TW200827483A - High performance coated material with improved metal dusting corrosion resistance - Google Patents

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, and at least one element selected from the group consisting of 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 mixtures thereof. 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

200827483 IX. INSTRUCTIONS OF THE INVENTION [Technical Field to Be Invented] The present invention relates to the field of process materials for syngas generation. μ # is a material that is exposed to corrosive reactants and carbon supersaturated environments. More particularly, the present invention relates to coating materials for controlling reactor systems, gas heat exchanger systems, and metal dust corrosion in synthetic m process pipes and piping devices exposed to high carbon activity and lower oxygen activity. , composition and method. [Prior Art] One of the most abundant fossil fuels is natural gas, which is mainly a hospital. In high temperature processes involving the conversion of methane to high-priced hydrazine products such as liquid hydrocarbons, chemicals such as ethylene, or electricity, environmental conditions involving very high carbon activity and lower oxygen activity are often encountered. A similar environment is encountered in many other syngas generation processes. In many syngas generation processes, such as conversion of syngas, coke to syngas, coal to syngas, heavy oil, and bitumen to syngas, an environment with high carbon activity and low oxygen activity will be encountered. The high temperature reactor materials, heat exchanger materials, and synthetic gas tubing and piping materials used in this process will be damaged by the corrosion of metal dust in the form of intrusive uranium. Metal dust is Fe, Ni and Co-based alloys in a carbon supersaturated (carbon active > 1 ) environment having a low (about 1 〇 1 () to about 1 〇 2 () atmosphere) oxygen partial pressure. An unfavorable form of high temperature uranium that is experienced at temperatures ranging from 50 to 1 0 5 . This form of corrosion is characterized by the collapse of the entire piece of metal into powder or dust. Most of the alloys available on the market today -5-200827483 will be ablated by this corrosion process. Although many superalloys are designed in the form of an in-situ surface film of chromium oxide (Cr203) in a low oxygen partial pressure environment, chromium oxide reacts at high temperatures (i.e., > 1 000 ° C) in the presence of oxygen. Cr〇3 is formed which is vapor and will evaporate resulting in a chromium-poor alloy. The chromium-poor alloy does not form a protective chromium oxide film, so the carbon will enter the alloy from a highly reductive carbon-rich environment with a carbon activity of more than one. This will cause corrosion of the metal dust. Aluminum and niobium are strong oxide formers and can be added to the superalloy to improve corrosion resistance via the in-situ surface film forming alumina and yttria. However, excessive addition of these elements is expected to have excellent corrosion resistance, and generally causes poor mechanical strength at high temperatures using the alloy. Thus, alloys containing excess aluminum and bismuth cannot be used in the composition of the synthesis gas generation process. 方法 The methods disclosed in the literature for controlling metal dust corrosion involve the use of gaseous inhibitors, such as H2s. Suppression via H2S has two drawbacks. One is the most catalytic agent for H2s to poison the hydrocarbon conversion process. Second, H2S must be removed from the effluent stream, which can substantially increase process costs. U.S. Patent No. 6,692,838 to Ramanarayanan et al. discloses a metal dust resistant composition and a method for preventing metal dust from being exposed to a metal surface of a carbon supersaturated environment. The composition comprises (a) a gold alloy, and (b) a protective oxide coating on the alloy. The alloy includes an alloyed metal and a base metal, wherein the alloyed metal comprises a mixture of chromium and manganese, and the base metal comprises iron, nickel, and cobalt. The entire disclosure of U.S. Patent No. 6,6,92,83, hereby incorporated herein by reference. U.S. Patent No. 6,737,175 to Ramanarayanan et al. The method comprises forming a surface or a coated surface with a copper-based alloy. The entire disclosure of U.S. Patent No. 6,737,175 is incorporated herein by reference. U.S. Patent Application Serial No. 1 1 / 1 2 6 5 G07, filed on May 10, the entire disclosure of which is incorporated herein by reference in its entirety, the disclosure of the entire disclosure of the disclosure of the disclosure of the disclosure of the disclosure of the disclosure of the disclosure of . The alloy includes an alloy (PQR) and a multilayer (at least three layers) oxide film on the surface of the alloy (PQR), wherein the alloy (PQR) comprises a metal (P) selected from the group consisting of Fe, Ni, Co, and mixtures thereof, including Cr, Μη and any Al, Si or Al/Si alloying metal (Q) and alloying element (R). The multilayer oxide film is formed in situ when the alloy composition is used in a carbon supersaturated environment. The entire disclosure of U.S. Patent Application Serial No. 1 1/1,26, 007 is incorporated herein by reference. New alloys and coating materials that are resistant to metal dust corrosion are required. More particularly, there is a need for advanced coating material compositions in which the coated metal is at a low (about 1 (Γ1() to about 1 (Γ2() atmosphere) oxygen partial pressure carbon supersaturation (carbon activity > 1) Metallic dust corrosion in the environment and includes the base metal of the coating material providing the required high temperature strength and other properties such as creep strength and toughness. This advanced coating material composition should form an external protective oxide. The layer prevents carbon transfer by acting as a diffusion barrier layer that carbon enters. [Abstract] According to this disclosure, an advantageous metal-resistant coating material composition comprises: (PQR), wherein the oxide layer on the surface , Q is a base metal between P and R, wherein P comprises alumina, mullite, or a mixture thereof, and Q comprises one less selected from the group consisting of Cr, Si, Mn, Fe, Co, B, C, As, In, Sn, Sb, Pb, Sc, La, Y, C e V, Nb, Ta, Mo, W, Ru, Rh, Ir, Pd, Au elements or mixtures thereof, and R series Selected from carbon steel body stainless steel, Worthite iron stainless steel, duplex non-inconel alloy, Incoloy Incoloy alloy, Ni-based alloy or Co-based alloy. Another aspect of this disclosure is an advantageous method for preventing corrosion of metal dust exposed to a carbon supersaturated ring by a genus composition (PQR), wherein P is (oxide layer, Q is a gold-coated metal between P and R, wherein P comprises alumina, chromium oxide, di, or a mixture thereof, Q includes Ni and A1, and at least, Mn, Fe , Co, B, C, N, P, Ga, Ge, Pb, Sc, La, Y, Ce, Ti, Zr, Hf, V, W, Ru, Rh, Ir, Pd, Pt, Cu, Ag or Au and R are selected from carbon steel, low chromium steel, ferritic stainless steel, duplex stainless steel, Inco high nickel alloy, Ni-based alloy, Ni-based alloy or Co-corrosion