WO2006044819A2 - Combustion a haute temperature catalysee et stable dans des reacteurs de combustion integres a microcanaux, methodes de mise en oeuvre de combustion catalytique dans un reacteur multizone et methode de fabrication d'un support catalytique thermiquement stable - Google Patents

Combustion a haute temperature catalysee et stable dans des reacteurs de combustion integres a microcanaux, methodes de mise en oeuvre de combustion catalytique dans un reacteur multizone et methode de fabrication d'un support catalytique thermiquement stable Download PDF

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WO2006044819A2
WO2006044819A2 PCT/US2005/037290 US2005037290W WO2006044819A2 WO 2006044819 A2 WO2006044819 A2 WO 2006044819A2 US 2005037290 W US2005037290 W US 2005037290W WO 2006044819 A2 WO2006044819 A2 WO 2006044819A2
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zone
hydrocarbon
catalyst
conversion
parts
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WO2006044819A3 (fr
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Francis P. Daly
Junko M. Watson
Yong Wang
Jianli Hu
Richard Long
Rachid Taha
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Velocys Inc
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Velocys Inc
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Priority claimed from US10/966,158 external-priority patent/US7566441B2/en
Priority claimed from US10/966,162 external-priority patent/US8062623B2/en
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Publication of WO2006044819A2 publication Critical patent/WO2006044819A2/fr
Publication of WO2006044819A3 publication Critical patent/WO2006044819A3/fr
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Definitions

  • the invention relates to integrated combustion microreactors, chemical systems utilizing these integrated combustion microreactors, and methods of providing heat to endothermic reactions in integrated combustion microreactors.
  • ICRs integrated combustion reactors
  • heat from a combustion reaction that is conducted in one portion of a ICR is transferred to an endothermic reaction in another portion of the ICR.
  • the combustion is catalysed by a solid catalyst.
  • methane steam reforming the combustion reaction must occur at high temperature and, for most applications, it is desired that the combustion reaction be stable over a long time.
  • Niu et al. in Publication No. US 2003/0180215 Al describes a controlled pore structure for partial oxidation.
  • Barnes et al. in U.S. Patent No. 6,488,907 describes a partial oxidation reaction over a noble metal catalyst on an aluminum-containing oxide-dispersion- strengthened alloy and an oxide surface layer.
  • the metal support has longitudinal channels permitting high space velocities with minimal pressure drop.
  • Dalla Betta et al. in U.S. Patent No. 5,259,754 describes a partial oxidation process over a Pd on zirconia catalyst, optionally with another noble metal.
  • Preferred substrates are aluminum-containing steels that are oxidized to form alumina whiskers that are then treated with a zirconium oxide sol.
  • Gaffney et al. in Publication No. U.S. 2002/0177628 Al describe a partial oxidation process over a Ni-Rh monolith catalyst.
  • Dalla Betta et al. in U.S. Patent No. 5,281 ,128 and Kazunori et al. in U.S. Patent No. 5,425,632 describe a 3-stage combustion catalyst system having a first stage with Pd/ZrO 2 on a ceramic honeycomb, a second stage with Pd/ZrO 2 on a Fe/Cr/Al foil, and a third stage with about 20 % Pt on an alumina coating on a Fe/Cr/Al alloy foil.
  • the invention provides a method of providing heat to an endothermic reaction in an integrated combustion reactor, comprising: passing a composition comprising a hydrocarbon fuel and oxygen into a microchannel reaction chamber; wherein the hydrocarbon fuel is at least partially oxidized in the combustion chamber and heat is generated; wherein a thermally conductive wall separates the microchannel reaction chamber from an endothermic reaction chamber; and wherein at least a portion of the heat generated passes through the thermally conductive wall to drive an endothermic reaction occurring in the endothermic reaction chamber.
  • the microchannel reaction chamber includes a combustion catalyst that comprises an alumina support and a catalyst metal.
  • the combustion catalyst comprises alumina and at least 30 weight percent Pt.
  • the invention further provides an integrated combustion microreactor, comprising: a combustion chamber comprising a microchannel comprising a combustion catalyst; an endothermic reaction chamber that is adjacent the combustion chamber, wherein the endothermic reaction chamber comprises an endothermic reaction catalyst; and a thermally conductive wall separating the combustion chamber and the endothermic reaction chamber.
  • the combustion catalyst comprises a support and catalyst metal.
  • the support comprises alumina and the catalyst metal comprises Pt.
  • the catalyst comprises at least 30 weight percent Pt.
  • the invention provides an integrated combustion reactor (ICR) with a continuous combustion channel having at least two zones: a first zone comprising a catalyst that comprises Pt and essentially no Re; and a second zone comprising a catalyst that comprises Pt-Re.
  • ICR integrated combustion reactor
  • the invention provides a method of reacting a fuel composition, comprising: in a reactor with three zones positioned such that a gas can travel from a first zone to a second zone and then to a third zone; passing a first gas composition comprising 60-90 parts (by mole) hydrocarbon, 35-60 parts CO, 100-160 parts H 2 and 90-140 parts O 2 ; reacting the first gas composition in the first zone over a first solid catalyst in the first zone to form a first product gas comprising H 2 O and CO; passing the first product gas into the second zone; reacting a second gas composition in the second zone over a second solid catalyst in the second zone to form a second product gas comprising H 2 O and CO; wherein the second gas composition comprises 10-70 parts (by mole) hydrocarbon, 40-80 parts CO, 20-100 parts H 2 and 30-90 parts O 2 ; passing the second product gas into the third zone; reacting a third gas composition in the third zone over a third solid catalyst in the third zone to form a third product gas comprising H 2 O
  • oxygen conversion in the first zone is greater than 90%, wherein oxygen selectivity for the conversion of H 2 to H 2 O is less than 80% (this assumes hydrogen is much easier to burn than methane) and oxygen selectivity in the first zone for the conversion of hydrocarbon to CO is the same as or greater than the oxygen selectivity for the conversion of CO to CO 2 .
  • the hydrocarbon conversion at the end of the second zone is 50% or greater, the CO conversion is 30% or less, and oxygen selectivity for oxidation of hydrocarbon is 40% or greater.
  • the hydrocarbon conversion is 95% or greater and the CO conversion is 95% or greater.
