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WO2012135583A1 - Appareil et procédés pour le reformage d'éthanol à basse température à l'aide de catalyseurs pulvérulents - Google Patents

Appareil et procédés pour le reformage d'éthanol à basse température à l'aide de catalyseurs pulvérulents Download PDF

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Publication number
WO2012135583A1
WO2012135583A1 PCT/US2012/031382 US2012031382W WO2012135583A1 WO 2012135583 A1 WO2012135583 A1 WO 2012135583A1 US 2012031382 W US2012031382 W US 2012031382W WO 2012135583 A1 WO2012135583 A1 WO 2012135583A1
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WIPO (PCT)
Prior art keywords
catalyst
reformer
alcohol
exhaust
reforming
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PCT/US2012/031382
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English (en)
Inventor
David A. Morgenstern
Erik D. Sall
James W. Taylor
Kandaswamy Duraiswamy
Anand S. Chellappa
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Monsanto Technology Llc
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Publication of WO2012135583A1 publication Critical patent/WO2012135583A1/fr

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    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J19/00—Chemical, physical or physico-chemical processes in general; Their relevant apparatus
    • B01J19/24—Stationary reactors without moving elements inside
    • B01J19/248—Reactors comprising multiple separated flow channels
    • B01J19/2495—Net-type reactors
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J8/00—Chemical or physical processes in general, conducted in the presence of fluids and solid particles; Apparatus for such processes
    • B01J8/02—Chemical or physical processes in general, conducted in the presence of fluids and solid particles; Apparatus for such processes with stationary particles, e.g. in fixed beds
    • B01J8/06—Chemical or physical processes in general, conducted in the presence of fluids and solid particles; Apparatus for such processes with stationary particles, e.g. in fixed beds in tube reactors; the solid particles being arranged in tubes
    • B01J8/065—Feeding reactive fluids
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J8/00—Chemical or physical processes in general, conducted in the presence of fluids and solid particles; Apparatus for such processes
    • B01J8/02—Chemical or physical processes in general, conducted in the presence of fluids and solid particles; Apparatus for such processes with stationary particles, e.g. in fixed beds
    • B01J8/06—Chemical or physical processes in general, conducted in the presence of fluids and solid particles; Apparatus for such processes with stationary particles, e.g. in fixed beds in tube reactors; the solid particles being arranged in tubes
    • B01J8/067—Heating or cooling the reactor
    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
    • C01B3/00—Hydrogen; Gaseous mixtures containing hydrogen; Separation of hydrogen from mixtures containing it; Purification of hydrogen
    • C01B3/02—Production of hydrogen or of gaseous mixtures containing a substantial proportion of hydrogen
    • C01B3/32—Production of hydrogen or of gaseous mixtures containing a substantial proportion of hydrogen by reaction of gaseous or liquid organic compounds with gasifying agents, e.g. water, carbon dioxide, air
    • C01B3/323—Catalytic reaction of gaseous or liquid organic compounds other than hydrocarbons with gasifying agents
    • C01B3/326—Catalytic reaction of gaseous or liquid organic compounds other than hydrocarbons with gasifying agents characterised by the catalyst
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J2208/00—Processes carried out in the presence of solid particles; Reactors therefor
    • B01J2208/00008—Controlling the process
    • B01J2208/00716—Means for reactor start-up
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J2208/00—Processes carried out in the presence of solid particles; Reactors therefor
    • B01J2208/00796—Details of the reactor or of the particulate material
    • B01J2208/00823—Mixing elements
    • B01J2208/00831—Stationary elements
    • B01J2208/0084—Stationary elements inside the bed, e.g. baffles
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J2208/00—Processes carried out in the presence of solid particles; Reactors therefor
    • B01J2208/02—Processes carried out in the presence of solid particles; Reactors therefor with stationary particles
    • B01J2208/023—Details
    • B01J2208/024—Particulate material
    • B01J2208/025—Two or more types of catalyst
    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
    • C01B2203/00—Integrated processes for the production of hydrogen or synthesis gas
    • C01B2203/02—Processes for making hydrogen or synthesis gas
    • C01B2203/0205—Processes for making hydrogen or synthesis gas containing a reforming step
    • C01B2203/0227—Processes for making hydrogen or synthesis gas containing a reforming step containing a catalytic reforming step
    • C01B2203/0233—Processes for making hydrogen or synthesis gas containing a reforming step containing a catalytic reforming step the reforming step being a steam reforming step
    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
    • C01B2203/00—Integrated processes for the production of hydrogen or synthesis gas
    • C01B2203/06—Integration with other chemical processes
    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
    • C01B2203/00—Integrated processes for the production of hydrogen or synthesis gas
    • C01B2203/10—Catalysts for performing the hydrogen forming reactions
    • C01B2203/1041—Composition of the catalyst
    • C01B2203/1047—Group VIII metal catalysts
    • C01B2203/1052—Nickel or cobalt catalysts
    • C01B2203/1058—Nickel catalysts
    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
    • C01B2203/00—Integrated processes for the production of hydrogen or synthesis gas
    • C01B2203/10—Catalysts for performing the hydrogen forming reactions
    • C01B2203/1041—Composition of the catalyst
    • C01B2203/1076—Copper or zinc-based catalysts
    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
    • C01B2203/00—Integrated processes for the production of hydrogen or synthesis gas
    • C01B2203/12—Feeding the process for making hydrogen or synthesis gas
    • C01B2203/1205—Composition of the feed
    • C01B2203/1211—Organic compounds or organic mixtures used in the process for making hydrogen or synthesis gas
    • C01B2203/1217—Alcohols
    • C01B2203/1229—Ethanol
    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
    • C01B2203/00—Integrated processes for the production of hydrogen or synthesis gas
    • C01B2203/14—Details of the flowsheet
    • C01B2203/141—At least two reforming, decomposition or partial oxidation steps in parallel
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
    • Y02P20/00—Technologies relating to chemical industry
    • Y02P20/50—Improvements relating to the production of bulk chemicals
    • Y02P20/52—Improvements relating to the production of bulk chemicals using catalysts, e.g. selective catalysts