High P is a (PQR) coated metal layer, and chromium, cerium oxide, Ni and A1, and to, N, P, Ga, Ge, Ti, Zr, Hf, Pt, Cu, Ag or, low chromium a genus layer on the surface of steel, ferritic I steel, and high-nickel nickel (Fe-Ni as the base of the metal surface PQR under high-efficiency coating), and R is a ruthenium oxide or a mullite selected from the group consisting of Cr, S i As, In, Sn, Sb 'Nb, Ta, Mo, an element thereof or a mixed rust steel thereof, a Worthite iron alloy, an alloy of F e · bottom; wherein -8 - 200827483 the method includes providing (PQR) Steps of the metal surface. Many advantages stem from the advantageous high-efficiency coating material composition comprising (PQR), where p is the oxide layer on the (PqR) surface and Q is the coating metal between P and R Layer, and R is the base metal layer disclosed herein and its use/application. For example, in an illustrative embodiment of this disclosure, a high efficiency coating material composition comprising (PQR) exhibits improved resistance to metal dust uranium at elevated temperatures in a carbon supersaturated environment containing a relatively low oxygen partial pressure. In another illustrative embodiment of this disclosure, a highly effective coating material composition comprising (PQR) exhibits the ability to form a thermodynamically stable, slowly growing, adherent, passive oxide film capable of acting as a diffusion barrier for carbon entry. . In another illustrative embodiment of this disclosure, a high efficiency coating material composition comprising (PQR) does not poison most of the catalyst used in the hydrocarbon conversion process. In another exemplary embodiment of this disclosure, a high efficiency coating material composition comprising (PQR) will result in improved adhesion of the surface oxide or layer which will enhance chip resistance. In another illustrative embodiment of this disclosure, a high efficiency coating material composition comprising (PQR) will result in reduced carbon deposition in a carbon supersaturated environment. In another exemplary embodiment of this disclosure, the oxide layer (P) on the surface thereof will be formed when the high-efficiency coating material composition containing (PQR) is exposed to a metal dust environment having a low oxygen partial pressure.

In another illustrative embodiment of this disclosure, the oxide layer (p) on the surface of the high efficiency coating material composition comprising (PQR 200827483) will be formed in situ when the alloy is used in a carbon supersaturated environment. In another illustrative embodiment of this disclosure, the oxide layer (P) on the surface of the high efficiency coating material composition comprising (PQR) will be exposed to carbon supersaturation and a low oxygen partial pressure environment. Or formed under controlled low oxygen partial pressure environment before use. In another illustrative embodiment of this disclosure, the coated metal layer (Q) on the surface of the high-efficiency coating material composition comprising (PQR) has low porosity. Another advantage of a highly effective coating material composition comprising (PQR) is that if the protective surface oxide layer (P) is cleaved when the composition is used in a carbon supersaturated environment, the protective surface oxide layer (P) The oxide layer will be reconstituted upon cleavage to protect the alloy from metal dust during use. The disclosed high-efficiency coating material composition comprising (PQR) can be applied to a syngas processing apparatus that is in contact with a carbon supersaturated environment at any time during use. The apparatus includes a reactor, a gas/gas heat exchanger, and a syngas generation process. Pipe and piping. The disclosed high efficiency coating material composition comprising (PQR) can be provided to the surface via: 1) consisting of (PQR) to form the device, 2) coextruding Q and R to form the surface of the device 'or 3) The Q is coated on the R to form a surface of the device exposed to the metal dust environment for protection. The disclosure and the various advantages, features and attributes of the highly effective coating material composition comprising (PQR) and its advantageous applications and/or uses will be apparent from the detailed description of the column 10-200827483, in particular in conjunction with the accompanying graphics. Come to read. [Embodiment] The present invention relates to a highly efficient coating material capable of forming a surface film of a stable alumina. The high-efficiency coating material composition resistant to metal dust corrosion of the present invention differs from the prior art in that it comprises a surface oxide layer, a coating metal on one side of the surface oxide layer, and a coating relative to the oxide layer. Base metal on the metal side. More particularly, the coated metal of the present invention differs from prior art in that it produces an adhesion of the surface oxide film or layer which will enhance chipping resistance. The coated metal of the present invention is also different from the prior art in that it produces an improved adhesion of the base metal which will improve coating integrity. Moreover, the coated metal of the present invention will produce reduced carbon deposition in a carbon supersaturated environment relative to the prior art. The highly efficient coating of the metal composition of the present invention provides significant advantages over prior art alloy compositions as a protective coating for metal dust exposed to metal surfaces in a carbon supersaturated environment. The advantageous properties and/or characteristics of the disclosed high-efficiency coated metal composition are, at least in part, based on the structure of the aluminum oxide film formed on the surface of the coated metal, the aluminum oxide film including, in particular, improved resistance Metal dust uranium, reduced carbon deposition, reduced tendency to poison catalysts used in hydrocarbon conversion processes, improved in situ formed surface oxide film adhesion, improved chip resistance, exposure to carbon supersaturated environments, and The improvement is easy to form. The highly effective coating metal composition of the metal powder resistant ruthenium of the present invention is represented by the formula (PQR) by 200827483. p is an oxide layer comprising aluminum oxide, chromium oxide, cerium oxide, mullite, or a mixture thereof. P forms the outer surface layer ' of the high efficiency coating material composition' and thus the layer is in direct contact with the carbon supersaturation and low oxygen partial pressure environment. Adjacent to the oxide layer p is a coating metal, Q comprises Ni and A1, and at least one species selected from the group consisting of Cr, Si, Mn, Fe, Co, B, C, N, P, Ga, Ge, As, In Or an element of Sn, Sb, Pb, Sc, La, Y, Ce, Ti, Zr, Hf, V, Nb, Ta, Mo, W, Ru, Rh, Ir, Pd, Pt, Cu, Ag or Au or mixture. Located on the opposite side of the coated metal layer Q is selected from the group consisting of carbon steel, low chromium steel, ferritic stainless steel, Worthite iron stainless steel, duplex stainless steel, Inco high nickel alloy, Incoloy, Fe-Ni Base metal R of the underlying alloy, Ni-based alloy or Co-based alloy.

