Heat integrated reformer with catalytic combustion for hydrogen production

Abstract

A heat integrated steam reformer, which incorporates a catalytic combustor, which can be used in a fuel processor for hydrogen production from a fuel source, is described. The reformer assembly comprises a reforming section and a combustion section, separated by a wall. Catalyst (21) able to induce the reforming reactions is placed in the reforming section, either in the form of pellets or in the form of coating on a suitable structured catalyst substrate such as fecralloy sheets. Catalyst (22) able to induce the combustion reactions is placed in the combustion section in the form of coating on suitable structured catalyst substrate such as fecralloy sheet. A steam and fuel mixture (30) is supplied to the reforming section (14) where it is reformed to produce hydrogen. A fuel and an oxygen (32) containing gas mixture is supplied to the combustion section where it is catalytically combusted to supply the heat for the reformer. The close placement of the combustion and reforming catalysts facilitate efficient heat transfer. Multiple such assemblies can be bundled to form reactors of any size. The reactor made of this closely packed combustion and reforming sections is very compact.

Claims

1. An apparatus for the production of hydrogen from a fuel source, comprising: a combustor configured to receive at least a combustor fuel and convert the combustor fuel into a combustor heat; a reformer disposed annularly about the combustor, wherein the reformer and the combustor define a gap therebetween and the reformer is configured to receive the combustor heat; and a removable structured catalyst support disposed within the gap and coated with a catalyst to induce combustor fuel combustion reactions that convert the combustor fuel to the combustor heat, the structured catalyst support being in contact with the combustor and the reformer, forming heat exchange zones where heat is transferred between a feed of the combustor and products of the reformer, and between a feed of the reformer and products of the combustor, wherein the reformer being configured to receive at least a reformer fuel and to produce a reformate containing primarily hydrogen, wherein the reformer further containing a reforming catalyst to induce reformer fuel reforming reactions to produce the reformate, wherein the structured catalyst support of the combustor is made of corrugated fecralloy sheets, wherein the corrugated fecralloy sheets are coated with a high surface area alumina film containing a dispersed metal phase of palladium or platinum metal, and mixtures thereof, and wherein the dispersed metal phase is between 0.1-10% of the alumina film.

2. An apparatus according to claim 1, wherein the reforming catalyst includes a nickel based catalyst.

3. The apparatus of claim 1, wherein the reformer fuel to be reformed and the combustor fuel to be combusted are in countercurrent flow configuration to each other.

4. An apparatus according to claim 1, wherein the reforming catalyst includes catalyst pellets.

5. An apparatus according to claim 1, wherein the reforming catalyst includes a structured catalyst support coated with a catalyst.

6. An apparatus according to claim 5, wherein the structured catalyst support is coated with a catalyst is removable.

7. An apparatus according to claim 1, wherein the reforming catalyst is fecralloy sheets coated with a catalyst.

8. An apparatus according to claim 7, wherein the fecralloy sheets being in close contact with the combustor and the reformer.

9. An apparatus for the production of hydrogen from a fuel source, comprising: a combustor configured to receive at least a combustor fuel and convert the combustor fuel into a combustor heat; a reformer disposed annularly about the combustor, wherein the reformer and the combustor define a gape therebetween and the reformer is configured to receive the combustor heat; and a removable structured catalyst support disposed within the gap and coated with a catalyst to induce combustor fuel combustion reactions that convert the combustor fuel to the combustor heat, the structured catalyst support being in contact with the combustor and the reformer, wherein the structured catalyst support of the combustor is made of corrugated fecralloy sheets, wherein the corrugated fecralloy sheets are coated with a high surface area alumina film containing a dispersed metal phase of palladium or platinum metal, and mixtures thereof, and wherein the dispersed metal phase is between 0.1-10% of the alumina film.

10. An apparatus according to claim 9, wherein the reformer further containing a reforming catalyst to induce reformer fuel reforming reactions to produce the reformate, and wherein the reforming catalyst is a nickel based catalyst.