  • the invention provides a method of reacting a fuel composition, comprising: in a reactor with three zones positioned such that a gas can travel from a first zone to a second zone and then to a third zone; passing a first gas composition comprising hydrocarbon, and O 2 into a first zone; reacting the first gas composition in the first zone, at a first average temperature, over a first solid catalyst in the first zone to form a first product gas comprising H 2 O and CO; wherein oxygen conversion in the first zone is greater than 90%; passing the first product gas into the second zone; reacting a second gas composition in the second zone, at a second average temperature, over a second solid catalyst in the second zone to form a second product gas comprising H 2 O and CO; wherein the second gas composition comprises hydrocarbon, CO, and O 2 ; wherein the hydrocarbon conversion at the end of the second zone is 50% or greater, the CO conversion is 30% or less, wherein oxygen selectivity for oxidation of hydrocarbon is 40% or greater; passing the second product gas into the third zone;
  • the invention provides a method of reacting a fuel composition, comprising: in a reactor with three zones positioned such that a gas can travel through a contiguous bulk flow path from a first zone to a second zone and then to a third zone; passing a first gas composition comprising hydrocarbon, and O 2 into the first zone; reacting the first gas composition in the first zone over a first solid catalyst in the first zone to form a first product gas comprising H 2 O and CO; wherein oxygen conversion in the first zone is greater than 90%; passing the first product gas into the second zone; reacting a second gas composition in the second zone over a second solid catalyst in the second zone to form a second product gas comprising H 2 O and CO; wherein the second gas composition comprises hydrocarbon, CO, and O 2 ; wherein the hydrocarbon conversion at the end of the second zone is 50% or greater, the CO conversion is 30% or less, wherein oxygen selectivity for oxidation of hydrocarbon is 40% or greater; passing the second product gas into the third zone; reacting a third gas composition
  • the methods will be used to generate heat to drive an endothermic reaction.
  • the method oxidizes a hydrocarbon fuel (a compound or compounds containing C-H bonds); in one embodiment, the hydrocarbon contains 90% or greater methane.
  • the average temperature in the third zone is greater than the average temperature in the second zone which is greater than the average temperature in the first zone; in a preferred embodiment, the temperature in the first zone is in the range from 650 to 810 0 C, the temperature in the second zone is in the range from 750 to 830 0 C, and the temperature in the third zone is in the range from 780 to 910 0 C.
  • the catalyst in each zone comprises Pt, with the catalyst in the third zone additionally comprising Re, while Re is substantially without Re.
  • the solid catalyst in one or more of the zones preferably contains at least 30 wt % Pt.
  • each of the first, second and third zones comprises a microchannel (that is, at least one microchannel); and the contiguous bulk flow path is present in the microchannel in each of the first, second and third zones.
  • the first gas composition comprises 60-90 parts (by mole) hydrocarbon, 35-60 parts CO, 100-160 parts H 2 and 90-140 parts O 2 ; and oxygen selectivity in the first zone for the conversion of hydrocarbon to CO is the same as or greater than the oxygen selectivity for the conversion of CO to CO 2 ;
  • the second gas composition comprises 10-70 parts (by mole) hydrocarbon, 40-80 parts CO, 20-100 parts H 2 and 30-90 parts O 2 ;
  • the third gas composition comprises 2-30 parts (by mole) hydrocarbon, 10-40 parts CO, and 20-70 parts O 2 .
  • the hydrocarbon conversion at the end of the third zone is 99% or greater, and the CO conversion is 99% or greater.
  • the zones refer to the descriptions herein, for example, in preferred embodiments the first zone corresponds to the H2/CO zone and the second zone corresponds to the Pox zone.
  • there is a contiguous bulk flow path through the First, second and third zones and contact time of hydrocarbon in the first zone is 40 ms or less, wherein contact time of hydrocarbon in the second zone is 150 ms or less, and wherein contact time of hydrocarbon in the third zone is 500 ms or less.
  • the invention provides a method of making a thermally stable high temperature catalyst, comprising: depositing fumed alumina on a substrate to form a coated ⁇ substrate that comprises a coating comprising fumed alumina, and heat treating the coated substrate.
  • the fumed alumina particles have a surface area of about 40 to about 60 m 2 /g. Coatings made from fumed alumina particles in this size range have surprisingly been found to have superior stability.
  • conversion percent refers to absolute conversion percent throughout these descriptions.
  • Contact time is defined as the total catalyst chamber volume (including the catalyst substrate volume and bulk flow path if present) divided by the total volumetric inlet flowrate of reactants at standard temperature and pressure (STP: 273 K and 1.013 bar absolute).
  • Catalyst chamber volume includes any volume between a catalyst coating (or other flow-by catalyst arrangement) and the opposite wall of a reaction channel.
  • compositions consisting essentially of a set of components allow other components that so not substantially affect the character of the invention, and, similarly, compositions that are "essentially” without a specified element do not contain amounts of the element as would substantially affect the desired properties.
  • the present invention is defined as catalysts or catalyst systems containing stabilized alumina and Pt that are characterized by surprisingly good stability and conversion or selectivity. It may be subsequently discovered that other supports or catalyst metals may perform equivalently if substituted for the stabilized alumina and/or Pt in these catalysts or catalyst systems; however, the inventors are not presently aware of any such equivalent materials.
  • the invention includes methods of combusting, reactors, and systems that use the catalysts described herein.
  • Various embodiments of the invention can provide numerous advantages such as one or more of the following: improved catalyst performance, high stability under high temperature conditions, high conversions at relatively short contact times, selectivity control, lower cost, and ease of manufacturing.
  • FIG. 1 schematically illustrates one design for an integrated combustion reactor.
  • Fig. 2 shows the effect of Pt loading on Pt dispersion in Pt-based catalysts.
  • Fig. 3 shows the effect of platinum loading on a catalyst tested with a gas composition of 2% CH 4 ,
  • Fig. 4 shows the effect of adding Re to the Pt catalyst. Testing conditions (mol%): 2% CH 4 , 4.4% O 2 , 10% H 2 O, 0.68 msec contact time and 85O 0 C.
  • Fig. 5 shows methane conversion over 30% Pt and 8% Re - 19% Pt on 3% La-Al 2 O 3 catalysts that were calcined at 850 0 C and 1000 0 C and tested under fuel lean conditions (2%CH 4 , AA 0 AO 2 ,
  • Fig. 6 shows conversion vs time on stream (TOS) for Pt and Re-Pt powder catalysts on various support materials.
  • Fig. 7 shows BET surface area of 4 support materials as a function of aging time.