External Oxide Layer P The oxide layer P is formed on the coated metal Q in situ when the coating material is used in a carbon supersaturated environment. Alternatively, the oxide layer P is formed on the coating metal Q prior to use by exposing the coating material to carbon supersaturation and low oxygen partial pressure. Alternatively, an oxide layer p, formed on the coated metal Q, prior to use, by exposure of the coating material to a controlled low oxygen partial pressure. The oxide layer P is an oxide layer containing aluminum oxide, chromium oxide, oxidized chopped mullite, mullite, or a mixture thereof and may contain some impurity oxides formed of elements constituting the coating metal Q and the base metal R . The preferred oxide layer P is ruthenium oxide. The oxide layer P has a thickness of at least about 1 nm -12 - 200827483 to about 100 μπι, preferably at least about 1 〇 nm to about 50 μηι, more preferably at least about 100 nm to about ΙΟμηι. The oxide layer ρ described herein is formed on the coated metal surface by exposing the coating material to a metal dust environment. A non-limiting example of a metal dust environment is a gaseous 50CO: 50Η2 mixture. The metal dust may further contain other gases such as CH4, ΝΗ3, Ν2, 02, He, Ar or hydrocarbons and form a stable oxide layer P on the coating metal Q, the oxide layer P comprising alumina, oxidized Chromium, cerium oxide, mullite, or a mixture thereof. Thus, the protective oxide layer can be formed at or before the use of the alloy under reaction conditions similar to exposure to a metal dust environment. The metal dust environment preferably has a temperature in the range of from about 305 ° C to about 1200 ° C, preferably from about 550 ° C to about 1 200 ° C. Typical exposure times range from about 1 hour to about 500 hours, preferably from about 1 hour to about 300 hours, and more preferably from about 1 hour to about 100 hours. The oxide layer P described herein, on the coated metal Q, may also be formed on the coated metal surface by exposing the coating material to a controlled low oxygen partial pressure. A non-limiting example of a controlled low oxygen partial pressure environment is a gaseous H20:H2 mixture and a gaseous CO2:CO mixture. The controlled low oxygen partial pressure environment may further contain other gases such as CH4, NH3, N2, 02, He, Ar or hydrocarbons and form a stable oxide layer P on the coating metal Q, the oxide layer P comprises aluminum oxide, chromium oxide, cerium oxide, mullite, or a mixture thereof. Therefore, the protective oxide layer is formed before the alloy is used in a metal dust environment. Preferably, the controlled low oxygen partial pressure environment has a temperature in the range of from about 350 ° C to about 1 20 ° C, and -13 - 200827483 is preferably from about 5 50 ° C to about 1 2 0 0 °. C. Typical exposure times range from about 1 hour to about 50,000 hours, preferably from about 1 hour to about 30,000 hours, and more preferably from about 1 hour to about 1000 hours.

Coating metal layer Q The coating metal Q comprises a mixture of Ni and A1, and at least one selected from the group consisting of Cr, Si, Mn, Fe, C ο, B, C, N, P, Ga, Ge, As, In, Sn An element of Sb, Pb, Sc, La, Y, Ce, Ti, Zr, Hf, V, Nb, Ta, Mo, W, Ru, Rh, Ir, Pd, Pt, Cu, Ag or Au or a mixture thereof. The coated metal composition of the present invention provides significant advantages over prior art alloy compositions as a protective coating for metal dust exposed to metal surfaces in a carbon supersaturated environment. For non-limiting examples, alloying elements such as Sc, La, Y or Ce will provide improved adhesion of the surface oxide film formed in situ, which will enhance chipping resistance. Alloying elements such as Ga, Ge, As, In, Sn, Sb, Pb, Pd, Pt, Cu, Ag or Au will provide reduced carbon deposition because these elements are not catalytic for surface carbon transfer reactions. The coating metal Q comprises from about 4% by weight to about 70% by weight aluminum, more preferably from about 4% by weight to about 50% by weight aluminum, and more preferably from about 4% by weight to about 30% by weight aluminum. In a preferred embodiment, the coating metal Q comprises a small amount of Fe in the coating metal Q than in the base metal R. The coated metal layer Q comprises less than about 12% by weight Fe, preferably about 10% by weight Fe, and more preferably about 8% by weight Fe. A coating metal layer Q containing much more than 12% by weight of Fe will cause undesirable metal dust corrosion resistance in the case of carbon supersaturation and low oxygen partial pressure ring 14-200827483. Ni, which acts as a component of the coated metal layer, also reduces the rate of dust corrosion, which is about one grade lower than the rate of dust corrosion in pure Fe. The coated metal of the present invention has low porosity which contributes to improved carbon deposition resistance in a carbon-saturated environment. The coating metal layer Q contains less than about 8% by volume of porosity, preferably about 3% by volume of porosity, more preferably about 2% by volume of porosity, and still more preferably about 1% by volume of porosity. . Excess porosity in the coated metal layer will act as a means of transferring corrosive gases in the metal dust environment to the coated metal and base metal surfaces. This carbon