:0.5 of the Fe:1.25 of surplus, 0.5 Si, 0.3 Mn, 0.15 C, 0.045 P, 0.045 S
T22 K21590 The Mo of the Cr:1.0 of the Fe:2.25 of surplus, 0.5 Si, 0.3 Mn, 0.15 C, 0.035 P, 0.035 S
T5 S50100 The Mo of the Cr:0.5 of the Fe:5 of surplus, 0.5 Si, 0.3 Mn, 0.15 C, 0.04 P, 0.03 S
T9 J82090 The Si of the Cr:1.0 of the Fe:9 of surplus, 0.35 Mn, 0.02 C, 0.04 P, 0.045 S
Ferritic stainless steel 409 S40900 The Si of the Cr:1.0 of the Fe:10.5 of surplus, 1.0 Mn, 0.5 Ni, 0.5 Ti, 0.08 C, 0.045 P, 0.045 S
410 S41000 The C of the Cr:0.15 of the Fe:11.5 of surplus, 0.045 P, 0.03 S
430 S43000 The Si of the Cr:1.0 of the Fe:16.0 of surplus, 1.0 Mn, 0.12 C, 0.045 P, 0.03 S
Austenitic stainless steel 304 S30400 The Mn of the Cr:2.0 of the Ni:18 of the Fe:8 of surplus, 0.75 Si, 0.08 C, 0.04 P, 0.03 S
310 S31000 The Mn of the Cr:2.0 of the Ni:24 of the Fe:19 of surplus, 1.5 Si, 0.75 Mo, 0.25 C, 0.045 P, 0.03 S
253MA S30815 The Si of the Cr:1.7 of the Ni:21 of the Fe:11 of surplus, 0.04 Ce, 0.17 N, 0.08 C
RA85H S30615 The Al of the Si:1.0 of the Cr:3.5 of the Ni:18.5 of the Fe:14.5 of surplus, 0.2 C
Two phase stainless steel 2205 S32205 The Mn of the Cr:2.0 of the Ni:22 of the Fe:4.5 of surplus, 1.0 Si, 3.0 Mo, 0.03 C, 0.14 N, 0.03 P, 0.02 S
2507 S32507 The Mn of the Cr:1.2 of the Ni:24 of the Fe:6 of surplus, 0.8 Si, 3.0 Mo, 0.5 Cu, 0.03 C, 0.2 N, 0.035 P, 0.02 S
Because of the Cornell alloy Inconel 600 N06600 The Cr of the Fe:25.5 of the Ni:8.0 of surplus, 0.08
Inconel 601 N06601 The Al of the Mn:1.4 of the Cr:0.3 of the Fe:23.0 of the Ni:14.4 of surplus, 0.5 Si, 0.1 C
Inconel 602CA N/A The Al of the Cr:2.2 of the Fe:25.0 of the Ni:9.5 of surplus, 0.18 C
Inconel 690 N06690 The Al of the Mn:1.4 of the Cr:0.3 of the Fe:29.0 of the Ni:9.0 of surplus, 0.5 Si, 0.1 C
Inconel 693 N06693 The Al of the Cr:3.1 of the Fe:29.0 of the Ni:4.0 of surplus
InconelMA754 N/A The Al of the Mn:1.4 of the Cr:0.3 of the Fe:29.0 of the Ni:9.0 of surplus, 0.5 Si, 0.1 C
The Yin Keluoyi alloy Incoloy 800H N08810 The C of the Ti:0.07 of the Si:0.5 of the Al:0.4 of the Mn:0.5 of the Cr:0.8 of the Ni:21.0 of the Fe:33.0 of surplus
Incoloy 825 N08825 The C of the Cu:0.03 of the Mo:2.2 of the Cr:3.0 of the Fe:21.5 of the Ni:30.0 of surplus
Fe-Ni base alloy KHR-45A (35/45 Alloy) N/A The C of the Ti:0.4 of the Nb:0.1 of the Si:0.9 of the Mn:1.7 of the Cr:1.0 of the Ni:32.1 of the Fe:43.6 of surplus
Ni base alloy Haynes 214 N07214 The C of the Ti:0.05 of the Mo:0.5 of the Si:0.5 of the Al:0.2 of the Mn:4.5 of the Cr:0.5 of the Co:16.0 of the Fe:2.0 of the Ni:3.0 of surplus
Co base alloy Haynes 188 R30188 The C of the La:0.1 of the W:0.04 of the Fe:14.0 of the Cr:3.0 of the Ni:22.0 of the Co:22.0 of surplus
MP35N R30035 The Mo of the Cr:10.0 of the Ni:20.0 of the Co:35.0 of surplus
The formation methods and applications of high-performance application composition
The invention also discloses a kind of method that is used to prevent be exposed to the metal surface metal dustingization of carbon supersaturated environments.This method can provide high performance coated material composition to the metal surface, wherein this material compositions comprises: (PQR), wherein P is at (PQR) lip-deep oxide skin(coating), Q is the metallizing layer between P and R, R is a foundation metal layer, wherein P comprises aluminium oxide, chromium oxide, silica, mullite or its mixture, Q comprises Ni and Al, with at least a Cr that is selected from, Si, Mn, Fe, Co, B, C, N, P, Ga, Ge, As, In, Sn, Sb, Pb, Sc, La, Y, Ce, Ti, Zr, Hf, V, Nb, Ta, Mo, W, Ru, Rh, Ir, Pd, Pt, Cu, Ag, the element of Au and composition thereof, R is selected from carbon steel, low-chrome steel, ferritic stainless steel, austenitic stainless steel, two phase stainless steel, because of the Cornell alloy, the Yin Keluoyi alloy, Fe-Ni base alloy, Ni base alloy and Co base alloy.