  • Fig. 8 shows methane conversion through various powder catalysts under fuel lean conditions
  • Fig. 9 shows performance of 30% Pt on La-stabilized fumed alumina (51 nr/g) on FeCrAlY in a microchannel test apparatus: (a) methane conversion; (b) CO conversion; (c) O 2 conversion; and
  • Fig. 10 shows performance of 30% Pt on La-stabilized fumed alumina (81 m 2 /g) on FeCrAlY in a microchannel test apparatus: (a) methane conversion; (b) CO conversion; (c) O 2 conversion; and
  • FIG. 1 1 shows performance of 30% Pt on La-stabilized fumed alumina (81 m 2 /g) on FeCrAlY in a microchannel test apparatus: (a) methane conversion; (b) CO conversion; (c) O 2 conversion; and
  • Fig. 12 shows performance of 8% Re - 30% Pt on La-stabilized (sol-derived) alumina on FeCrAlY in a microchannel test apparatus: (a) methane conversion; (b) CO conversion; (c) O 2 conversion; and (d) O 2 selectivity.
  • Fig. 13 shows performance of 8% Re - 30% Pt on La-stabilized fumed alumina (81 nr/g) on
  • FeCrAlY in a microchannel test apparatus (a) methane conversion; (b) CO conversion; (c) O 2 conversion; and (d) O 2 selectivity.
  • Fig. 14 shows performance of a catalyst in which Pt was directly applied to FeCrAlY: (a) methane conversion; (b) CO conversion; (c) O 2 conversion; and (d) O 2 selectivity.
  • the FeCrAlY was initially coated with an aluminum layer (by CVD) and an oxide layer grown from the aluminized layer prior to depositing Pt.
  • Fig. 15 shows performance of Re - Pt directly applied to FeCrAlY: (a) methane conversion; (b) CO conversion; (c) O 2 conversion; and (d) O 2 selectivity.
  • the FeCrAlY was initially coated with an aluminum layer (by CVD) and an oxide layer grown from the aluminized layer prior to depositing Pt.
  • Fig. 16 shows performance of Pt on La-stabilized sol-derived alumina on FeCrAlY in a microchannel test apparatus: (a) methane conversion; (b) CO conversion; (c) O 2 conversion; and (d) O 2 selectivity.
  • the FeCrAlY was initially coated with an aluminum layer (by CVD) and an oxide layer grown from the aluminized layer prior to depositing Pt.
  • Fig. 17 shows performance of Pt-Re on La-stabilized sol-derived alumina on FeCrAlY in a microchannel test apparatus: (a) methane conversion; (b) CO conversion; (c) O 2 conversion; and (d) O? selectivity.
  • the FeCrAlY was initially coated with an aluminum layer (by CVD) and an oxide layer grown from the aluminized layer prior to depositing Pt.
  • Fig. 18 shows CH4 conversion for a catalyst prepared as follows: 1 coat La-PVA, 1 coat 20%sol (0.9mg/in 2 ), 1 coat La nitrate, 4 coats (NH 3 ) 4 Pt(OH) 2 (4.0mg/in 2 ); final calcination 85O 0 C 4hrs.
  • Fig. 19 shows CH4 conversion for a catalyst prepared as follows: 1 coat La-PVA, 3 coats 20%sol (2.8mg/in 2 ), 1 coat La nitrate, 7 coats (NHj) 4 Pt(OH) 2 (4.5mg/in 2 ) final calcination 85O 0 C 4hrs.
  • Fig. 20 shows CH4 conversion for a catalyst prepared as follows: 1 coat La-PVA, 3 coats 20%sol (2.8mg/in 2 ), 1 coat La nitrate, 7 coats (NH 3 ) 4 Pt(OH) 2 (4.5mg/in 2 ) final calcination 85O 0 C 4hrs.
  • Fig. 21 shows CH4 conversion for a catalyst prepared as follows: 1 coat La-PVA, 3 coats 20%sol (2.8mg/in 2 ), 1 coat La nitrate, 3 coats (NH 3 ) 4 Pt(OH) 2 (2.5mg/in 2 ) final calcination 85O 0 C 4hrs.
  • the invention comprises a combustion catalyst that includes an alumina support for catalytically active material or materials.
  • An "alumina support” contains aluminum atoms bonded to oxygen atoms, and additional elements can be present.
  • the alumina support comprises a stabilizing element or elements that improve the stability of the catalyst in conditions accompanying the high temperature combustion of hydrocarbons. Stabilizing elements typically are large, highly charged cations.
  • the alumina support is stabilized by La.
  • a "stabilized alumina support” is an alumina support containing at least one stabilizing element.
  • the stabilized alumina support contains 1 to 10, more preferably 3 to 7 weight percent of a stabilizing element or elements (preferably La).
  • the combustion catalyst preferably contains Pt.
  • the platinum content in a catalyst can be described either in terms of weight percent or in terms of mass per geometric surface area of substrate. Weight percent is based on the weight of platinum as a percent of catalyst powder, catalyst pellets, or washcoat; it does not include the weight of an underlying substrate and does not include the weight of interlayers between a washcoat (or washcoats) and an underlying substrate. For example, in the case of an alloy felt washcoated with alumina and Pt, the weight % would be PtZ(Pt + AI 2 O 3 ) x 100%.
  • the catalyst contains at least 30 wt % Pt, preferably at least 50 wt%, in some embodiments at least 70 wt%, and in some embodiments 30 to 90 wt %.
  • the catalyst contains at least 3.0 mg/in 2 Pt, more preferably 4.5 mg/in 2 Pt (15 mg/in 2 of a 30 wt % Pt on alumina washcoat), in some preferred embodiments at least 6 mg/in 2 Pt, and in some embodiments 6 to 12 mg/in 2 Pt.
  • the area refers to the geometrical area of the substrate; for a flat surface such as a foil or coupon, this area is quite simple, for a honeycomb or finned substrate or reaction channel, it would include all the surfaces that are coated by catalyst.
  • the amount of Pt or the weight percent of Pt can be determined by known methods of chemical analysis.
  • a stabilized alumina layer is coated over, and preferably in direct contact with, a high surface area material such as alumina, preferably (gamma)-alumina.
  • a high surface area material such as alumina, preferably (gamma)-alumina.
  • This configuration provides high surface area for good metal dispersion and/or high metal loadings and also provides a stabilized alumina layer for excellent stability.
  • the high surface area material is porous; the meaning of a stabilized alumina "disposed over" or “coated over" a high surface area material means that the stabilized alumina may also coat crevices and cavities within a high surface area material (such as gamma-alumina) or within a large pore substrate (such as a felt).
  • the catalyst comprises a metal, ceramic or composite substrate having a layer or layers of a catalyst material or materials deposited thereon.
  • the substrate is thermally conductive.