11. The apparatus of claim 10, wherein the reformer fuel to be reformed and the combustor fuel to be combusted are in countercurrent flow configuration to each other.

12. An apparatus according to claim 10, wherein the reforming catalyst includes catalyst pellets.

13. An apparatus according to claim 10, wherein the reforming catalyst includes a structured catalyst support coated with a catalyst.

14. An apparatus according to claim 13, wherein the structured catalyst support is coated with a catalyst is removable.

15. An apparatus according to claim 10, wherein the reforming catalyst includes fecralloy sheets coated with a catalyst.

16. An apparatus according to claim 15, wherein the fecralloy sheets being in close contact with the combustor and the reformer.

Description

BRIEF DESCRIPTION OF THE DRAWINGS

(1) FIG. 1a is a perspective view of one embodiment of the heat integrated reformer with catalytic combustion of the invention.

(2) FIG. 1b is a perspective view of another embodiment of the heat integrated reformer with catalytic combustion of the invention.

(3) FIG. 1c is a perspective view of another embodiment of the heat integrated reformer with catalytic combustion of the invention.

(4) FIG. 2a is a perspective view of one embodiment of the heat integrated reforming reactor with catalytic combustion of the invention.

(5) FIG. 2b is a perspective view of another embodiment of the heat integrated reforming reactor with catalytic combustion of the invention.

DETAILED DESCRIPTION OF THE PREFERRED EMBODIMENTS

(6) The present invention is described in detail with reference to a few preferred embodiments illustrated in the accompanying drawings. The description presents numerous specific details included to provide a thorough understanding of the present invention. It will be apparent, however, to one skilled in the art that the present invention can be practiced without some or all of these specific details. On the other hand, well known process steps, procedures and structures are not described in detail as to not unnecessarily obscure the present invention.

(7) FIG. 1A illustrates the heat integrated reformer according to one embodiment of the present invention. The integrated combustor/steam reformer assembly includes a tubular section defined by a cylindrical wall 10 that separates the combustion zone 15 from the reforming zone 14. The assembly housing 11 acts as the reactor wall and defines an axially extending concentric annular passage in heat transfer relation with the tubular section. A fuel and air mixture 32 is supplied to the tubular section through flow passage 42. The tubular section contains a structured combustion catalyst. An example of a structured catalyst is a fecralloy sheet, preferably corrugated, which is coated with a combustion catalyst 22 that induces the desired reaction in the combustor feed. The products of the combustion reactions 33 exit the tubular section through flow passage 43. A fuel and steam mixture 30 is supplied to the annular passage through flow passage 40. The outside area of the tubular section contains either catalyst pellets 21 capable of inducing the desired reaction in the reformer feed or fecralloy sheets, preferably corrugated, which are coated with the catalyst 21. The products of the reforming reactions 31 exit the annular passage through flow passage 41.

(8) The fuel to the combustor can be any available and suitable fuel. Such fuels include methane, natural gas, propane, butane, liquefied petroleum gas, biogas, methanol, ethanol, higher alcohols, ethers, gasoline, diesel etc. For the embodiment illustrated in FIG. 1A, the fuels normally available in liquid form must be vaporized before entering the combustion zone. The same fuels can be fed to the reforming zone to undergo the hydrogen producing reforming reactions. Another potential fuel to the combustor is the hydrogen depleted off-gas from the anode of a fuel cell when the reformer is used as a part of a fuel processor producing hydrogen for a fuel cell. Yet another potential fuel to the combustor is the hydrogen depleted off-gas from the pressure swing adsorption (PSA) or any other hydrogen purification devise when the reformer is used as a part of a fuel processor producing a hydrogen rich stream that feeds such a device to produce high purity hydrogen.