transfer will initiate the carbon precipitation in the coated metal layer and the delamination of the coating metal at the coating/base metal interface. It is therefore advantageous to achieve a coated metal layer that contains a minimum amount of porosity. The low porosity coating metal layer can be established by a coating method such as CVD, MOCVD, PVD, slurry coating, pack cementation, over-welding, and powder plasma welding. The coated metal layer can be post-fired or laser melted to achieve higher density coating. In contrast, conventional thermal spray methods such as plasma, HVOF, and explosive spray guns produce a coated metal layer with higher porosity. The conventional thermal spray method is a method of applying molten or softened particles to a substrate via impact. The coating often contains a rapidly solidified relief or sheet-like grain structure resulting from droplets that flatten at a high velocity impact on the cooling surface. It is almost impossible to determine that all particles are exactly the same size and reach the same temperature and speed. Thus, changes in the individual particle wash conditions during the thermal spray process will result in a heterogeneous structure of the cermet layer that includes excess porosity. -15- 200827483

Preferred specific examples of the high-efficiency coating material composition of the present invention include coated metal Q comprising: (1) Ni and A1, or (2) Ni, AlS: Cr. The coating metal composition NiAl is an intermediate metal phase which is said to be a β phase. The NiAl coating can be applied to the base metal R via a method such as CVD, MOCVD, PVD, slurry coating or embedding. The β-NiAl has a thickness of from about 1 μηι to about 300 μηη, preferably from about 1 μηι to about 20 0 μχη, and more preferably from about 1 μπι to about 1 μ μπι. The coating metal composition NiAl comprises from about 17% by weight to about 39% by weight of A1, and from about 61% by weight to about 83% by weight of Ni. Preferably, the coating metal composition NiAl comprises about 18% by weight of A1, and about 82% by weight of Ni. The coating metal composition NiCrAl can be applied to the base metal R by a welding method such as powder plasma welding. The NiCrAl has a thickness of from about 100 μηι to about 5 mm, preferably from about 100 μηι to about 4 mm, and more preferably from about 100 μηη to about 3 mm. The coating metal composition NiCrAl comprises from about 4% by weight to about 1% by weight. A1 of 〇, about 15% by weight to about 30% by weight of Cr, and about 60% by weight to about 81% by weight of Ni. Preferably, the coating metal Q comprises about 6% by weight of A1, about 25% by weight of Cr, and about 69% by weight of Ni.

Base metal R The base metal R is selected from the group consisting of carbon steel, low chromium steel, ferritic stainless steel, Worthite iron stainless steel, duplex stainless steel, Inco high nickel alloy, Incomoloy, Fe_Ni based alloy, Ni - a base alloy or a Co-based alloy. The base metal R can also be any commercially available alloy that is intended to be used in the synthesis gas generation process equipment. Non-16-200827483 exemplified examples of the base metal R used in the present invention are shown in Table 1. These base metals are suitable for the manufacture of a highly efficient coating material (PQR) resistant to metal dust rot.

-17- 200827483 Table 1

Base metal alloy UNS No. Alloy composition ί% by weight Carbon steel 1018 G10180 Bal.Fe,0·6·0.9Μη, 0.14-0.20C 4130 G41300 Bal.Fe, 0.35-0.60Mn, 0.80-1.15Cr, 0.27- 0.34C low-volume steel T11 K11562 Bal.Fe: 1.25Cr: 0.5Mo, 0.5Si, 0.3Mn, 0.15C, 0.045P, 0.045S Γ22 K21590 Bal.Fe: 2.25Cr: 1,0Mo, 0.5Si, 0.3Mn, 0.15C, 0.035P, 0.035S T5 S50100 Bal.Fe: 5Cr: 0.5Mo, 0.5Si, 0.3Mn, 0.15C, 0.04P, 0.03S T9 J82090 BaLFe: 9Cr: 1.0Si, 0.35Mn5 0.02C, 0.04P, 0.045S ferritic stainless steel 409 S40900 Bal.Fe: 10.5Cr: 1.0Si, l.OMn, 0.5Ni, 0.5Ti, 0.08C, 0.045P, 0.045S 410 S41000 Bai.Fe:l 1.5Cr:0.15C, 0.045 P, 0.03S 430 S43000 Bal.Fe: 16.0Cr: 1.0Si, l.OMn, 0.12C, 0.045P, 0.03S Vostian Iron Stainless Steel [304 S30400 BaLFe: 8Ni: 18Cr: 2.0Mn, 0.75Si, 0.08C , 0.04P, 0.03S 310 -------- S31000 BaI.Fe:19Ni:24Cr:2.0Mn, 1.5Si, 0.75M〇, 0.25C, 0.045P, 0.03S l2S3MA S30815 Bal.Fe:! lNi :21Cr:1.7Si, 0.04Ce, 0.17N, 0.08C RA85H S30615 Bal.Fe: 14.5Ni: 18.5Cr: 3.5Si: 1.0A1, 0.2C duplex stainless steel 2205 --- S32205 Bal.Fe:4.5Ni:22Cr :2.0Mn, l.OSi, 3.0M〇, 0.03C, 0.14N, 0.03P, 0.02S 2507 S32507 Bal.Fe:6Ni:24Cr:1.2Mn, 0.8Si, 3.0M〇, 0.5Cu, 0.03C, 0.2N, 0.035P, 0.02S English Barium alloy nickel 600 N06600 Bal.Ni: 8.0Fe: 25.5Cr, 0.08 Yanggao 601 N06601 Bal.Ni: 14.4Fe: 23.0Cr: 0.3Mn: 1.4Als 0.5Si, 0.1C -3⁄4 咼 Nickel 602CA N/A Bal.Ni: 9.5Fe: 25.0Cr: 2.2Al, 0.18C One inch high nickel 690 N06690 Bal. Ni: 9.0Fe: 29.0Cr: 0.3Mn: 1.4AI, 0.5Si, 0.1C Inco high nickel 693 N06693 Bal.Ni : 4.0Fe: 29.0Cr: 3.1Al Inch high nickel MA754 N/A BaLNi: 9.0Fe: 29.0Cr: 0.3Mn: L4Al, 0.5Si, 0.1C Incoloy alloy Incory 800H N08810 Bal.Fe: 33.0 Ni: 21.0Cr: 0.8Mn: 0.5Al: 0.4Si: 0.5Ti: 0.07C Incoloy 825 N08825 Bal. Ni: 30.0Fe: 21.5Cr: 3.0Mo: 2.2Cu: 0.03C Fe-Ni base alloy KHR-45A (35/45 Alloy) N/A Bal.Fe: 43.6Ni: 32.1Cr: 1.0Mn: L7Si: 0.9Nb: 0.1Ti: 0.4C Ni-based alloy Haines 214 N07214 Bal.Ni: 3.0Fe: 2.0Co: 16, 0Cr: 0, 5Mn: 4.5Al: 0.2Si: 0, 5Mo: 0.5Ti: 0.05C Co» as the base alloy Haines 188 R30188 Bal. Co: 22.0Ni: 22.0Cr: 3.0Fe: 14.0W: 0.04La: 0.1C