The present invention relates to a flanged tube outlet assembly of a steam methane reformer and a method of assembling or retrofitting same.
Steam methane reforming processes are widely used in the industry to make hydrogen and/or carbon monoxide. Typically, in a steam reforming process a fossil-fuel hydrocarbon containing feed such as natural gas, steam and an optional recycle stream such as carbon dioxide, are fed into catalyst-filled tubes where they undergo a sequence of net endothermic reactions. The catalyst-filled tubes are located in the radiant section of the steam methane reformer. Since the reforming reaction is endothermic, heat is supplied to the tubes to support the reactions by burners firing into this radiant section of the steam methane reformer. Fuel for the burners mainly comes from by-product sources such as purge gas from pressure swing adsorption (PSA), and some make-up natural gas. The following reactions take place inside the catalyst packed tubes:
CH4+H2O<=>CO+3H2
CH4+CO2<=>2CO+2H2
CO+H2O<=>CO2+H2
The crude synthesis gas product (i.e., syngas) from the reformer, which contains mainly hydrogen, carbon monoxide, and water, is further processed in downstream unit operations. An example of steam methane reformer operation is disclosed in Drnevich et al (U.S. Pat. No. 7,037,485), and incorporated by reference in its entirety.
Syngas exiting the steam methane reformer is at high temperature, typically between 1450-1650° F., depending on the plant rate and product slate. Outside the heated zone of the reformer, syngas from the individual tubes is collected and sent downstream for further processing in the aforementioned unit operations. In reformers where the tube outlets are not encased in refractory or placed in refractory lined enclosures, the exposed flanged tube outlet is typically fitted with both internal and external insulation. The design of the tube outlet assembly insulation is critical to preventing premature tube failure as insufficient insulation can lead to temperatures favorable for metal dusting in some areas of the tube outlet, and dew point condensation-related failures in other sections. On the other hand, too much insulation can result in high temperatures at the flanges and eventual weakening or decarburization. The external insulation comprises a high temperature fibrous insulation blanket wrapped around the tube outlet. The internal insulation is sheet metal formed into a shape, hereinafter referred to as a can, and filled with high temperature fibrous insulation material. One end of the can is securely attached to a blind flange such as by welding, and the other end is sealed to enclose the insulation material. The can is positioned inside the reformer tube with a clearance or gap, which as utilized herein refers to the spacing between the outside surface of the can and the inner wall of the reformer tube.
Garland et al (U.S. Pat. No. 8,776,344 B2) disclose a cylindrical can with an angled base, and a ‘seal’ for use in the inlet of a reformer tube assembly. In a reforming furnace, hot feed gas (typically <1300° F.) is delivered into the individual reformer tubes. In tube assemblies where the inlet port enters from the side, it has been discovered that the hot process gas swirls on entering the tube and some gas can flow upwards toward the flanges, causing them to overheat. This is detrimental to the lifespan and performance of the reformer tubes. The cylindrical, angled base plug disclosed in this patent is positioned adjacent to the inlet port to direct the fluid introduced through said inlet port away from the flanges. The seal placed in the gap limits passage of hot fluid upwards along the gap, thereby preventing overheating of the flanges. However, the invention of the Garland et al disclosure is only applicable to the reformer tube inlet assembly. It aims to reduce flange and weld neck temperatures of the tube inlet. No considerations were given to metal dusting or hydrogen attack of the tube inlets as there is no carbon monoxide (CO) and very little hydrogen (H2) in the process feed gas.
While Hohmann et al (U.S. Pat. No. 5,490,974), Roll et al (U.S. Pat. No. 5,935,517) and Boll et al (U.S. Pat. No. 6,099,922) disclose some methods for preventing metal dust corrosion in outlet pipes and headers containing syngas, the disclosures in these documents concern only outlet pipes and headers that are lined with refractory on the inside. In such cases, carbon monoxide can diffuse through the refractory and come into contact with sections of the metal whose temperatures are in the metal dusting favorable range. This can lead to carburization and catastrophic failure of the material. In the '974 and '517 documents, a hot gas purge is applied to the refractory to arrest syngas diffusion and prevent metal dusting. In the '922 document, the refractory is infused with nickel-based catalyst that promotes reaction of carbon monoxide with the hydrogen and water in the syngas to form CO2, H2O, H2 or CH4, thereby eliminating the potential for metal dust corrosion.
For reformer furnaces in which the tube outlets are exposed to the ambient, the insulation design is critical to preventing a deleterious temperature profile. In the presence of high CO partial pressures, as typically would occur in a reformer tube, areas of the tube inner wall metal surfaces at temperatures between 900-1400° F. are susceptible to high rates of metal dusting. Also, it is important that the wall temperatures stay above the dew point temperature of the syngas to prevent dew point condensation related failures. However, putting too much insulation on the tube outlet to avert the two aforementioned material failure mechanisms will result in high flange temperatures which can lead to decarburization or weakening and cracking of the steel. Premature tube failure can result in extended, unplanned plant shutdown and possible contractual penalties.