  • a preferred substrate is a finned substrate that is characterized by the presence of fins (such as square-wave type fins) on the substrate's surface. These fins may, for example, take the form of fins etched in the wall of an integrated reactor or a finned insert (such as a flat metal plate with one grooved surface) that can be inserted into a combustion chamber of a microreactor. In some cases, the reactor can be refurbished by replacing an insert.
  • One method of fabrication within a microchannel comprises the use of a slitting saw, partial etching using a photochemical process, or a laser EDM.
  • This type of support provides numerous advantages including: high heat flux with short heat transfer distances, high surface area, and low pressure drop.
  • the support has a height (including fins) of less than 5 mm and preferably less than 2 mm and a fin-to-fin separation of 1000 ⁇ m or less, and in some embodiments, a fin-to-fin separation of 150 to 500 ⁇ m.
  • the catalyst may take any conventional form such as a powder or pellet.
  • the catalyst includes an underlying large pore substrate. Examples of preferred large pore substrates include commercially available metal foams and metal felts.
  • a "large pore substrate” Prior to depositing any coatings, a "large pore substrate” has a porosity of at least 5%, more preferably 30 to 99%, and still more preferably 70 to 98%.
  • a large pore substrate has a volumetric average pore size, as measured by BET, of 0.1 ⁇ m or greater, more preferably between 1 and 500 ⁇ m.
  • Preferred forms of porous substrates include foams and felts and these are preferably made of a thermally stable and conductive material, preferably a metal such as stainless steel or FeCrAlY alloy. These porous substrates can be thin, such as between 0.1 and 1 mm. Foams are continuous structures with continuous walls defining pores throughout the structure.
  • Felts are nonwoven fibers with interstitial spaces between fibers and include tangled strands like steel wool. Felts are conventionally defined as being made of nonwoven fibers.
  • the large-pore substrate has a corrugated shape that could be placed in a reaction chamber (preferably a small channel) of a steam reformer.
  • a reaction chamber preferably a small channel
  • Various substrates and substrate configurations are described in U.S. Patent No. 6,680,044 which is incorporated by reference.
  • a catalyst having a large pore support (and including the alumina-supported catalytically active sites) preferably has a pore volume of 5 to 98%, more preferably 30 to 95% of the total porous material's volume, with at least 20% (more preferably at least 50%) of the material's pore volume is composed of pores in the size (diameter) range of 0.1 to 300 microns, more preferably 0.3 to 200 microns, and still more preferably 1 to 100 microns. Pore volume and pore size distribution are measured by mercury porisimetry (assuming cylindrical geometry of the pores) and nitrogen adsorption.
  • the catalyst including the presence of catalytically active surface sites, as measured by BET, has a volumetric average pore size of less than 0.1 micrometer ( ⁇ m).
  • Some catalysts of this invention have a surface area, as measured by N 2 adsorption BET, of at least 5 nr/g, more preferably at least 10 m 2 /g, and in some embodiments 5 to about 50 m 2 /g; and preferably maintain a surface area at or above these values after exposure to air at 1000 0 C for 200 hours.
  • a catalyst support can be made from a composition that includes an alumina precursor.
  • An "aluminum precursor” is any form of aluminum (such as an alumina slurry) that can be used to form solid alumina.
  • the catalyst may be made starting from an alumina sol and/or solid alumina (including fumed alumina). Suitable, commercially available materials include colloidal alumina suspended in aqueous medium from Sasol, or Engelhard alumina ground to a particle size of 70- 100 mesh.
  • the alumina precursor comprises fumed alumina particles. Fumed alumina is typically made by oxidizing aluminum chloride and is typically in the form of highly stable nanoparticles.
  • an alumina slurry or sol can be coated over the substrate at any stage in the preparative process.
  • particles of a stabilized and heat- treated alumina can be slurry coated onto the substrate followed by depositing, drying and activating a metal via the impregnation method.
  • a vapor coat or soluble form of alumina could be applied onto a substrate prior to addition of a catalytic metal.
  • the substrate may be coated with a buffer layer formed in situ using chemical vapor deposition.
  • the buffer layer may not have a high surface area, but may be used to create a layer with a CTE (coefficient of thermal expansion) between that of the base metal substrate and that of the higher surface area catalyst support to promote good adhesion of the layers.
  • the buffer layer may also be used to inhibit corrosion of the base metal substrate by creating a near dense and almost pin-hole free coating.
  • solution such as spray coating
  • slurry coating is typically less expensive, vapor coating of the various materials could also be employed.
  • a buffer layer is formed by vapor depositing a layer of aluminum that is heat treated in air to form a layer of alumina. A hydrothermal or thermal pre- aging treatment of a buffer layer can be conducted either before or after applying an alumina washcoat to a substrate.
  • Hydrocarbons according to the present invention include: alkanes, alkenes, alkynes, alcohols, aromatics, and combinations thereof including fuels such as gasoline, kerosene, diesel, JP-8.
  • hydrocarbons refers to fuels containing C-H bonds that combust to produce heat; although not desirable in a combustion fuel, less preferred embodiments of a "hydrocarbon” may include, for example, alcohols; since these can be combusted.
  • the hydrocarbon is an alkane or a fuel.
  • Preferred alkanes are C
  • fuel comprises methane, ethane, propane, butane, or combinations of these.
  • the preferred oxidant is oxygen which, in some preferred embodiments, is in the form of air.
  • the present invention includes methods and systems in which a combustion catalyst is disposed within a microchannel reaction channel.
  • the height and/or width of a reaction microchannel is preferably 5 mm or less, and more preferably 2 mm or less, and in some embodiments 50 to 1000 ⁇ m. Both height and width are perpendicular to the direction of flow.
  • the length of a reaction channel is parallel to flow through the channel and is typically longer than height and width.
  • the length of a reaction chamber is greater than 1 cm, more preferably in the range of 1 to 100 cm.
  • the sides of the reaction channel are defined by reaction channel walls.
  • reaction chamber walls are preferably made of a hard material such as a ceramic, an iron based alloy such as steel, or a nickel-based alloy.
  • the reaction chamber walls are comprised of stainless steel or inconel which is durable and has good thermal conductivity.
  • a combustion microchannel can be straight, curved or have a complex shape. Typically, the combustion channel will be adjacent to and conformal with an endothermic reaction channel.
  • fuel and oxidant enter together at the entrance of a channel; however, this configuration can lead to a hot spot wherever the conditions are sufficient for combustion, and may even lead to detonation.
  • the fuel or oxidant is added in a staged fashion along the length of channel; this allows careful control of temperature profile along the length of microchannel. The temperature may rise monotonically in a linear fashion or may rise more quickly near either the front or end of the catalyst bed.