Under 350～1050 ℃ temperature, in carbon supersaturation (carbon activity〉1) and have relative low oxygen partial pressure (about 10 -10～about 10 -20Individual atmospheric pressure) in the environment, metal surface to be protected can be by high performance coating material structure, can with this coating material co-extrusion pressure, can be with this coating material coating, perhaps with the combination of these three kinds of modes.At execution mode that is used for providing high performance coated material composition (PQR) of the present invention,, form said composition by by metallizing layer Q and foundation metal layer R construction process equipment.Be used for providing another execution mode of high performance coated material composition (PQR) in the present invention, by using the steel coextrusion techniques of knowing as those of ordinary skills, co-extrusion pressure metallizing layer Q and foundation metal layer R form said composition.Another is used for providing the execution mode of high performance coated material composition (PQR) in the present invention, by the paint-on technique that uses those of ordinary skills to know, with the surface of metallizing Q coating underlying metal R, from the existing surface of the process equipment of metal dusting sensitivity is formed said composition.Be suitable for applying the exemplary coating technology of underlying metal R, include but not limited to CVD, MOCVD, PVD, slurry coating, solid state diffusion, plasma powder welding, thermal spraying and sputter with coated metal composition described herein.Therefore, high performance coated material composition of the present invention (PQR) or the high performance coated material composition structure that can describe from here, apply perhaps with high performance coated material composition coextrusion described herein, or with high performance coated material composition described herein.
Above-mentioned protectiveness oxide layer P can form with device operating period original position in the carbon supersaturated environments.More precisely, for each of three kinds of methods that form metallizing and underlying metal combination (QR), this protectiveness oxide layer P can form (original position formation) being exposed to when equipment between the metal dusting environment operating period.Perhaps, above-described protectiveness oxide layer P can be before equipment uses, and forms by this metallizing and underlying metal combination (QR) are exposed to the carbon supersaturated environments.One exemplary but nonrestrictive metal dusting environment is that the high performance coating material of the present invention is exposed to metal dust environment, such as 50CO:50H 2Mixture.As selection, above-mentioned protectiveness oxide layer P can be before equipment uses, and forms by this metallizing and underlying metal combination (QR) are exposed to controlled low oxygen partial pressure environment.The limiting examples of controlled low oxygen partial pressure environment is the H that high performance coated material of the present invention is exposed to gaseous state 2O:H 2The CO of mixture or gaseous state 2: the CO mixture.Preferred temperature range is about 350 ℃～about 1200 ℃, preferred about 550 ℃～about 1200 ℃.Typical open-assembly time, scope was about 1 hour～about 300 hours, preferred about 1 hour～about 100 hours.Therefore, this protective oxide coatings P, can alloy be exposed to alloy under the reaction condition of metal dusting environment between the operating period or before form.
The high performance coated material composition of the present invention that can utilize the present invention to describe (PQR) structure is exposed to the equipment surface of metal dusting environment.Fig. 1 schematically example be used for the purposes that synthesis gas produces the coating material (PQR) of process equipment.As non-limiting instance, depend on the corrosive needs of antagonism metal dusting, can be coated on inside diameter, outer dia or the inner and outer diameter of synthesis gas process pipe arrangement or pipeline.The synthesis gas process equipment surface of benefiting from high performance coated material of the present invention comprises, during use whenever with contacted equipment of carbon supersaturated environments and reactor system.These equipment and reactor system include but not limited to that reactor, gas/gas heat exchangers and synthesis gas produce craft piping and pipeline.