Thus, to overcome the disadvantages in the related art, one of the objectives of the present invention is to provide an internal insulation design to the tube outlet assembly that leads to a desired tube metal temperature profile.
It is an object of the invention that the tube outlet assembly insulation ensures that areas of the tube outlet with temperatures favorable to metal dusting occur only in low syngas flow areas in the annular gap between the internal insulation can and reformer tube inner wall in order to greatly minimize the rate of metal dusting corrosion.
It is another object of the invention that the tube outlet assembly insulation reduces the convection of hot syngas to the flanges thereby reducing flange temperatures and preventing high temperature hydrogen attack of the steel flanges.
It is a further object of the invention to prevent dew point condensation related failures by maintaining the entire length of the tube outlet above the syngas dew point temperature.
Another object of the invention is to coat the internal walls of the reformer tubes, which receive and process the feedstock, with an aluminized diffusion coating thereby reducing the metal dusting.
A further object of the invention is to process a hydrocarbon feedstock with the reformer tubes of the present invention in a steam methane reformer in order to obtain a syngas product.
Other objects and aspects of the present invention will become apparent to one skilled in the art upon review of the specification, drawings and claims appended hereto.
This invention pertains to the flanged outlet of a steam methane reformer tube assembly. In accordance with one aspect of the invention, a flanged tube outlet assembly of a steam methane reformer assembly is provided. The assembly includes:
at least one or more reformer tubes having an inlet for allowing the process gas to be introduced into the tube outlet assembly for the removal of the process gas, wherein the process gas exiting an outlet port is syngas,
the tube outlet assembly is disposed outside the confines of the reformer and includes a reformer tube having an interior space accommodating an internal insulation can therein wherein the insulation can is fitted in the interior space of the reformer tube, and the exterior of the reformer tube is covered with insulation extending in close proximity to the tube-flange weld neck;
the outlet port disposed upstream of the distal end of the insulating can for delivering the syngas to downstream process units, and
the insulation can is connected to a blind flange and extends into the reformer tube toward the outlet port, wherein the gap between the can and the interior of the reformer tube is larger at the distal end than at the blind flange end.
In another aspect of the invention, the flanged outlet of a reformer tube outlet assembly is provided. It includes at least one or more reformer tubes having an inlet for allowing the process gas to be introduced into a tube outlet assembly for removal of the process gas, wherein the process exiting the outlet port is syngas.
The tube outlet assembly is disposed outside the confines of the reformer and includes:
at least one or more reformer tubes having an inlet for allowing the process gas to be introduced into a tube outlet assembly for removal of the process gas, wherein the process exiting an outlet port is syngas,
the tube outlet assembly is disposed outside the confines of the reformer and includes a reformer tube having an interior space accommodating an internal insulation can therein wherein the insulation can is tapered or stepped in the interior space of the reformer tube and wherein the exterior of the reformer tube is covered with insulation extending in close proximity to the tube-flange weld neck;
the outlet port is disposed upstream of the distal end of the insulation can for delivering the syngas to downstream process units, and
the insulation can is connected to a blind flange and extends into the reformer tube toward the outlet port and securely connected to the blind flange, wherein the gap between the can and the interior of the reformer tube is in the range between about 0.1 to 0.5 inches at the blind flange end of the tube outlet, and 0.1 to 1 inches at the distal end, allowing a larger volume of hot syngas to be maintained at the distal end of the gap so the tube metal temperature in the vicinity of the distal end of the can is above metal dusting favorable temperatures, yet regulating the flow of hot gas towards the flange to maintain the whole length of the tube outlet above the syngas dew point temperatures to eliminate condensation/evaporation thermal cycling induced fatigue cracking while lowering the flange temperatures to minimize occurrence over-temperature induced metal failures.
The above and other aspects, features, and advantages of the present invention will be more apparent from the following drawings, wherein:
The present invention addresses the susceptibility of tube outlets to the aforementioned material degradation mechanisms that lead to premature tube failure in steam methane reformers. Specifically, this invention is utilized with a flanged tube outlet assembly of a steam methane reformer, an example of which is a bottom-fed cylindrical reformer. As utilized herein the term “bottom-fed cylindrical reformer or reactor” will be understood by those skilled in the art to refer to a can reformer or the like where feed gas is introduced into the bottom of the reformer tubes, and the burners are fired at the bottom of the reformer, and the process gas and flue gas flow co-currently from the bottom to the top of the reformer. In this type of reformer, the tube outlet is outside the furnace refractory wall/roof and exposed to the ambient.