MP35N R30035 Bal.Co: 35.0Ni: 20.0Cr: 10.0Mo -18- 200827483 High-efficiency coating Was formed and applied to a method of the present invention also discloses a method exposed to metal dusting of metal over the surface of the carbon saturation of the environment prevents corrosion of uranium. The method is necessarily accompanied by providing a metal surface having a highly efficient coating of a metal composition, wherein the material composition comprises: (PQR), wherein P is an oxide layer on the (PQR) surface and Q is between P and R a metal coating layer, and R is a base metal, wherein P comprises alumina, chromium oxide, ceria, mullite, or a mixture thereof, Q comprises Ni and A1, and at least one is selected from the group consisting of 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 or Au elements or mixtures thereof, and R series selected from carbon steel, low chromium steel, ferritic stainless steel, Worthite iron stainless steel, duplex stainless steel, Inco Nickel alloy, Incomoloy, Fe-Ni based alloy, Ni-based alloy or Co-based alloy. The metal surface to be protected at a temperature in the range of 350 to 1050 ° C in a carbon supersaturated (carbon active > 1) environment having a low oxygen partial pressure of about 1 〇 1 α to 1 (Γ 2 〇 atmospheric pressure) can be efficiently used. a coating material composition, coextruded with the coating material, coated with the coating material, or a combination of the three. In the high-efficiency coating material composition (PQR) for providing the present invention - a specific example The composition may be formed by constructing the process equipment by coating the metal Q and the base metal R. In another specific example for providing the high-efficiency coating material composition (PQR) of the present invention, the composition may be used in The steel coextrusion technique known in the art is formed by co-extruding a coating metal Q and a base metal R. The high-efficiency coating material composition (PQR) for providing the present invention is another -19-200827483 In one embodiment, the composition may be formed from the surface of an existing surface processing apparatus susceptible to metal dust, the surface being coated with the coated metal Q of the present invention using coating techniques well known to those skilled in the art. The surface is made of base metal R. Suitable for use here. Exemplary coating techniques for coating the base metal R with a coated metal composition include, but are not limited to, CVD, MOCVD, PVD, slurry coating, embedding, powder plasma welding, thermal spraying, and sputtering. Thus, the high performance coating material composition (PQR) of the present invention can be optionally coextruded or coated with the high efficiency coating material composition described herein. The above protective surface oxide layer P can be in a carbon supersaturated environment. The unit is formed in situ when operating the unit. More specifically, the protective surface oxide layer P can be exposed to metal dust for each of the three methods used to form the coated metal and base metal combination (QR). The environment is formed during the use of the device (formed in situ). Alternatively, the protective surface oxide layer P described above may be formed prior to exposure of the coated metal and base metal combination (QR) to the carbon supersaturated environment prior to use of the device. An exemplary but non-limiting metal dust environment is to expose the high efficiency coating material of the present invention to a metal dust environment, such as a 50CO-50H2 mixture. Alternatively, the protective surface oxide described above Layer P may be formed prior to use of the apparatus by exposing the coated metal and base metal combination (QR) to a controlled low oxygen partial pressure. A non-limiting example of a controlled low oxygen partial pressure environment is to make the invention The high efficiency coating material is exposed to a gaseous H20:H2 mixture and a gaseous CO2:CO mixture. Preferably, the temperature range is from about 305 ° C to about 120 (TC, preferably from about 5 50 ° C to about 1 200 ° C. A typical exposure time is from about 1 hour to about 300 hours -20 to 200827483, preferably from about 1 hour to about 1000 hours. Thus, the protective oxide layer P can be used at or before the alloy is used. They are formed under exposure to conditions in a metal meal environment. The high performance coating material composition (pQR) of the present invention as described herein can be used to construct equipment surfaces that are exposed to a carbon metal dust environment. The figure 槪 schematically illustrates the use of a coating material (PQR) for protecting a syngas generating apparatus. For non-limiting examples, syngas process tubing or tubing can be applied to the inner, outer or inner and outer diameters, depending on the resistance to metal dust corrosion. The surface of the syngas process equipment that can benefit from the highly efficient coating materials of the present invention includes equipment and reactors that are in contact with the carbon supersaturated environment at any time during use. These equipment and reactor systems include, but are not limited to, reactors, gas/gas heat exchangers or syngas to produce process tubing and piping. Applicants attempt to disclose specific examples and applications