The applicant attempts to disclose the execution mode and the application of the disclosure theme that all can rational expectation.Yet change unpredictalbe, unsubstantiality remains equivalent of the present invention.Although the present invention is described in conjunction with its concrete, exemplary execution mode, but clearly under the situation that does not deviate from the open spirit or scope of the present invention, according to description above, many variations, modification and change are conspicuous for the ordinary skill in the art.Therefore, all these variations, modification and the change that openly is intended to comprise above-mentioned detailed description of the present invention.
The following examples explanation the present invention and advantage thereof, rather than limit the scope of the invention.
Test method
The percentage by weight of energy dispersion X-ray spectrometer (EDXS) the assay determination element in material (PQR) by standard.For can the commercial alloy (Inconel 601 and Inconel693) that obtains, from the rectangle sample of 0.5 inch * 0.25 inch * 0.06 inch of alloy sheet preparation.Prepare Inconel 601 samples that β-NiAl applies by pack cementation method.Underlying metal Inconel601 stood chromaking before calorize solid state diffusion process handles.Under about 800 ℃, carry out diffusion reaction on the surface of underlying metal Inconel 601, to form δ-Ni 2Al 3Phase.Heat-treat under 1079 ℃ subsequently, so that low-melting δ inversion of phases is β-NiAl phase, wherein the aluminium content range is about 17～about 39wt%.By the plasma powder welding method, alloy 35/45 sample that Inconel 601 that preparation NiCrAl applies and NiCrAl apply.As a comparative example, prepare Inconel 601 samples that NiCrAl applies by air plasma spray body, conventional heat spraying method.From sample, cut 0.5 inch * 0.25 inch rectangular specimen.Polish this sample surfaces to 600 particulate fineness or Linde B (0.05 micrometer alumina powder) fineness, and in acetone, clean.Under 550 ℃～1050 ℃ test temperatures, be exposed to 50CO-50H by making sample 2Until 300 hours, study the corrosion kinetics of various alloy samples in the environment of (volume %).Use the carbon increment of Cahn 1000 electric equilibrium measuring samples.The carbon increment is the index of metal dusting corrosion.Same surface and cross section of using scanning electron microscopy (SEM) sample survey.
Embodiment
Embodiment 1
According to above-described test method, 35/45 alloy that Inconel 601 that Inconel 601, the NiCrAl that the alloy sample that test is following: Inconel 601 (prior art), Inconel 693 (prior art), β-NiAl apply applies and NiCrAl apply.The results are shown among Fig. 2 of weight measurement.Fig. 2 has described at 50CO-50H 2In the admixture of gas, after 650 ℃ were reacted 160 hours down, the quality that carbon laydown causes on the alloy of Linde B polishing increased (tolerance of metal dusting corrosion).After metal dusting exposes, the sample surfaces that the is coated with carbon metal dusting corrosion that invariably accompanies.Measure the carbon laydown of obvious amount on can commercial prior art alloy (Inconel 601 and the Inconel 693) surface that obtains.On the contrary, on coating material of the present invention (35/45 alloy that Inconel 601 that Inconel 601, the NiCrAl that β-NiAl applies applies and NiCrAl apply), measure the carbon laydown of insignificant or minimum.
Check further research metal dusting sensitivity of corrosion by erosional surface being carried out section S EM.Section S EM image in Fig. 3 demonstrates, at 50CO-50H 2In the admixture of gas, after 650 ℃ are reacted 160 hours down, the pit surface form of the Inconel 601 alloy expression characteristicses of prior art.In this pit, can see the metal dust in carbon laydown.The about 120 μ m of this pit diameter, the about 20 μ m of the degree of depth.Section S EM image in Fig. 4 demonstrates, at 50CO-50H 2In the admixture of gas, after 650 ℃ are reacted 160 hours down, the pit surface form of the Inconel 693 alloy expression characteristicses of prior art.In this pit, can see the metal dust in carbon laydown.The about 12 μ m of this pit diameter, the about 8 μ m of the degree of depth.
Embodiment 2