Definitions

  • the present invention generally relates to apparatus and methods for reforming alcohols.
  • Alcohol reforming is an endothermic catalytic process that converts alcohols to a mixture of hydrogen and other gases.
  • the product, "alcohol reformate,” may be superior to the parent alcohol as a fuel for internal combustion engines.
  • the superiority of alcohol reformate, particularly those formed from methanol and ethanol, is primarily due to the presence of hydrogen. Reformate burns faster than the starting alcohol and is more tolerant of dilution with air or exhaust. At part load, dilution benefits efficiency by reducing throttling losses and loss of heat of combustion to the coolant. In addition, the heat of combustion of reformate is greater than that of the starting alcohol.
  • Both alcohols and reformate are high octane fuels which can tolerate high compression ratios.
  • the degree of dilution is typically described by the parameter lambda ( ⁇ ) which represents the ratio of air introduced into the cylinders to that required stoichiometrically for combustion of the fuel.
  • lambda ⁇
  • Methanol reforming is typically conducted at temperatures above 250°C.
  • the methanol reforming reaction is given in equation 1.
  • a reformer for reforming an alcohol to a gaseous reformate mixture comprising hydrogen for combustion in an engine generally comprises a catalytic reactor assembly, and inlet manifold assembly, and an outlet manifold.
  • the catalytic reactor assembly includes a plurality of parallel reactor tubes having open first longitudinal ends and closed second longitudinal ends, and a plurality of catalyst assemblies disposed in the plurality of parallel reactor tubes.
  • Each catalyst assembly includes a thermally-conductive, porous catalyst substrate, and a powder catalyst loaded on the substrate for reforming alcohol to the gaseous reformate mixture comprising hydrogen.
  • the inlet manifold assembly includes an inlet plenum for receiving alcohol from an alcohol source, and a plurality of parallel inlet tubes extending axially through the open first longitudinal ends of the parallel reactors tubes for delivering alcohol to the catalyst assemblies.
  • the inlet tubes have inlets disposed in the inlet plenum and outlets adjacent the closed second longitudinal ends of the reactor tubes.
  • the outlet manifold includes an outlet plenum in fluid communication with the open first longitudinal ends of the reactor tubes for receiving the reformate mixture from the reactor tubes.
  • a reformer for reforming an alcohol to a gaseous reformate mixture comprising hydrogen for combustion in an engine generally comprises a generally cylindrical, rolled reformer housing including opposing sheets of thermally conductive material defining a catalyst chamber therebetween.
  • a catalyst assembly is disposed in the catalyst chamber.
  • the catalyst assembly includes a thermally-conductive, porous catalyst substrate, and a powder catalyst loaded on the substrate for reforming alcohol to the gaseous reformate mixture comprising hydrogen.
  • the reformer further comprises an inlet header for delivering alcohol into the catalyst chamber, an outlet header for removing the reformate mixture from the catalyst chamber, and a spacer disposed between adjacent turns of the rolled reformer housing to define a plurality of exhaust plenums between the adjacent turns of the rolled reformer housing and extending longitudinally with respect to the reformer housing.