(9) The temperatures and pressures of the two streams entering the combustor and the reformer, respectively, need not be the same. Typically, combustion takes place at low or near-atmospheric pressure, although high pressure combustion is widely practiced. Reforming can take place at pressures somewhat above atmospheric to moderately high (up to 50 barg). The cylindrical wall of the tubular section should be of sufficient strength to allow for the pressure differential between the two streams. It is also apparent that different geometries can be used instead of cylindrical shapes should they offer advantages in particular applications. The composition of the mixture entering the combustor should be such as to ensure complete combustion of the fuel. Although a stoichiometric ratio of air to fuel is sufficient, higher ratios can be employed with the present invention. The composition of the mixture entering the reforming section of the assembly is determined by the stoichiometries of the reforming reactions for the given fuel. It is typical practice to provide a higher than stoichiometric steam-to-fuel ratio to minimize possible side reactions that can cause shoot or carbon formation to the detriment of the catalyst and/or the reactor. All suitable steam-to-carbon ratios in the range from 1 to 25 can be employed with the present invention.

(10) The major advantage of the present invention is the heat integration between the combustion 15 and the reforming 14 zones. Combustion takes place on the catalytic film which is coated on the structured catalyst 22 placed on one side of the wall 10 separating the two zones. The heat that is generated on the combustion side is quickly transferred and used on the reforming side. This rapid heat transfer is critical in maintaining the combustion side catalyst at temperatures below 1200 C and, more preferably, below 1000 C. These temperatures ensure acceptable catalyst life and permit the use of a very compact combustion zone which allows the reactor assembly to be dramatically smaller compared with a flame-based reformer which needs to maintain a significant distance between the flame generation and the reforming sections. The lower temperatures also allow the use of less expensive alloys for the construction of the reactor. The lower temperatures also mean no nitrogen oxide emissions as their formation requires much higher temperatures.

(11) The structured combustion catalyst can preferably be in the form of a corrugated metal foil made of a high temperature resistant metal or metal alloy. A metal alloy such as an alloy with the formula FrCrAlY, commonly referred to as fercalloy, can be used for high temperature combustion catalyst support. The corrugated foil is supported on a rod or tube placed inside tube 10. The corrugated foil is wrapped on the tube or rod so that the corrugated channels run parallel to the axis of the tube 10. Reforming takes place on the catalyst placed in reforming zone 14 enclosed between tube 10 and reactor wall 11. The catalyst 21 can be in the form of pellets or it can be a structured catalyst or monolith. The wall 10 can be constructed from any material, but materials that offer low resistance to heat transfer such as metals and metallic alloys are preferred. In this configuration, heat is generated by combustion in the catalytic chamber 22 and is transported very easily and efficiently though the wall 10 to the reforming chamber 21 where the heat demanding reforming reactions take place. Heat is generated where it is needed and does not have to overcome significant heat transfer resistances to reach the demand location resulting in high efficiencies. The presence of a catalyst and lower temperatures permit significantly higher space velocities to be used compared to flame based reformers. Space velocity is defined as the ratio of the feed flow at standard conditions to the empty volume of the reactor. For the catalyst section of the heat integrated reformer, space velocities of 1000 to 100000 hr.sup.1, more preferably 5000-50000 hr.sup.1 and even more preferably 10000 to 30000 hr.sup.1 can be used. In flame based reformers space velocities are typically below 2000 hr.sup.1.

(12) The catalyst on the reforming side can be a pellet catalyst or it can also be a structured catalyst on support. In the case of a pellet catalyst, space velocities similar to the ones used in flame based reformers can be used (1000-10000 hr.sup.1). In the case of structured catalyst much higher space velocities can be used preferably 10,000-100000 hr.sup.1 or more preferably 10,000-50000 hr.sup.1.