of all disclosed subject matter that are reasonably foreseeable. However, it may not be possible to foresee an insubstantial modification that is still considered an equivalent. Although the present invention has been described in connection with the specific embodiments of the present invention, it is apparent that many changes, modifications and variations may be made without departing from the spirit and scope of the disclosure. Therefore, the disclosure is intended to cover all alternatives, modifications, and variations of the above detailed description. The following examples illustrate the invention and its advantages without limiting the scope of the method for determining the weight percent of elements in the coating material (PQR). It is determined by the standard energy dispersive X-ray spectrometer (EDXS) by 200827483. / For the commercially available alloys (Inco High Nickel 601 and Inco High Nickel 693), rectangular samples of 〇 5 吋χ 0·25 吋χ 0·06 系 are prepared from alloy flakes. The β-NiAl coated Inco nickel 601 sample was prepared by an embedding method. The base metal, Inco nickel 6〇1', was chromed prior to the aluminizing embedding process. The diffusion reaction was carried out at 800 ° C to form a δ-Ν^ΑΙ3 phase on the surface of the base metal, Inco-Chen 601. Subsequent heat treatment is carried out at 100 ° C to convert the low melting δ phase into a β-NiAl phase, wherein the A1 content is from about 17 to about 39% by weight. The NiCrAl-coated Inco nickel 601 and NiCrAl-coated alloy 3 5/45 samples were prepared by powder plasma welding. For the comparative example, the NiCrAl-coated Inco nickel 601 sample was prepared by air plasma spraying, conventional thermal spraying. A rectangular sample of 0·5 吋χ θ.25 切 was cut out from the sample. The test piece was polished to a 6-inch grain finish or Linde B (0.05 micron alumina powder) and cleaned in acetone. The corrosion kinetics of the different alloy test pieces were investigated by exposing the test piece to a 50 CO-50 H2 (% by volume) environment at a test temperature of 550 ° C to about 10,000 ° C for up to 300 hours. The carbonization of the test piece was measured using a cahn 1 000 electronic balance. Carbon addition is an indicator of corrosion of metal dust. The surface and cross section of the test piece were also examined using a scanning electron microscope (SEM). Example 1 Following the above test method, the following alloy samples were tested: Inco High Nickel 60 1 -22-200827483 (formerly known), Angkor Nickel 693 (previously crafted), beta-NiAl coated Inco nickel 601, NiCrAl-coated Inco nickel 601 and NiCrAl coated alloy 35/45 alloy. The weight measurement results are shown in Fig. 2. Figure 2 depicts the mass gain due to carbon deposition (metal dust rot) on the finished Linde B alloy after 60 hours of reaction at 65 °C in a 50CO-50H2 gas mixture. After metal dust exposure, the surface of the sample is covered with carbon, which is always accompanied by metal dust corrosion. Significant amounts of carbon deposition were detected on the surface of commercially available prior art alloys (Inco Crown 601 and Inco Nickel 693). In contrast, the coating material of the present invention (β_ΝίΑ1 coated Inco nickel 601, NiCrAl-coated Inco nickel 601, and NiCrAl-coated alloy 3 5/45 alloy) was found to be insignificant or small. Carbon deposition. Further, the susceptibility of the metal dust is examined through the cross-section S EM of the etched surface. The cross-sectional SEM image in Figure 3 reveals the characteristic cavity morphology of the prior art Inco high nickel 601 alloy after a 160 hour reaction at 60 °C in a 50CO-5〇H2 gas mixture. Metal dust in carbon deposits is seen in the cavity. The cavities have a diameter of about 120 microns and a depth of about 20 microns. The cross-sectional SEM image in Figure 4 reveals the characteristic cavity morphology of the prior art Inco high nickel 693 alloy after reacting at 65 (TC for 160 hours) in a 50 CO-50 H2 gas mixture. Metal dust. The diameter of the cavity is about 20 microns and the depth is about 8 microns. Example 2 The β-NiAl coated Inco high nickel 601 was tested at 50 ° C in a 50 CO-50 H 2 gas mixture following the above test method. After 300 hours. -23- 200827483

The thickness of the aluminum oxide layer is about 5, and the EDXS line data near the surface of the surface is plotted in terms of the concentration by weight. 釆5 is a graph depicting the high-efficiency coating of the present invention after 50 hours of mixing with 50CO-50H2 gas for 30,000 hours. The oxide layer P is composed of aluminum oxide. Ηηι. The coating metal Q is β-NiAl, wherein the cerium 1 content is about 18% by weight. The thickness of the p_NiA1 layer is about 55 φ μιη. The Fe content in the coating metal Q was about 9.8 wt%. A thick layer of cr having a thickness of about 6 μηι was also observed at the β-NiAl/Incoal Nickel 601 interface. The base metal R is Inco Crown 601. Figure 6 is a SEM image of the surface and cross-section of this sample (p_NiA1/Inco High Nickel 601) after 300 hours at 1 050 °C in a 50CO-50H2 gas mixture. Figure 6 illustrates an aluminum oxide layer, a coated metal (NiAl) layer, and a base metal (Inco Crown 601). φ Example 3 Following the above test method, NiCrAl-coated Inco High Nickel 601 was tested at 50 °C to 50 ° C for 3 00 hours at 1 050 °C. Figure 7 depicts the EDXS line data plot near the surface of the coating material prior to testing. The concentration of the different elements (Ni, Al, Cr, and Fe) in % by weight is plotted as a function of the distance from the coated surface. The coating metal Q is NiCrAl and comprises about 6% by weight of A1, about 24% by weight of Cr, about 68% by weight of Ni, and about 2% by weight of Fe. The coated metal NiCrAl has a thickness of about 2.1 mm. The base metal R is Inco Crown 601. Figure 8 is a SEM image of the surface and section of the sample after testing at 050 °C for 300 hours in a 50CO-50H2 -24-200827483 gas mixture. The oxide layer comprises an alumina layer of about 3 μη thick and other oxides comprising chromium oxide and aluminum oxide-chromium oxide. Example 4