  • the section of the catalyst-containing microchannel that exceeds 800 0 C may only include the final 75%, or 50%, or 25%, or 10% of the catalyst bed, or any value therewithin.
  • the reaction may equilibrate near 840 0 C and demonstrate an approach to equilibrium greater than 80% as defined by the peak temperature.
  • the equivalent contact time spent in the reaction zone that exceeds 800 0 C may be considerably less than the overall reaction contact time as defined by the entire reaction channel volume (i.e., the volume of the channel containing catalyst).
  • the contact time within the entire reaction channel volume may be 5 ms, but only 1 ms in the reactor section at temperatures in the range of 800 to 850 0 C.
  • the temperature of the catalyst-containing microchannel may be highest near the end of the reaction zone, or, alternatively, may be higher near the front or middle of the reactor rather than near the end of the reaction zone.
  • a fuel i.e., hydrocarbon
  • the oxygen then passes through orifices 12 where it combines with the hydrocarbon.
  • a combustion catalyst 14 can be disposed in the channel where oxygen and hydrocarbon combine.
  • the combusted gases flow out of the device through exhaust channel 16. Heat from the combustion passes through wall 18 to endothermic reaction channel 20.
  • integrated combustion reactors can take many other configurations; for example, with reference to Fig. 1 , a mixture of hydrocarbon and oxygen could be passed into Fluid B inlet where they combust to provide heat for an endothermic reaction in the channel connected to the Fluid A inlet.
  • microchannel or non- microchannel endothermic reaction channels may be present.
  • MicroChannel reaction channels are preferred. Having combustion microchannels adjacent endothermic reaction channels enable temperature in the reaction channels to be controlled precisely to promote steam reforming, or other endothermic reaction, and minimize unselective reactions in the gas phase.
  • the thickness of a wall between adjacent process channels and combustion channels is preferably 5 mm or less.
  • Each of the process or combustion channels may be further subdivided with parallel subchannels.
  • the flow through adjacent endothermic reaction and combustion channels may be cross flow, counter-flow or co-fiow.
  • combustion channels may be formed of a fuel subchannel and a oxidant subchannel that are connected to allow the controlled mixing of fuel and oxidant (sometimes called staged addition).
  • a hydrocarbon fuel can be added at one end of a fuel subchannel and oxygen is added from an adjacent oxygen subchannel through holes along the length (typically only part of the total length) of the fuel subchannel.
  • the combustion channels have a u-shape in which fuel enters one end of the "u,” is combusted, and exhaust exits from the other side of the "u.”
  • a hydrocarbon fuel such as methane further comprises hydrogen and CO (such as might be come from a part of the product stream of a steam reforming reaction that is powered by the combustion reaction) and this mixture is combusted with oxygen in a first zone of a combustion channel.
  • the hydrogen combusts quickly and a second zone of the combustion channel contains a fuel-rich mixture of hydrocarbon, CO and oxygen.
  • a third zone (the afterburner or exhaust zone) contains a fuel-lean mixture of hydrocarbon, CO and oxygen.
  • the reactors preferably include a plurality of microchannel reaction channels and/or a plurality of adjacent combustion microchannels.
  • a plurality of combustion microchannels may contain, for example, 2, 10, 100, 1000 or more channels.
  • multiple combustion layers are interleaved with multiple reaction microchannels (for example, at least 10 combustion layers interleaved with at least 10 layers of reaction microchannels).
  • 3 alternating, interleaved layers would comprise layers in the order combustion : reaction : combustion : reaction : combustion : reaction.
  • flow into and/or out of some or all of a plurality of combustion and/or endothermic reaction channels passes through a manifold or manifolds that combines or distributes the fluid flow.
  • microchannels are arranged in parallel arrays of planar microchannels; preferably a layer comprising a parallel array of planar microchannels is adjacent with another layer comprising a parallel array of planar microchannels where the adjacent layers exchange heat.
  • Preferred reactors usable in the present invention include those of the microcomponent sheet architecture variety (for example, a laminate with microchannels). Examples of integrated combustion reactors that could be used in the present invention are described in U.S. patent application serial no. 10/222,196, filed Aug. 15, 2002, which is incorporated herein by reference. Some other suitable reactor designs and methods of making reactors are disclosed in U.S. patent application serial no. 10/306,722, filed November 27, 2002, and 10/408,744, filed April 7, 2003, which are also incorporated herein, in full, by reference.
  • reactors, catalysts and chemical systems of the present invention can also be described in terms of the data presented in the examples section.
  • a preferred reactor of the invention can be characterized by testing under the conditions of run plan 2 (see Examples section) to obtain a given level of conversion or selectivity.
  • inventive reactors, catalysts and chemical systems can be characterized by a selected level of conversion or selectivity when tested under the conditions of any of run plans 1-10.
  • These layers may also be described as "about” or "at least about” or “no more than about” the values shown in the Examples; it should be understood that these values are characteristic of various embodiments of the invention that can be obtained through routine experimentation in view of the descriptions herein.
  • the catalyst can fill up a cross-section of a combustion and/or endothermic reaction channel (a flow-through catalyst) or only occupy a portion of the cross-section of a reaction channel (flow-by).
  • a flow-by catalyst configuration can create an advantageous capacity/pressure drop relationship.
  • gas preferably flows in a 0.1-2.0 mm gap adjacent to a catalyst insert or a thin layer of catalyst that contacts a microchannel wall (preferably the microchannel wall that contacts the catalyst is in direct thermal contact with a endothermic reaction channel, preferably an endothermic reaction process stream contacts the opposite side of the wall that contacts the catalyst).
  • bulk flow path refers to an open path (contiguous bulk flow region) within the reaction chamber.
  • a contiguous bulk flow region allows rapid gas flow through the reaction chamber without large pressure drops.
  • Bulk flow regions within each reaction channel preferably have a cross-sectional area of 5 x 10 "8 to 1 x 10 "2 m 2 , more preferably 5 x 10 "7 to 1 x 10 "4 m 2 .
  • the bulk flow regions preferably comprise at least 5%, more preferably 30-80% of either 1) the internal volume of the reaction chamber, or 2) the cross-section of the reaction channel.
  • One example of a bulk flow path is the space between fins in a finned catalyst.
  • the endothermic reaction channel(s) also preferably contains a bulk flow path having the properties discussed above.
  • the present invention also provides methods of combustion in which a hydrocarbon is reacted with oxygen at short residence times (or alternatively, described in contact times) over the catalysts described herein.
  • the residence time is preferably less than 0.1 s.
  • short contact times e.g., hydrocarbon contact time
  • Combustion reactions are preferably carried out at more than 650 0 C, more preferably more than 750 0 C, and in some embodiments in the range of 675 to 900 0 C.