According to above-described test method, at 50CO-50H 2In the admixture of gas, Inconel 601 alloys that test β-NiAl applies under 1050 ℃ 300 hours.Fig. 5 has described after test near the distribution of the EDXS line of coated material surface.With the various concentration of element (nickel, aluminium, chromium and iron) that wt% represents,, draw as the function of distance coating surface distance.Fig. 5 has described at 50CO-50H 2In the admixture of gas, after 1050 ℃ are tested 300 hours down, the CONCENTRATION DISTRIBUTION of high performance coated material of the present invention (PQR).Oxide skin(coating) P is made up of aluminium oxide.The thickness of alumina layer is about 5 μ m.Coating metal Q is β-NiAl, and wherein aluminium content is about 18wt%.The thickness of β-NiAl layer is about 55 μ m.In coating metal Q, iron content is about 9.8wt%.Observe the thick rich chromium layer of about 6 μ m at the interface at β-NiAl/Inconel 601 equally.Underlying metal R is Inconel 601.
Fig. 6 is that same sample (Inconel 601 that β-NiAl applies) is at 50CO-50H 2In the admixture of gas, after 1050 ℃ are tested 300 hours down, the SEM image in surface and cross section.What describe in Fig. 6 is alumina layer, metallizing (NiAl) layer and underlying metal (Inconel601).
Embodiment 3
According to above-described test method, at 50CO-50H 2In the admixture of gas, reach 300 hours in 1050 ℃ of Inconel 601 that test the NiCrAl coating down.Fig. 7 had described before test and has distributed near the EDXS line at coated material surface place.With the various concentration of element (nickel, aluminium, chromium and iron) that wt% represents,, draw as the function of distance coating surface distance.Metallizing Q is NiCrAl, comprises the nickel of the chromium of the aluminium of about 6wt%, about 24wt%, about 68wt% and the iron of about 2wt%.The thickness of metallizing NiCrAl is about 2.1 millimeters.Underlying metal R is Inconel 601.Fig. 8 is that same sample is at 50CO-50H 2In the admixture of gas, the surface after 1050 ℃ are tested 300 hours down and the SEM image in cross section.This oxide skin(coating) comprises the thick alumina layer of about 3 μ m and other oxides (comprising chromium oxide and aluminium oxide-chromium oxide).
Embodiment 4
According to above-described test method, at 50CO-50H 2In the admixture of gas, 35/45 alloy that test NiCrAl applies under 1050 ℃ 300 hours.Fig. 9 had described before test and has distributed near the EDXS line at coated material surface place.With the various concentration of element (nickel, aluminium, silicon, chromium and iron) that wt% represents,, draw as the function of distance coating surface distance.Metallizing Q is NiCrAl, comprises the silicon of the nickel of the chromium of the aluminium of about 5wt%, about 26wt%, about 65wt%, about 1wt% and the iron of about 3wt%.The thickness of metallizing NiCrAl is about 2.6 millimeters.This underlying metal R is 35/45 alloy.Figure 10 is that same sample is at 50CO-50H 2In the admixture of gas, the surface after 1050 ℃ are tested 300 hours down and the SEM image in cross section.This oxide skin(coating) comprises the thick alumina layer of about 4 μ m.
Embodiment 5: the comparative example of highly porous coating
According to above-described test method, prepare Inconel 601 samples that NiCrAlY applies by air plasma spray body, conventional heat spraying method.The NiCrAlY powder that uses is Praxair NI-278.This metallizing comprises the aluminium of the chromium of the nickel of about 69.2wt%, about 23.2wt%, about 6.9wt% and the yttrium of about 0.7wt%.The thickness of this metallizing NiCrAlY is about 200 μ m.The NiCrAlY coating of air plasma spray body comprises many holes between the droplet that solidifies, therefore show the interface adhesion of going on business between metallizing and base alloy.Under 650 ℃, at 50CO-50H 2Inconel 601 alloys that test NiCrAlY applies in the admixture of gas 160 hours.Figure 11 be identical sample after test the surface and the SEM image in cross section.Excessive porosity in this metallizing layer is transferred to metallizing and underlying metal surface as passage with corrosive gas in the metal dusting environment.Carbon diffusion causes inner carbon laydown, the expansion in the metallizing layer, and in the coating metal layering at the interface of coating/underlying metal.Observe the particle of rich nickel in this carbon laydown, they are features of metal dusting corrosion.