The NiCrAl-coated 3 5/45 alloy was tested for 300 hours at 50 ° C in a 50 CO-50 H 2 gas mixture following the above test method. Figure 9 depicts the EDXS line data plot near the surface of the coating material prior to testing. The concentration of the different elements (Ni, A, Si, Cr, and Fe) in % by weight is plotted as a function of the distance from the coated surface. The coating metal Q is NiCrAl and contains about 5% by weight of A1, about 26 parts by weight. /. Cr, about 65 wt% Ni, about 1 wt% Si, and about 3% wt% Fe. The coated metal NiCrAl has a thickness of about 2·6 μm. The base metal R is a 35/45 alloy. Figure 10 is a SEM image of the surface and section of the sample after 300 hours of testing at 50 °C in a 50CO-50H2 gas mixture. The oxide layer comprises an alumina layer of about 4 μm thick. Example 5: Comparative Example of High Porosity Coating A NiCrAlY-coated Inco Nickel 601 sample was prepared by air jet spraying, conventional thermal spraying, following the above test method. The NiCrAlY powder used was Praxair NI-278. The coating metal comprises about 69.6% by weight of Ni, about 23.2% by weight of Cr, about 6.9 % by weight of A1, and about 0.7% by weight of Y. The coated metal NiCrAlY has a thickness of about 200 μm. The air plasma sprayed NiCrAlY coating contains a number of fine pores between the solidified droplets and a poor adhesion between the coated metal and the base alloy. NiCrAlY-coated Inco-Chen 601 was tested at 65 °C for 160 hours in a 50CO-50H2 gas mixture. Figure 11 is a SEM image of the surface and section of the sample after the test. Excess porosity in the coated metal layer acts as a means of transferring the hunger gas in the metal dust environment to the metal and substrate metal surfaces. This carbon transfer will result in internal carbon precipitation and bulging in the coated metal layer and delamination of the coating metal at the coating/substrate metal interface. Ni-rich particles were observed in the carbon deposits, which were characteristic of metal dust corrosion. [Simple description of the schema] In order to assist the general familiarity of the relevant craftsman to complete and use the theme of this, in accordance with the accompanying graphics, wherein: Figure 1 depicts the different positions of the pipe or piping used to protect the syngas generation process equipment. A schematic illustration of the invention of an efficient coating material. Figure 2 depicts a bar graph of mass gain due to carbon deposition (metal dust uranium metric) on the finished Linde B alloy after 160 hours of reaction at 65 °C in a 50 CO-50 H2 gas mixture. Figure 3 depicts a cross-sectional scanning electron microscopy (SEM) image of the etched surface of the Uncoated Nickel 601 alloy (previously crafted) after 160 hours of reaction at 650 ° C in a 50 CO-50 H 2 gas mixture. Figure 4 depicts a cross-sectional SEM image of the surface of the uranium uncoated with the Inco high nickel 693 alloy (previously crafted) after a 160 hour reaction at 65 °C in a 50CO-50H2 gas mixture. -26- 200827483 Figure 5 depicts the EDXS line data plot of the high efficiency NiAl-coated Ingone nickel 6〇1 material of the present invention after 300 hours of testing at 50 °C to 0 °C in a 50 CO-50 H2 gas mixture. Figure 6 depicts the surface and cross-sectional SEM images of the high efficiency NiAl-coated Ingone nickel 6〇1 material of the present invention after 300 hours of testing at 50 °C in a 50CO-50H2 gas mixture. Figure 7 depicts an EDXS line data plot of the high efficiency NiCrAl-coated Inco high nickel 601 material of the present invention at 50 (3 〇-5 (^2 gas mixture) at 100 ° C for 30 hours. The figure depicts the surface and cross-sectional image of the high-efficiency NiCrAl-coated Inco high-nickel 601 material of the present invention approaching the coated surface after 300 hours of testing in a 50CO-50H2 gas mixture at 30,000 hours. Figure 9 depicts The EDXS line data of the high-efficiency NiCrAl-coated 3 5/45 alloy of the present invention approaching the coated surface before testing at 100 ° C for 30 hours in a 0 CO-50 H 2 gas mixture. Figure 10 depicts the 50 CO- The high-efficiency NiCrAl-coated 3 5/45 alloy of the present invention is close to the surface and cross-sectional image of the coated surface after testing in a 50H 2 gas mixture at 100 ° C for 300 hours. Figure 11 depicts the gas at 50CO-50H2 The high-efficiency NiCrAl-coated Inco High Nickel 601 material of the present invention (previously crafted) in the mixture after testing at 605 ° C for 160 hours is close to the surface and cross-sectional image of the coated surface.