Referring to the figures and commencing with
With reference to
The very short height of the external insulation leads to increased heat losses and low flange temperatures. In this example, the maximum temperature on the weld flange was found to be ˜237° F. While this is beneficial to minimizing the occurrence of high temperature hydrogen attack, metal temperatures for the upper parts of the tube outlet are below the syngas dew point temperature, which is ˜311° F. in this case. As a result, water will condense on the inner walls of the tube. At a lower location where the tube is hotter, the water evaporates. This repeated condensation/evaporation cycle can cause thermal fatiguing and cracking of the reformer tube. In other cases too, the condensed water can become slightly acidic due to dissolved gases such as CO2, and can cause corrosion of the tube. These material degradation mechanisms are herein referred to as dew point condensation related failures. The term “high temperature hydrogen attack” as utilized herein will be understood by those skilled in the art to mean a form of decarburization at elevated temperatures (typically >400° F. for carbon steel) whereby hydrogen can dissociate into atomic form and diffuse into steel, reacting with unstable carbides to form methane gas. This eventually leads to cracking and equipment failure.
Referring now to an exemplary embodiment of the invention, as shown in
An internal insulation can of the tube outlet assembly 300a-c includes a blind flange 311a-c and a non-cylindrical can 308a-c that is positioned in the interior space of the steam reformer tube 305a-c. The can portion 308a-c fits into the inside of the reformer tube and is securely attached to the blind flange 311a-c such as through a weld. Internal insulation can 308a-c is a sheet metal formed into the non-cylindrical can and filled with insulation material and extends toward the outlet port 307a-c at its distal end.
In an assembled form of the tube assembly 300a-c as shown, the internal insulation can 308a-c is tapered or stepped as shown in
As illustrated in
The choice of internal can design for the tube assembly outlet will depend on the process conditions and geographic location of the reformer. For processes where the temperature of the syngas exiting the reformer is very high (>1600° F.), a shallow taper or stepping will be most appropriate as it is not desirable to have large volumes of very hot syngas contact the flanges. Conversely, if the reformer is located in a very cold climate, then a more pronounced tapering or stepping will be appropriate as more syngas can be directed into the gap to help maintain temperatures above the dew point. By considering the process conditions and climate, an appropriate internal and external insulation tube outlet assembly design can be selected that greatly improves its reliability and lifespan.
Alternatively, or in addition to the redesign of the internal insulation can 308a-c, the inner walls of the reactor tubes are coated with an aluminum diffusion coating by pack cementation process. While the reactor tube material or substrate can be austenitic stainless steels, nickel based alloys and nickel centrifugal cast alloys, it is preferred that it is a micro-alloyed nickel centrifugal cast alloy such as an HP-Nb-MA (micro-alloyed) material with addition of carbides or intermetallic compounds forming elements to improve microstructural stability in long term exposure to high temperatures, and, therefore, better resistance to high temperature stress and creep deformation.
The coating process on the inside walls of the reactor tubes is performed in a furnace or retort with a protective atmosphere. The substrate material to be aluminized is prepared so that it is free of surface flaws or defect detrimental to the coating process. Therefore, thorough cleaning and grit blasting is used for preparing the surface such that there will be minimal contamination during the coating process. The inside of the reactor tubes are then packed with pack compound which consists of an aluminum source, an activator which is normally a halogen compound, and an inert phase. At high temperature, a chemical reaction occurs that a gaseous aluminum halide forms and the aluminum is transferred by the gas to the reactor tube inside diameter surface (i.e., interior wall). The gas decomposes at the substrate surface depositing aluminum and releasing the halogen activator. The halogen activator returns to the pack and reacts with the Al source again. Thus, the transfer process continues until all of the aluminum in the pack is consumed or until the process is stopped by cooling. The aluminum diffuses into the reactor tube inside diameter surface forming metal aluminides diffusion coating at temperatures ranging from 700 to 1100° C. The coating thickness is controlled by time and temperature.
In order to have sufficient metal dusting protection and also maintain the mechanical properties of the reactor tube, the thickness of aluminizing diffusion coating can be in the range of about 10-300 μm, and is preferably controlled to a range of about 60 to 100 μm. The weldability of the reactor tube is preferably evaluated by ASTM A488 after coating.
The composition of the coating is dependent on the substrate chemistry. For HP-Nb microalloyed reactor tubes, the chemical composition as measured by energy dispersive spectroscopy (EDS) preferably can have an aluminum content 20-50 wt % from the surface to the substrate interface, preferably an aluminum content 30-35 wt % from the surface to a distance at least 50% of the coating thickness. A typical example of the coating composition vs. distance from surface is shown in
For ease of explanation, and with reference to
The invention is further explained through the following examples, which compare the base case with a standard design at the outlet tube, and those based on various embodiments of the invention, which are not to be construed as limiting the present invention.
In an alternative example of the related art, and as shown in
The design which is the subject of this invention involves an internal insulation can that is tapered where the annular gap is larger at the distal end than at the blind flange end (
The results shown in
Although various embodiments have been shown and described, the present disclosure is not so limited and will be understood to include all such modifications and variations as would be apparent to one skilled in the art.
This application is a continuation-in-part application of U.S. patent application Ser. No. 15/433,340 filed Feb. 15, 2017 and entitled STEAM METHANE REFORMER TUBE OUTLET ASSEMBLY.
Number | Date | Country | |
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Parent | 15433340 | Feb 2017 | US |
Child | 15949655 | US |