Claims (41)

1. high performance metal dusting resistant corrosion coated metal composition, it comprises (PQR), wherein
P is at (PQR) lip-deep oxide skin(coating), and Q is the metallizing layer that inserts between P and R, and R is a underlying metal, wherein
P comprises aluminium oxide, chromium oxide, silica, mullite or its mixture,
Q comprises Ni and Al, with at least a element that is selected from Cr, Si, Mn, Fe, Co, B, C, N, P, Ga, Ge, As, In, Sn, Sb, Pb, Sc, La, Y, Ce, Ti, Zr, Hf, V, Nb, Ta, Mo, W, Ru, Rh, Ir, Pd, Pt, Cu, Ag, Au and composition thereof, and
R is selected from carbon steel, low-chrome steel, ferritic stainless steel, austenitic stainless steel, two phase stainless steel, because of Cornell alloy, Yin Keluoyi alloy, Fe-Ni base alloy, Ni base alloy and Co base alloy.
2. according to the coated metal composition of claim 1, wherein said oxide skin(coating) P is an aluminium oxide.
3. according to the coated metal composition of claim 1, wherein said oxide skin(coating) P is that about 1nm～about 100 μ m are thick.
4. according to the coated metal composition of claim 1, wherein said metallizing layer Q comprises the iron less than about 12wt%.
5. according to the coated metal composition of claim 1, wherein said metallizing layer Q comprises the porosity less than about 3 volume %.
6. according to the coated metal composition of claim 5, wherein said metallizing layer Q comprises the porosity less than about 1 volume %.
7. according to the coated metal composition of claim 4, wherein said metallizing layer Q comprises the aluminium of about 4wt%～about 70wt%.
8. according to the coated metal composition of claim 7, described metallizing layer Q is NiAl.
9. coated metal composition according to Claim 8, wherein said metallizing layer Q comprises the aluminium of about 17wt%～about 39wt% and the nickel of about 61wt%～about 83wt%.
10. according to the coated metal composition of claim 9, wherein said metallizing layer Q is that about 1 μ m～about 300 μ m are thick.
11. according to the coated metal composition of claim 7, wherein said metallizing layer Q is NiCrAl.
12. according to the coated metal composition of claim 11, wherein said metallizing layer Q comprises the aluminium of about 4wt%～about 10wt%, the chromium of about 15wt%～about 30wt% and the nickel of about 60wt%～about 81wt%.
13. according to the coated metal composition of claim 12, wherein said metallizing layer Q is that about 100 μ m～about 5mm is thick.
14. according to the coated metal composition of claim 1, wherein said coated metal composition (PQR) comprises that the synthesis gas that is exposed to the carbon supersaturated environments produces the process equipment surface.
15. according to the coated metal composition of claim 14, wherein said synthesis gas produces process equipment and is selected from reactor, gas/gas heat exchangers and craft piping and pipeline.
16. a metal surface metal dusting corroding method that prevents to be exposed to the carbon supersaturated environments, it comprises high performance coated metal composition (PQR), wherein
P is at (PQR) lip-deep oxide skin(coating), and Q is the metallizing layer that inserts between P and R, and R is a underlying metal, wherein
P comprises aluminium oxide, chromium oxide, silica, mullite or its mixture,
Q comprises Ni and Al, with at least a element that is selected from Cr, Si, Mn, Fe, Co, B, C, N, P, Ga, Ge, As, In, Sn, Sb, Pb, Sc, La, Y, Ce, Ti, Zr, Hf, V, Nb, Ta, Mo, W, Ru, Rh, Ir, Pd, Pt, Cu, Ag, Au and composition thereof, and
R is selected from carbon steel, low-chrome steel, ferritic stainless steel, austenitic stainless steel, two phase stainless steel, because of Cornell alloy, Yin Keluoyi alloy, Fe-Ni base alloy, Ni base alloy and Co base alloy;
Wherein said method comprises the step that (PQR) is provided to described metal surface.
17. according to the method for claim 16, wherein said oxide skin(coating) P is an aluminium oxide.
18. according to the method for claim 16, wherein said oxide skin(coating) P is that about 1nm～about 100 μ m are thick.
19. method according to claim 16, wherein, described coated metal composition between the operating period or before, by described coated metal composition being exposed to the oversaturated low oxygen partial pressure environment of carbon, perhaps be exposed to controlled low oxygen partial pressure environment, original position forms described oxide skin(coating) P.
20. according to the method for claim 19, the oversaturated low oxygen partial pressure environment of wherein said carbon is the gaseous state 50CO:50H under about 350 ℃～about 1200 ℃ temperature 2Mixture, open-assembly time is about 1 hour～about 500 hours.
21. according to the method for claim 20, the oversaturated low oxygen partial pressure environment of wherein said carbon also comprises and is selected from CH 4, NH 3, N 2, O 2, He, Ar, hydrocarbon and composition thereof gas.
22. according to the method for claim 19, wherein said controlled low oxygen partial pressure environment is the gaseous state H under about 350 ℃～about 1200 ℃ of temperature 2O:H 2Mixture or gaseous state CO 2: the CO mixture, be about 1 hour～about 500 hours time of contact.
23. according to the method for claim 22, wherein said controlled low oxygen partial pressure environment also comprises and is selected from CH 4, NH 3, N 2, O 2, He, Ar, hydrocarbon and composition thereof gas.
24. according to the method for claim 16, wherein said metallizing layer Q comprises the iron less than about 12wt%.
25. according to the method for claim 16, wherein said metallizing layer Q comprises the porosity less than about 3 volume %.
26. according to the method for claim 25, wherein said metallizing layer Q comprises the porosity less than about 1 volume %.
27. according to the method for claim 24, wherein said metallizing layer Q comprises the aluminium of about 4wt%～about 70wt%.
28. according to the method for claim 27, wherein said metallizing layer Q is NiAl.
29. according to the method for claim 28, wherein said metallizing layer Q comprises the aluminium of about 17wt%～about 39wt% and the nickel of about 61wt%～about 83wt%.
30. according to the method for claim 29, wherein said metallizing layer Q is that about 1 μ m～about 300 μ m are thick.
31., wherein saidly provide the step of (PQR) to comprise to the metal surface to be selected from following step according to the method for claim 30:
A) construct described metal surface by described high-performance coated metal composition (PQR),
B) the described metal level Q of co-extrusion pressure on described foundation metal layer R,
C) on described foundation metal layer R, apply described metal level Q and
D) step a), b) and combination c).
32., wherein said coating step c) be selected from CVD, MOCVD, PVD according to the method for claim 31, slurry applies and solid state diffusion.
33. according to the method for claim 32, it also comprises the step of after-baking or the described metal level of lf (Q).
34. according to the method for claim 27, wherein said metallizing layer Q is NiCrAl.
35. according to the method for claim 34, wherein said metallizing layer Q comprises the aluminium of about 4wt%～about 10wt%, the chromium of about 15wt%～about 30wt% and the nickel of about 60wt%～about 81wt%.
36. according to the method for claim 35, wherein said metallizing layer Q is that about 100 μ m～about 5mm is thick.
37., wherein saidly provide the step of (PQR) to comprise to the metal surface to be selected from following step according to the method for claim 36:
A) construct described metal surface by described high-performance coated metal composition (PQR),
B) the described metal level Q of co-extrusion pressure on described foundation metal layer R,
C) on described foundation metal layer R, apply described metal level Q and
D) step a), b) and combination c).
38. according to the method for claim 37, wherein said coating step c) be the welding of powder plasma body.
39. according to the method for claim 38, it also comprises the step of after-baking or the described metal level of lf (Q).
40. according to the method for claim 16, wherein said coated metal composition (PQR) comprises that the synthesis gas that is exposed to the carbon supersaturated environments produces the process equipment surface.
41. according to the method for claim 40, wherein said synthesis gas produces process equipment and is selected from reactor, gas/gas heat exchangers and craft piping and pipeline.
CN 200780032107 2006-07-18 2007-07-13 High pergormance coated material with improved metal dusting corrosion resistance Pending CN101512674A (en)