(13) The suitable combustion and, where applicable, the reforming catalysts, can be prepared by coating a relatively thin (5-1000 m thick) catalytic film on the fecralloy sheets. Suitable catalysts typically consist of a metal oxide film and one or multiple metal phases dispersed on the film. The film is typically a metal oxide that may contain oxides of one or multiple elements from the IA, IIA, IIIA, IIIB and IVB groups of the periodic table of elements. The most typical combustion catalysts support is high surface area aluminum oxide. The dispersed metal phase catalyst may contain one or multiple elements from the IB, IIB, VIB, VIIB and VIII groups of the periodic table of elements. A common dispersed metal phase catalyst is palladium or platinum and mixtures thereof. The dispersed metal phase is typically 0.1-10% of the metal oxide film and more preferably 0.3-3%.

(14) One method to prepare the catalytic film that ensures good adhesion to the fercalloy is to heat the fecralloy sheet to elevated temperatures in air. During the heating, aluminum, which is a component of the fercalloy, is diffusing out of the bulk of the alloy and forms an aluminum oxide surface layer. Upon this surface layer it is easy to coat alumina or other metal oxide supports for the desired dispersed metal phase which may be a precious or non-precious metal. Typical supports for reforming and combustion catalysts consist of oxides of aluminum, silicon, lanthanum, cerium, zirconium, calcium, potassium and sodium. The metal phase of reforming catalysts may contain nickel, cobalt, copper, platinum, rhodium and ruthenium. Nickel based catalysts are the most commonly used for reforming reactions.

(15) Coating of the catalysts support on the fecralloy sheets can be accomplished by many techniques. After heating up so as to form the aluminum oxide layer at the surface, techniques such as dip coating from a solution of dispersed metal oxide particles or from a slurry which contains the metal oxide particles can be employed. Alternatively, catalyst can be deposited on the fecralloy sheets by spraying the catalytic components onto their surface, or by plasma deposition, etc. The catalyst support is then dried by calcination at elevated temperatures. The dispersed metal phase can be added to the support forming solution or slurry of the metal oxide particles or it can be added in a separate step from a solution of the desirable metal salt after the calcination step.

(16) FIG. 1B illustrates the heat integrated reformer according to another embodiment of the present invention. The integrated combustor/steam reformer assembly includes a tubular section defined by a cylindrical wall 10 that separates the combustion zone 15 from the reforming zone 14. The assembly housing 11 acts as the reactor wall and defines an axially extending concentric annular passage in heat transfer relation with the tubular section. A fuel and air mixture 32 is supplied to the annular passage through flow passage 40. The outside wall of the tubular section contains fecralloy sheets coated with a catalyst film 22 that induces the desired reaction in the combustor feed. The products of the combustion reactions 33 exit the annular passage through flow passage 41. A fuel and steam mixture 30 is supplied to the tubular section through flow passage 42. The tubular section contains reforming catalyst pellets 21 or fecralloy sheets coated with a reforming catalyst film 21 that induces the desired reaction in the reformer feed. The products of the reforming reactions 31 exit the tubular section through flow passage 43.

(17) FIG. 1C illustrates the heat integrated reformer according to yet another embodiment of the present invention. The integrated combustor/steam reformer assembly includes a tubular section defined by a cylindrical wall 10 that separates the combustion zone 15 from the reforming zone 14. The assembly housing 11 acts as the reactor wall and defines an axially extending concentric annular passage in heat transfer relation with the tubular section. A fuel and air mixture 32 is supplied to the tubular section through flow passage 42. In this embodiment, only the middle part of the inside wall of the tubular section contains the catalyst film 22 that induces the desired reaction in the combustor feed. Similarly, only the middle part of the outside of the tubular section contains catalyst 21 or fecralloy sheets coated with catalyst 21 that induces the desired reaction in the reformer feed. The parts of the reactor assembly which do not contain catalyst function as heat exchange regions of the reformer. Heat exchange zone 16 transfers heat from the hot combustion products to preheat the reforming section feed. Heat exchange zone 17 transfers heat from the hot reforming products to preheat the combustion section feed. In this manner, greater heat integration and utilization is accomplished inside the reformer. The products of the combustion reactions 33 exit the tubular section through flow passage 43. A fuel and steam mixture 30 is supplied to the annular passage through flow passage 40 counter-current to the combustion gases. The products of the reforming reactions 31 exit the annular passage through flow passage 41.