Claims (1)

200827483 X. Patent application scope 1. A high-efficiency coating metal composition resistant to metal powder ruthenium uranium, which comprises (PQR), wherein P is an oxide layer on the surface of (PQR), Q is between P and R Between the coated metal layers, and R is a base metal, wherein P comprises aluminum oxide, chromium oxide, ceria, mullite, or a mixture thereof, Q comprises Ni and A1, and at least one is selected from Cr , Si, Mn, Fe, Cο, 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 or Au elements or mixtures thereof, and R series selected from carbon steel, low chromium steel, ferritic stainless steel, Worth iron stainless steel, double Phase stainless steel, Inconel alloy, Incoloy alloy, Fe-Ni based alloy, Ni-based alloy or Co-based alloy. 2. The coated metal composition of claim 1, wherein the oxide layer P is alumina. 3. The coated metal composition of claim 1, wherein the thickness of the layer C is from about 1 nm to about 100 μm. 4. The coated metal composition of claim 1 wherein the coated metal layer q comprises less than about 12% by weight Fe. 5. The coated metal composition of claim 1, wherein the coated metal layer Q comprises less than about 3% by volume of porosity. The coated metal composition of claim 5, wherein the coated metal layer Q comprises less than about 1% by volume of porosity. 7. The coated metal composition of claim 4, wherein the coating metal layer Q comprises from about 4% by weight to about 70% by weight aluminum. 8. The coated metal composition of claim 7, wherein the coating metal layer Q is NiAl. 9. The coated metal composition of claim 8 wherein the coated metal layer Q comprises from about 17% to about 39% by weight of A1, and from about 61% by weight to about 83% by weight of m. . The coated metal composition of claim 9, wherein the coated metal layer Q has a thickness of from about 1 μm to about 3 μm. The coating metal composition of claim 7, wherein the coating metal layer Q is NiCrAl. The coating metal composition of claim 11, wherein the coating metal layer Q comprises from about 4% by weight to about 3% by weight of A1, from about 15% by weight to about 3% by weight of Cr, And about 60% by weight to about 81% by weight of Ni. 1 3. A coated metal composition according to claim 12, wherein the coating: $: the layer Q has a thickness of from about μηι to about 5 mm. The coated metal composition of claim 1, wherein the coated metal composition (PQR) comprises a surface of a synthesis gas generating process apparatus exposed to a carbon supersaturated environment. 15. The coated metal composition of claim 14, wherein the syngas production process equipment is selected from the group consisting of a reactor, a gas/gas heat exchanger or a process tube and piping. -29- 200827483 16·—A metal oxide dust on the metal surface in a carbon supersaturated environment by high-efficiency coating of metal composition (PQR). P is the oxide layer on the (PQR) surface, Q is between Coating a metal layer, and R is a base metal, wherein P comprises alumina, chromium oxide, ceria, mullite, Q comprises Ni and A1, and at least one is selected from the group consisting of Cr, Si, Co, B, C, N, P, Ga, Ge, As, In, Sn, Sb, La, Y, Ce, Ti, Zr, Hf, V, Nb, Ta, Mo, W, Ir, Pd, Pt, Cu, Ag or The element of Au or a mixture of R is selected from the group consisting of carbon steel, low chromium steel, ferritic stainless steel, Wool steel, duplex stainless steel, Inco high nickel alloy, Incoloy: alloy as bottom, Ni-based An alloy or a Co-based alloy; wherein the method comprises providing a metal surface having (PQR). The method of claim 16 wherein the layer P is oxidized. 18. The method of claim 16, wherein the layer P has a thickness of from about 1 nm to about 100 μm. 19. The method of claim 16, wherein the coating metal composition is exposed to a low oxygen partial pressure controlled by carbon supersaturation and a low oxygen partial pressure, before the use of the coated metal composition The formation of the oxide layer Ρ. a method for preventing exposure, which is followed by a step of R, or a mixture thereof of Mn, Fe, Pb, Sc, Ru, Rh, and a sinter iron, and a Fe-Ni surface. Or the method of the present invention, or the method of claim 19, wherein the environment of the carbon supersaturation and low oxygen partial pressure is between about 350 ° C and 1 2 0 0 ° C. The exposure time of about 1 hour to about 500 hours at a temperature is a gaseous 50CO: 50H2 mixture. 21. The method of claim 2, wherein the carbon supersaturated and low oxygen partial pressure environment further comprises a gas selected from the group consisting of ch4, NH3, N2, He, Ar, hydrocarbons, or mixtures thereof. 22. The method of claim 19, wherein the controlled low oxygen partial pressure environment is exposed to a temperature of from about 3 50 ° C to 120 (TC for about 1 hour to about 500 hours). The time is gaseous H2 〇: p, 2, or gaseous CO 2 :CO mixture. 23. The method of claim 22, wherein the low oxygen partial pressure environment further comprises a selected from the group consisting of ch4, nh3, Ar, hydrocarbon, or The gas of the mixture. 24. The method of claim 1, wherein the genus layer Q contains less than about 12% by weight of Fe. 25 · As in the method of claim 16 of the patent application, the genus layer Q contains less than A porosity of about 3% by volume. 26. The method of claim 25, wherein the genus layer Q comprises less than about 1% by volume of porosity. 27. The method of claim 24, _ Controlling, in 2, 〇 2, He _ in the coating gold _ in the coating gold # the coating metal layer _ wherein the coating metal layer Q comprises from about 4% by weight to about 70% by weight of aluminum. As in the method of claim 27, the coating metal layer Q in the β is NiAl. -31 - 200827483 2 9. Patent application The method of claim 28, wherein the coating metal layer Q comprises from about 17% by weight to about 39% by weight of A1, and from about 61% by weight to about 83% by weight of Ni. 30. The method of claim 29, wherein the coating metal layer Q has a thickness of from about 1 μm to about 300 μm. 3 1. The method of claim 30, wherein the step of providing a metal surface having (PQR) comprises It is selected from the steps of: a) constructing a metal surface of the highly efficient metal-clad composition (PQR), b) co-extending the metal layer Q on the base metal layer R, c) coating the base metal layer R The metal layer Q, and d) a combination of steps a), b) and c). The method of claim 31, wherein the coating step c) is selected from the group consisting of CVD, MOCVD, PVD, slurry coating or pack cementation 〇3 3 . The method of item 3, further comprising the step of annealing or laser melting the back portion of the metal layer (Q). 34. The method of claim 27, wherein the coated metal layer Q is NiCrAl. The method of claim 34, wherein the coating metal layer Q comprises from about 4% by weight to about 10% by weight of A1, from about 15% by weight to about 30% by weight of Cr, and about 60% by weight. % to about 81% by weight of Ni. The method of claim 35, wherein the coated metal layer Q has a thickness of from about 100 μm to about 5 mm. 37. The method of claim 36, wherein the step of providing a metal surface having -32-200827483 (PQR) comprises the step of: a) constructing the metal of the highly efficient coated metal composition (PQR) Surface, b) coextruding the metal layer Q on the base metal layer R, c) coating the metal layer Q on the base metal layer R, and d) a combination of steps a), b) and c). 38. The method of claim 37, wherein the coating step c) is by plasma welding. 3. The method of claim 38, further comprising the step of annealing or laser melting the back layer of the metal layer (Q). 40. The method of claim 16, wherein the coated metal composition (PQR) comprises a surface of a synthesis gas production process apparatus exposed to a carbon supersaturated environment. The method of claim 40, wherein the syngas generation process equipment is selected from the group consisting of a reactor, a gas/gas heat exchanger or a process tube and piping. -33-