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
US83169606P 2006-07-18 2006-07-18
US60/831,696 2006-07-18

Publications (1)

Publication Number Publication Date
CN101512674A true CN101512674A (en) 2009-08-19

Family

ID=38957075

Family Applications (1)

Application Number Title Priority Date Filing Date
CN 200780032107 Pending CN101512674A (en) 2006-07-18 2007-07-13 High pergormance coated material with improved metal dusting corrosion resistance

Country Status (5)

Country Link
CN (1) CN101512674A (en)
AR (1) AR062083A1 (en)
CA (1) CA2657782A1 (en)
TW (1) TW200827483A (en)
WO (1) WO2008010965A1 (en)

Cited By (10)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN102352142A (en) * 2011-04-07 2012-02-15 世林（漯河）冶金设备有限公司 High-temperature nano-grade anti-carburizing material and coating, and application thereof
CN102971440A (en) * 2010-03-23 2013-03-13 西门子公司 Metallic bondcoat with a high gamma/gamma' transition temperature and a component
CN103260810A (en) * 2010-10-21 2013-08-21 埃克森美孚研究工程公司 Alumina forming bimetallic tube and method of making and using
CN103282137A (en) * 2010-10-21 2013-09-04 埃克森美孚研究工程公司 Alumina forming bimetallic tube for refinery process furnaces and method of making and using
CN103354841A (en) * 2010-11-24 2013-10-16 西门子公司 Metallic bondcoat or alloy with a high [gamma]/[gamma]' transition temperature and a component
CN104889597A (en) * 2015-05-09 2015-09-09 芜湖鼎瀚再制造技术有限公司 Co-Mn-Si-Fe nanometer welding layer for welding and preparation method
CN104946953A (en) * 2015-06-24 2015-09-30 安徽再制造工程设计中心有限公司 Co-Mn-Cr2O3-Ti coating material and preparation method
CN111362673A (en) * 2020-04-28 2020-07-03 新化县众一陶瓷有限公司 Preparation method of iron gray aluminum oxide wear-resistant ceramic
CN114147169A (en) * 2020-09-08 2022-03-08 中国科学院金属研究所 Method for improving interface stability of metal core coating
CN115427603A (en) * 2020-04-24 2022-12-02 诺维尔里斯公司 Thermally modified oxide-based pretreatment for metals and method for producing said metals