  • the reaction can be run over a broad pressure range from sub-ambient to very high, in some embodiments the process is conducted at a pressure of from 1 atm to 10 atm, more preferably 1 atm to 2 atm.
  • the combustion reaction conditions can be described as having three zones: an initial, fuel-rich zone (that may also contain H 2 and CO) called the H 2 /CO zone; a middle partial oxidation (or POx) zone, and a fuel lean zone called the afterburner zone.
  • H 2 /CO zone an initial, fuel-rich zone (that may also contain H 2 and CO) called the H 2 /CO zone
  • POx middle partial oxidation
  • afterburner zone Typically, these three zones are not distinct, but one zone gradually changes into the next. Fuel compositions in these zones are described at the start of a zone.
  • Hydrocarbon conversion is preferably at least 50%, more preferably at least 80% and still more preferably at least 90%.
  • the foregoing conversion values can be either absolute or equilibrium conversions. If not specified, conversion refers to absolute conversion. Under conditions where conversion approaches 100% (as is the case in oxygen-rich, fuel-lean environments), absolute and equilibrium conversion is the same. "Equilibrium conversion” is defined in the classical manner, where the maximum attainable conversion is a function of the reactor temperature, pressure, and feed composition. In some embodiments, hydrocarbon equilibrium conversion is in the range of 70 to 100%.
  • Hydrocarbon can be a mixture of hydrocarbons, or, in some embodiments, the term "hydrocarbon” could be replaced by “methane” in any of the descriptions herein.
  • the amounts of "hydrocarbon” are based on methane and it should be understood that for heavier fuels the flow rate would be reduced proportionately based on the conversion to CO 2 and H 2 O; for example, for ethane the flow rate should be adjusted considering the stoichiometric ratio of oxygen to ethane now is 3.5 rather than 2.0 for oxygen to methane. So, if a patent claim states * 'a flow rate of 1.0 cc hydrocarbon", this means a flow rate of 1.0 cc methane or 0.57 cc ethane, etc.
  • the maximum temperature is preferably 810 0 C or less, more preferably 800 0 C or less, and in some embodiments the temperature is in the range of 670 0 C to 800 0 C.
  • the partial pressure of H 2 is preferably at least 0.13 atm, in some embodiments in the range of 0.1 1 to 0.27 atm.
  • the partial pressure of hydrocarbon is CO is preferably at least 0.044 atm, in some embodiments in the range of 0.04 to 0.1 atm.
  • the partial pressure of hydrocarbon is preferably at least 0.071 atm, in some embodiments in the range of 0.064 to 0.16 atm.
  • mole fractions of hydrocarbon, H 2 , CO, and O 2 are in the range of 0.06-0.08, 0.1 1- 0.13, 0.04-0.05 and 0.1-0.12.
  • Contact time of fuel (including both H 2 and hydrocarbon) in the H 2 /CO zone is preferably 5 msec or less, more preferably 2.8 msec or less, and in some embodiments is in the range of 2 to 5 msec.
  • Contact time of hydrocarbon in the H 2 /CO zone is preferably 200 msec or less, more preferably 40 msec or less, more preferably 20 msec or less, and in some embodiments is in the range of 5 to 20 msec.
  • Conversion of hydrocarbon in the H 2 /CO zone is preferably at least 40%, more preferably at least 50%, and in some embodiments 40 to 60%.
  • relative amounts (by mole) of various components entering the H 2 /CO zone are 50-100 parts hydrocarbon, 35-60 parts CO, 120-150 parts H 2 , and 80-140 parts O 2 , and in some embodiments, 60-90 parts hydrocarbon, 35-60 parts CO, 100-150 parts H 2 , and 100- 120 parts O 2 .
  • the hydrocarbon conversion is preferably at least 40%, in some embodiments 40 to about 70%, O 2 conversion is preferably at least 40%, oxygen selectivity to H 2 O is preferably 80% or less, more preferably less than 75%, and the oxygen selectivity of hydrocarbon to CO is the same or greater than the oxygen selectivity of CO to CO 2 .
  • O 2 is assumed to be used for converting CO to CO 2 , CH 4 to CO and H 2 , H 2 to H 2 O, and CH 4 to H 2 O.
  • the percent of O 2 used to selectively oxidize each of above mentioned compounds is calculated as O 2 selectivity.
  • the maximum temperature is preferably 850 0 C or less, in some embodiments 820 0 C or less, and in some embodiments the temperature is in the range of 750 to 850 0 C.
  • the partial pressure of H 2 is typically 0.02-0.07 atm.
  • the partial pressure of CO is preferably at least 0.03 atm, in some embodiments in the range of 0.03 to 0.1 atm.
  • the partial pressure of hydrocarbon is preferably at least 0.01 atm, in some embodiments in the range of 0.01 to 0.08 atm.
  • mole fractions of hydrocarbon, CO, and O 2 are preferably in the range of 0.01-0.04, 0.03-0.06 and 0.02-0.06, respectively.
  • Contact time of hydrocarbon in the POx zone is preferably at least 1.5 times that of the H 2 /CO zone, preferably 200 msec or less, more preferably 40 msec or less, in some embodiments 10 to 40 msec, even more preferably 20 msec or less, and in some embodiments 10 to 20 msec.
  • relative amounts (by mole) of various components entering the POx zone are 15-50 parts hydrocarbon, 50-70 parts CO, 20-80 parts H 2 , and 20-100 parts O 2 , and in some embodiments, 10-70 parts hydrocarbon, 30- 90 parts CO, 10-100 parts H 2 , and 25-70 parts O 2 .
  • Conversion of hydrocarbon through the POx zone is preferably at least 35%, more preferably at least 50%, more preferably at least 60% and in some embodiments 40 to 80%. Conversion of CO through the POx zone is preferably 30% or less, more preferably 20% or less. Oxygen selectivity of hydrocarbon to CO through the POx zone is preferably at least 40%, more preferably at least 50%, and in some embodiments in the range of 40 to 50%.
  • the maximum temperature is preferably 920 0 C or less, in some embodiments 850 0 C or less, and in some embodiments the maximum temperature is in the range of 750 to 900 0 C.
  • the partial pressure of CO entering the afterburner zone is preferably at least 0.02 atm, in some embodiments in the range of 0.015 to 0.045 atm.
  • the partial pressure of hydrocarbon entering the afterburner zone is preferably at least 0.006 atm, in some embodiments in the range of 0.005 to 0.015 atm.