(18) The production capacities of the reformers discussed in the previous examples are limited by their size, i.e. the diameter and length of the sections. Capacities of any size can be achieved by bundling together several such sub-assemblies. FIG. 2A illustrates one embodiment of such a heat integrated reforming reactor. The reactor consists of multiple tubes 10. The inside section of the tube contains the fecralloy sheets coated with a combustion catalyst film 22 that induces the desired combustion reactions. The outside section of the tube contains the reforming catalyst pellets 21 or the fecralloy sheets coated with a reforming catalyst film 21 that induces the desired reforming reactions. The tubes are supported on tube sheets 131 and 132 on each end. The tube sheets are machined as to allow flow contact between the combustor feed, the combustion zone and the combustion product collection spaces. The tubes are welded on the tube sheets as to prevent any mixing between the species participating in the reforming reactions and those participating in the combustion reactions. The tube bundles are enclosed by the reactor wall 11 which also attaches to tube sheets 131 and 132 and defines an enclosed space 14 between the tubes 10 and the tube sheets 131 and 132. This space is the reforming zone. The reactor further consists of reactor heads 121 and 122. Ceramic insulation 133 in the form of a hard cast ceramic or fiber blanket can be added to minimize heat loss of the reactor and maintain the reactor wall temperature below 500 C or more preferably below 200 C.

(19) The fuel and air feed to the combustor 32 enters the reactor through reactor nozzle 42. The mixture is distributed in the reactor head 121 by flow distributor 16 as to allow for uniform feeding of all tubes 10. Combustion takes place inside the tubes 10 on the combustion catalytic film 22. The combustion products 33 exit at the other end of the tubes supported on tube sheet 132, are collected in the reactor head 122 and leave the reformer through reactor nozzle 43. Since the tubes 10 and tube sheet 131 become very hot during operation, a flame arresting devise 17, which can be a perforated metallic sheet or a porous ceramic plate, is placed before tube sheet 131 to prevent back flash and uncontrolled combustion in the reactor head 121. The fuel and steam reforming feed 30 enters the reactor through reactor nozzle 40. The mixture comes in flow contact with the reforming catalyst pellets or reforming catalyst film 21 supported on the fecralloy sheets in contact with the outside wall of the tubes 10. The reforming catalyst induces the reforming reactions and the products 31 exit the reactor through flow passage 41. The reforming catalyst pellets can be supported in the reactor by a suitable metal plate 134 that is drilled to create holes that are sufficient large that present little resistance to reforming gas flow and keep the pellet catalyst in the desired location in the reactor. This metal plate also serves to distribute the reforming gas feed evenly along the radial dimension of the reactor.

(20) The reactor wall contains an expansion joint 135 to facilitate different thermal expansions between the reactor tubes and the reactor wall, due to the fact that they are at different temperatures.

(21) The reformer reactor shown in FIG. 2A operates in the so-called co-current mode, i.e. combustion and reforming mixtures flow in the same direction. The same reactor configuration can be employed in operation in the so-called counter-current mode, i.e.

(22) combustion and reforming mixtures flowing in opposite directions. This can be achieved easily by interchanging the reforming feed and reforming exit nozzles.

(23) FIG. 2B illustrates another embodiment of a heat integrated reforming reactor with catalytic combustion. The fuel and steam reforming feed 30 again enters the reactor through flow passage 40. One or multiple baffles 50 are placed inside the reactor and perpendicular to the tubes 10 as to force the reacting mixture in a cross-flow multi-passage path through the reactor. This ensures higher fluid velocities, greater turbulence and better contact with the catalyst pellets which are outside tubes 10. This in turn results in lower mass transfer resistances in the fluid phase and higher reaction efficiencies while increasing the heat transfer rates as well. The products of the reforming reactions 31 again exit the reactor through flow passage 41.