Families Citing this family (8)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US8748008B2 (en) 2008-06-12 2014-06-10 Exxonmobil Research And Engineering Company High performance coatings and surfaces to mitigate corrosion and fouling in fired heater tubes
JP4978755B2 (en) 2010-08-26 2012-07-18 住友金属工業株式会社 Cr-containing austenitic alloy tube and manufacturing method thereof
FR2974581B1 (en) 2011-04-29 2013-05-31 Snecma PIECE COMPRISING A COATING ON A METAL SUBSTRATE IN SUPERALLIAGE, THE COATING COMPRISING A METAL SUB-LAYER
ES2543046T3 (en) * 2012-01-18 2015-08-14 Sandvik Intellectual Property Ab Austenitic alloy
KR101921783B1 (en) 2012-03-28 2018-11-23 신닛테츠스미킨 카부시키카이샤 Cr-CONTAINING AUSTENITIC ALLOY AND METHOD FOR PRODUCING SAME
EP2835443B1 (en) 2012-04-04 2019-02-27 Nippon Steel & Sumitomo Metal Corporation Cr-containing austenitic alloy
US20180029884A1 (en) * 2015-02-23 2018-02-01 Sabic Global Technologies B.V. Methods for hydrogenation of carbon dioxide to syngas
US11819815B2 (en) * 2021-11-19 2023-11-21 Infinium Technology, Llc Catalytic reactor for the conversion of carbon dioxide and hydrogen to syngas

Family Cites Families (9)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US3637437A (en) * 1970-06-03 1972-01-25 Catalytic Technology Corp Raney metal sheet material
US5176964A (en) * 1991-04-12 1993-01-05 Martin Marietta Corporation Diffuse black plasma sprayed coatings
US6153313A (en) * 1998-10-06 2000-11-28 General Electric Company Nickel aluminide coating and coating systems formed therewith
US6454992B1 (en) * 2000-09-29 2002-09-24 Ohio Aerospace Institute Oxidation resistant and low coefficient of thermal expansion NiA1-CoCrAly alloy
US6565672B2 (en) * 2001-08-31 2003-05-20 General Electric Company Fabrication of an article having a protective coating with a flattened, pre-oxidized protective-coating surface
US7063145B2 (en) * 2001-10-24 2006-06-20 Shell Oil Company Methods and systems for heating a hydrocarbon containing formation in situ with an opening contacting the earth's surface at two locations
US6692838B2 (en) * 2002-03-15 2004-02-17 Exxonmobil Research And Engineering Company Metal dusting resistant alloys
US6737556B2 (en) * 2002-10-21 2004-05-18 Exxonmobil Chemical Patents Inc. Method and system for reducing decomposition byproducts in a methanol to olefin reactor system
SE526673C2 (en) * 2003-08-28 2005-10-25 Sandvik Intellectual Property Use of a metal sputtering resistant copper alloy

Cited By (16)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN102971440B (en) * 2010-03-23 2015-04-22 西门子公司 Metallic bondcoat with a high gamma/gamma' transition temperature and a component
CN102971440A (en) * 2010-03-23 2013-03-13 西门子公司 Metallic bondcoat with a high gamma/gamma' transition temperature and a component
US9074268B2 (en) 2010-03-23 2015-07-07 Siemens Aktiengesellschaft Metallic bondcoat with a high gamma/gamma' transition temperature and a component
CN103260810A (en) * 2010-10-21 2013-08-21 埃克森美孚研究工程公司 Alumina forming bimetallic tube and method of making and using
CN103282137A (en) * 2010-10-21 2013-09-04 埃克森美孚研究工程公司 Alumina forming bimetallic tube for refinery process furnaces and method of making and using
CN103354841B (en) * 2010-11-24 2015-09-09 西门子公司 There are the metallic bond coat of high γ/γ ' transition temperature or alloy and parts
CN103354841A (en) * 2010-11-24 2013-10-16 西门子公司 Metallic bondcoat or alloy with a high [gamma]/[gamma]' transition temperature and a component
CN102352142B (en) * 2011-04-07 2014-04-16 世林（漯河）冶金设备有限公司 High-temperature nano-grade anti-carburizing material and coating, and application thereof
CN102352142A (en) * 2011-04-07 2012-02-15 世林（漯河）冶金设备有限公司 High-temperature nano-grade anti-carburizing material and coating, and application thereof
CN104889597A (en) * 2015-05-09 2015-09-09 芜湖鼎瀚再制造技术有限公司 Co-Mn-Si-Fe nanometer welding layer for welding and preparation method
CN104946953A (en) * 2015-06-24 2015-09-30 安徽再制造工程设计中心有限公司 Co-Mn-Cr2O3-Ti coating material and preparation method
CN115427603A (en) * 2020-04-24 2022-12-02 诺维尔里斯公司 Thermally modified oxide-based pretreatment for metals and method for producing said metals
CN111362673A (en) * 2020-04-28 2020-07-03 新化县众一陶瓷有限公司 Preparation method of iron gray aluminum oxide wear-resistant ceramic
CN111362673B (en) * 2020-04-28 2023-10-10 新化县众一陶瓷有限公司 Preparation method of iron gray alumina wear-resistant ceramic
CN114147169A (en) * 2020-09-08 2022-03-08 中国科学院金属研究所 Method for improving interface stability of metal core coating
CN114147169B (en) * 2020-09-08 2022-12-20 中国科学院金属研究所 Method for improving interface stability of metal core coating