  • mole fractions of hydrocarbon, H 2 , CO, and O 2 are preferably in the range of 0.005-0.007, 0.006-0.008, and 0.04-0.05, respectively.
  • contact time of fuel in the afterburner zone is preferably at least 3.0 times the contact time in the H 2 /CO zone, preferably 1 sec or less, more preferably 500 msec or less, and in some embodiments is in the range of 50-500 msec.
  • relative amounts (by mole) of various components entering the afterburner zone are 1-20 parts hydrocarbon, 10-50 parts CO, 0-20 parts H 2 , and 20-100 parts O 2 , and in some embodiments, 2-10 parts hydrocarbon, 10-30 parts CO, 0-10 parts H 2 , and 30-60 parts O 2 .
  • Conversion of hydrocarbon in the afterburner zone is preferably at least 93%, more preferably at least 95%, more preferably at least 99%, and in some embodiments 93 to 100%. Conversion of CO in the afterburner zone is preferably at least 93%, more preferably at least 95%, more preferably at least 99%, and in some embodiments 93 to 100%.
  • the amounts of gases in each zone refer to components entering a zone. So the simplest case would be where all the components enter a zone together; however, one or more components could also be added in a distributed fashion along the length of a zone, or be added mid-zone, etc., and these would also be counted as entering the zone.
  • the catalyst is characterizable by the levels of stability and/or reactivity shown in the examples.
  • the catalyst (or reactor) is characterizable such that when exposed to a gas composition of 2% CH 4 , 4.4% O 2 , 10% H 2 O, at 0.68 msec contact time and 900°C for 100 hours continuous TOS, more preferably after 300 hours continuous TOS, at least about 80% of the methane is converted.
  • a catalyst's properties are defined by the following test procedure (referred to as "Test Procedure 1") and is based on the reactions described in the Examples in the section entitled “MicroChannel Insert Testing”. Catalysts should be tested as (or on) an insert in the test reactor. Reactors and systems can be characterized by adjusting the flow rates to obtain the same contact times as in the run plans. In this test procedure (which can be further understood with reference to the Examples), the catalyst is coated on to a FeCrAlY or aluminized alloy 617 substrate which is inserted into a single microchannel test reactor with a 10 mil gap for the reactant gases.
  • the catalysts are tested in three simulated gas compositions, namely H2/CO, POX, and Afterburner zones, where the gas compositions are shown in the table below: mole-f l ⁇ nol s 02 CO2 CH4 H2O H2 CO N2 O2.CH4 O2 f CO
  • the H 2 /CO zone consists Of H 2 , CO, and CH 4 as fuel at O 2 /CH 4 ratio of 1.54 and O 2 /CO ratio of 2.46 and temperature range lies between 675 to 800°C.
  • POX 1 -3 zones consist of similar streams at O 2 /CH 4 ratios ranging from 1.39-1.8 and O 2 /CO ratios ranging from 1.02-0.62 with temperature ranging from 737-825 0 C.
  • O 2 /CH 4 ratio of 7.34 and O 2 /CO ratio of 2.38 and temperature range lies between 830 to 900 0 C.
  • Nitrogen flowrate (seem) 265 265 265 601 799 929 615 615 615 615 615
  • the support material was La-stabilized alumina derived from Sasol 14N4-80 Boehmite which was calcined at 1000 0 C for 4hrs.
  • Precursor materials for metal solutions included perrhenic acid and tetraammineplatinum hydroxide.
  • a desired amount of perrhenic acid was impregnated First to incipient wetness and calcined at 45O 0 C for l hr, then tetraammineplatinum hydroxide was impregnated to incipient wetness and inter-calcined at 45O 0 C for lhr. Multiple impregnations were conducted and the final calcination temperature was between 850 to 1000 0 C.
  • MicroChannel Insert Testing Catalyst inserts were tested in a two inch long microreactor designed for fast screening of catalysts using an insertable coated coupon.
  • the reactor is made from a 0.5" OD alloy 617 rod which is 2" long.
  • the insertable coupons were made with either FeCrAlY or aluminized (CVD of alumina layer) alloy 617 and sized to 1.0" x 0.375" x 0.02".
  • a slot sized 0.377" x 0.021" x 2" was cut at the center to fit the insert and another slot adjacent to the insert is EDM (electro discharge machining) wire cut at 0.335" x 0.01 " x 2" for reactant gases to flow by the catalyst insert.
  • FeCrAlY coupons were heat treated in air at 1000 0 C for 8hrs to grow native aluminum oxide.
  • a alumina support typically stabilized
  • a catalyst metal or metals
  • the heat treated inserts were coated with slurry catalyst.
  • powder catalysts were ball milled for 24 hrs in slurry whose pH was adjusted to 4, 5 wt% solid content of Boehmite (18N4-80, Sasol) was added to the slurry before coating to the coupon, and the catalyst loading was targeted at 15mg/in 2 .
  • catalysts having supports made from fumed alumina were made by a process including three steps: 1) preparation of the support from 80% fumed alumina and 20% sol alumina, 2) stabilization of the support with La or Mg, and 3) impregnation of the stable support with active metal via incipient wetness.
  • step # 3 If the % moisture is more than 1 % then pre-calcine the material for 4 hour at 300°C before going to step # 3.
  • composition of the catalyst is: 30%Pt (metal) + 70% total support (6%La(metal) + 94%Alumina oxide)
  • Pt catalysts It is believed that the more metal is loaded to the surface, the more difficult it will be to disperse, thus forming big agglomerations. The difference in the dispersion of 30%Pt and 50%Pt catalysts is almost negligible, within the experimental error limits. Thus we conclude that there is not too much additional drop in metal dispersion once the loading surpasses 30%.
  • the method of preparation of the 50%Pt catalyst was different than the other two, because Pt "black” and alpha alumina (Engelhard) were mixed and bound by 5wt% Boehinite (18N4-80, Sasol) as opposed to depositing Pt(NH 3 ⁇ (OH) 2 precursor onto 3%La-Al 2 O 3 support by the incipient wetness technique.
  • Figure 3 shows the effect of Pt loading supported on La stabilized alumina impregnated with tetraammine platinum hydroxide.
  • the initial activity of the 50% Pt catalyst was lower than the 30%Pt catalyst but at 150 hours of operation, the activity was found very similar to the latter catalyst.
  • Figure 6 shows the results of lifetime screening for several formulations.
  • the lowest conversion was the baseline performance of 30%Pt/La-Al 2 ⁇ 3 (sol) calcined at 85O 0 C.
  • Initial methane conversion was high at 95+% but in 150 hours on stream, activity declined to 80% level.