(24) Yet another embodiment of a heat integrated reforming reactor with catalytic combustion can be envisioned. Since the tubes 10 and tube sheet 131 become very hot during operation, combustion can be initiated on the front surface of tube sheet 131 and back propagate through reactor head 121 and, possibly, through flow passage 42 if the fuel and air are pre-mixed. To avoid such a potentially very dangerous situation, the air and fuel can be kept separated until they enter the tubes 10 where combustion is desired. Air entering the reactor head 121 is distributed and uniformly enters the tubes 10 through tube sheets. Fuel enters through the manifold and is distributed to each tube through appropriately sized and shaped tips. Allowing for a slightly higher pressure for the fuel stream than the air stream also allows for the Venturi effect to develop and prevent any fuel from flowing back. Alternatively, increasing the flow of the air stream, pushes the mixture further along the tubes 10 delaying combustion until the mixture is well inside the tubes.

(25) Yet another embodiment can be envisioned having the reforming mixture flowing inside the tubes and the combustion mixture flowing in the annulus. Thus, in FIGS. 2A and 2B, the reforming catalyst, in pellet form or coated on fecralloy sheets, is placed inside tubes 10, while the combustion catalyst is placed in the space outside the tubes. The fuel and steam mixture is directed inside the tubes while the fuel and air mixture is directed in the space outside the tubes 10.

(26) The heat integrated reforming reactor offers several advantages over conventional flame based reforming reactors. The catalytic combustion takes place at lower temperatures that permit close coupling of the combustion and reforming zones. In a flame based reformer the flame must be at a significant distance from the tube containing the reforming catalyst to prevent the tube from melting. As a result the integrated reforming reactor is several times smaller than a flame based reforming reactor and consequently has a much lower capital and installation cost. The flame based reformers can consist of hundreds of tubes and burners and a sophisticated feed flow distribution system is required to distribute the combustion feed and reforming feed to all burners and tubes evenly. The heat integrated reformer has a single inlet for the reforming and single inlet for the combustion feed gases which results in simple and inexpensive feed flow system. The flame reformers even with the use of low NOx burners still produce significant emissions of NOx in the combustion gases that have to be controlled with a separate selective catalytic reduction (SCR) catalyst and ammonia injection. The heat integrated reformer operates at low temperatures on the combustion side at which NOx formation is negligible.

(27) The heat integrated reformer can be easily integrated with a hydrogen producing process that typically consists of a feed pretreatment system to remove impurities from natural gas, heat recovery equipment to recover heat to preheat the feed and raise steam, one or more water gas shift reactors to convert carbon monoxide to hydrogen and pressure swing adsorption system to separate hydrogen from syngas. The waste stream from the pressure swing adsorption system can be used as fuel to the heat integrated reformer combustion side. Another advantage of the hydrogen production process based on a heat integrated reformer is that the make up natural gas fuel that is normally supplied to ensure stable burner operation in flame based reformers can be reduced or eliminated. In that case most of the fuel requirement can be supplied by the PSA waste stream.

(28) The hydrocarbon feed to the reformer is typically natural gas but other fuels can be used such as liquefied petroleum gas (LPG), propane, naphtha, diesel, ethanol or biofuels.

(29) In addition to hydrogen, the heat integrated reformer can be used in the production of ammonia, production of methanol, Gas to Liquids, production of ethanol, production of oxo-alcohols and in general in processes where syngas (hydrogen and CO mixture) is required. For some processes it may be advantageous to co-feed carbon dioxide in the reforming zone to promote the conversion to carbon monoxide. In yet another application the heat integrated reformer can be used to produce hydrogen for fuel cells for the production of electricity.

(30) While this invention has been described in terms of several preferred embodiments, there are alterations, permutations and equivalents that fall within the scope of the present invention and have been omitted for brevity. It is therefore intended that the scope of the present invention should be determined with reference to appended claims.