Also Published As

Publication number Publication date
CA2657782A1 (en) 2008-01-24
AR062083A1 (en) 2008-10-15
WO2008010965A1 (en) 2008-01-24
TW200827483A (en) 2008-07-01
WO2008010965A8 (en) 2008-09-12

Similar Documents

Publication Publication Date Title
CN101512674A (en) High pergormance coated material with improved metal dusting corrosion resistance
US20080020216A1 (en) High performance coated material with improved metal dusting corrosion resistance
Sidhu et al. Studies on the properties of high-velocity oxy-fuel thermal spray coatings for higher temperature applications
Di Ferdinando et al. Isothermal oxidation resistance comparison between air plasma sprayed, vacuum plasma sprayed and high velocity oxygen fuel sprayed CoNiCrAlY bond coats
Kuroda et al. Current status and future prospects of warm spray technology
Milanti et al. Effect of spraying parameters on the microstructural and corrosion properties of HVAF-sprayed Fe–Cr–Ni–B–C coatings
CN1068387C (en) A process for producing an oxide dispersed mcraly-based coating
Sadeghi et al. Chlorine-induced high-temperature corrosion and erosion-corrosion of HVAF and HVOF-sprayed amorphous Fe-based coatings
Wang et al. Microstructures, properties and high-temperature carburization resistances of HVOF thermal sprayed NiAl intermetallic-based alloy coatings
CN1122377A (en) A process for producing carbide particles dispersed in a mcraly-based coating
AU2006244298A1 (en) High performance alloys with improved metal dusting corrosion resistance
Sadeghimeresht et al. Oxidation behavior of HVAF-sprayed NiCoCrAlY coating in H 2–H 2 O environment
Sadeghimeresht et al. Isothermal oxidation behavior of HVAF-sprayed Ni and NiCr coatings in H2-H2O environment
Sun et al. Anti-coking performance of Cr/CeO2 coating prepared by high velocity oxygen fuel spraying
CA2452097C (en) Metal dusting resistant copper based alloy surfaces
US6692838B2 (en) Metal dusting resistant alloys
Sidhu et al. Comparative characteristic and erosion behavior of NiCr coatings deposited by various high-velocity oxyfuel spray processes
Jegadeeswaran et al. Oxidation studies on as-received and HVOF sprayed Stellite-6 coating on turbine alloys at 800 C
Pérez et al. Adhesion properties of aluminide coatings deposited via CVD in fluidised bed reactors (CVD-FBR) on AISI 304 stainless steel
Singh et al. Cyclic oxidation behavior of some plasma-sprayed coatings in Na2SO4-60% V2O5 environment
CA2444707A1 (en) Ductile nial intermetallic compositions
Verma et al. Cyclic oxidation behaviour and characterization of HVOF deposited inconel 718 coatings at 700° C
XIANG et al. Oxidation behavior of Fe40Al-xWC composite coatings obtained by high-velocity oxygen fuel thermal spray
JP2007146268A (en) Corrosion protection-coated steel material and its production method
Setare et al. Effect of NiAl-(Cr2O3, TiO2) composite coating on oxidation resistance of HH heat resistant steel

Legal Events

Date Code Title Description
C06 Publication
PB01 Publication
C10 Entry into substantive examination
SE01 Entry into force of request for substantive examination
C12 Rejection of a patent application after its publication
RJ01 Rejection of invention patent application after publication

Application publication date: 20090819