  • the stability of the catalyst was improved and at 100 hours, the conversion level was 7-8% higher than that of 30% Pt.
  • Zr was incorporated into the support material, the conversion profile looked very similar to the Re-Pt catalyst without Zr.
  • Figure 7 shows the BET surface area of various support materials at aging times of 0, 24, and 100 hours. Aging of the materials was carried out in air at 1000 0 C. The highest initial surface area was achieved with La-stabilized alumina derived from sol. However, a decrease in surface area was observed until 200hrs. For fumed alumina containing supports, the initial surface area was lower on both 81 AA and 51AA; however, the relative change within 100 hrs was significantly smaller than the La/alumina (sol) sample. Surprisingly, the 51AA support was more stable than the 81AA sample. When Zr was incorporated into the La-fumed alumina (51), the initial surface area was the lowest among all four samples but appeared stable. Thus, applicants have shown that an active catalyst can be prepared on a support that is highly thermally stable with a surface area that changes by 10% or less (preferably 5% or less) after exposure to air for 24 hour.
  • Figure 8 shows the activity of catalysts under afterburner zone conditions (0.6%CH 4 , 4.7%O 2 , 2%CO, 0.7%H 2 , 14%H 2 O, 850 0 C, 9ms) for methane conversion.
  • the catalysts tested were 30%Pt, 8%Re-19%Pt, 8%Re-30%Pt, and trimetallic catalysts (19%Pt/10%Pd/7%Rh/3%La- AI 2 O 3 ). All catalysts outperformed the trimetallic catalyst. The presence of Rh and/or Pd inhibited the catalytic activity under these conditions.
  • Figures 9 (a-d) are the results for 30%Pt/La-fumed alumina (51 m 2 /g) calcined at 850 0 C on FeCrAlY substrate. High methane conversion in the Pox zone was obtained and the target conversion was met in the afterburner zone except for the point 9. Complete CO conversion was obtained in the afterburner zone; however, 100% utilization of oxygen was not attained in the
  • Figures 10 show data for 30%Pt/La-fumed alumina (81 AA) calcined at 85O 0 C on a FeCrAlY substrate.
  • the initial activity in H 2 /CO and Pox zones for methane conversion was significantly improved.
  • Particularly in the POX zone near 90% conversion was achieved.
  • Oxygen utilization (conversion) was also improved in these zones.
  • activity was about the same regardless of the type of fumed alumina.
  • the 2 nd day data for run points 3 and 4 showed some deactivation of the catalyst took place.
  • aqueous metal solution used as precursors were directly applied at room temperature.
  • 9% (atomic Pt) of tetraammineplatinum hydroxide solution was used.
  • the coupon was calcined at 45O 0 C for lhr in air. Once the desired weight gain was achieved, the coupon was calcined at 85O 0 C for 4hrs in air for the final calcination.
  • perrhenic acid or ammonium perrhenate can be used and was coated first before Pt was applied. The same calcinations protocol was used.
  • a sequential coating method (building catalyst in-situ) has also been studied.
  • La-PVA was coated on an aluminized coupon (the coupon was aluminized by CVD and thermally oxidized), then 7 layers of 20% alumina sol, 1 layer of 10% La nitrate, and 3 layers of 10% solution of tetraammineplatinum nitrate were sequentially coated on the coupon.
  • Figures 16 (a-d) present the results on this catalyst. In H 2 /CO and POX zones, this catalyst exceeded the target values significantly with great reproducibility data on the second day. In the afterburner zone, activity was comparable to that over slurry coated catalyst.
  • alumina sol can be strongly adhered on the aluminized surface for 1000 hrs under a simulated combustion exhaust environment.

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Abstract

L'invention concerne des catalyseurs contenant de préférence au moins 30 % en poids de platine. Ces catalyseurs présentent, de manière surprenante, une stabilité et une activité supérieures pour catalyser des réactions de combustion. L'ajout de rhénium permet d'améliorer la performance catalytique dans des conditions pauvres en fuel, mais présente des effets indésirables dans des conditions riches en fuel. L'invention concerne des microréacteurs de combustion intégrés, des systèmes chimiques faisant appel à ces microréacteurs, des méthodes de combustion et des méthodes pour fournir de la chaleur à des réactions endothermiques dans des microréacteurs de combustion intégrés. L'invention concerne également des méthodes de combustion d'un combustible dans un réacteur comprenant au moins trois zones, chaque zone contenant un catalyseur solide. L'invention concerne encore une méthode de fabrication d'un support d'alumine thermiquement stable à partir d'alumine sublimée.
PCT/US2005/037290 2004-10-15 2005-10-14 Combustion a haute temperature catalysee et stable dans des reacteurs de combustion integres a microcanaux, methodes de mise en oeuvre de combustion catalytique dans un reacteur multizone et methode de fabrication d'un support catalytique thermiquement stable Ceased WO2006044819A2 (fr)

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US10/966,158 US7566441B2 (en) 2004-10-15 2004-10-15 Methods of conducting catalytic combustion in a multizone reactor, and a method of making a thermally stable catalyst support
US10/966,162 2004-10-15
US10/966,162 US8062623B2 (en) 2004-10-15 2004-10-15 Stable, catalyzed, high temperature combustion in microchannel, integrated combustion reactors
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US11655421B2 (en) 2016-12-23 2023-05-23 Carbon Engineering Ltd. Method and system for synthesizing fuel from dilute carbon dioxide source

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US6117578A (en) * 1998-04-16 2000-09-12 International Fuel Cells, Llc Catalyzed wall fuel gas reformer
DE19825102C2 (de) * 1998-06-05 2001-09-27 Xcellsis Gmbh Verfahren zur Herstellung eines kompakten katalytischen Reaktors
DE19832386A1 (de) * 1998-07-18 2000-01-27 Dbb Fuel Cell Engines Gmbh Reformierungsreaktor mit katalytischer Brennereinheit
EP1195196A1 (fr) * 2000-10-06 2002-04-10 Akzo Nobel N.V. Support pour un catalyseur comprenant un papier à fibres imprégné avec des micro-fibres, procédé pour sa production et ses utilisations
US6960235B2 (en) * 2001-12-05 2005-11-01 The Regents Of The University Of California Chemical microreactor and method thereof
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Publication number Priority date Publication date Assignee Title
US11655421B2 (en) 2016-12-23 2023-05-23 Carbon Engineering Ltd. Method and system for synthesizing fuel from dilute carbon dioxide source
US12344803B2 (en) 2016-12-23 2025-07-01 Carbon Engineering Ulc Method and system for synthesizing fuel from dilute carbon dioxide source

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