  • the exhaust plenums define a flow path for exhaust gas from an engine to flow longitudinally through the rolled reformer in thermal contact with the opposing sheets of the rolled reformer housing.
  • a reformer for reforming an alcohol to a gaseous reformate mixture comprising hydrogen generally comprises a shell defining a catalyst plenum having opposite first and second longitudinal ends.
  • the shell has an inlet port adjacent the first longitudinal end of the catalyst plenum for receiving alcohol from an alcohol source, and an outlet port adjacent the second longitudinal end of the catalyst plenum for receiving the reformate mixture from the catalyst plenum.
  • a plurality of exhaust tubes within the catalyst plenum define an exhaust flow path for an exhaust gas to flow.
  • a catalyst assembly in catalyst plenum includes a heat-conducting, porous catalyst substrate, and a powder catalyst loaded on the substrate for reforming alcohol to the gaseous reformate mixture comprising hydrogen.
  • the catalyst substrate includes a plurality of openings through which the exhaust tubes extend in thermal contact with the catalyst substrate.
  • a catalyst assembly for reforming an alcohol to a gaseous reformate mixture comprising hydrogen for combustion in an engine generally comprises a thermally-conductive, porous catalyst substrate, and an unpassivated, copper-nickel powder catalyst loaded on the substrate for reforming alcohol to the gaseous reformate mixture comprising hydrogen.
  • FIG. 1 is an enlarged, fragmentary top plan view of a first embodiment of a catalyst assembly, including a single catalyst substrate;
  • FIG. 2 is an side view of the catalyst assembly in Fig. 1 ;
  • FIG. 3 is a side view of a second embodiment of a catalyst assembly, including a plurality of catalyst substrates and filters disposed between adjacent catalyst substrates;
  • FIG. 4 is a perspective of a reformer for reforming an alcohol to a gaseous mixture comprising hydrogen;
  • Fig. 5 is a longitudinal sectional view of the reformer in Fig. 4;
  • FIG. 6 is a perspective of a catalytic reactor assembly of the reformer in Fig.
  • Fig. 7 is an enlarged view of one of a plurality of reactor tubes that are part of the catalytic reactor assembly of the reformer in Fig. 4;
  • Fig. 8 is a flow diagram for an alcohol reformate power system, such as for a vehicle, incorporating the alcohol reformer in Fig. 4;
  • Fig. 9 is a schematic section of modified embodiment of the reformer, similar to Fig. 7, and including an electrical heating system;
  • FIG. 10 is a perspective of a third embodiment of an alcohol reformer including a generally cylindrical, rolled reformer housing;
  • Fig. 1 1 is a cross section of the alcohol reformer in Fig. 10;
  • Fig. 12 is a sectional view of a fourth embodiment of an alcohol reformer configured in a shell and tube arrangement
  • Fig. 13 is a top plan view of a catalyst substrate of the alcohol reformer in
  • Figs. 14A and 14B are graphs of results obtained from an experiment performed in Example 4 of the present disclosure.
  • Figs. 15A and 15B are graphs of results obtained from an experiment performed in Example 5 of the present disclosure.
  • Fig. 16 is an experimental setup for Example 6 of the present disclosure.
  • Fig. 17 are graph results from the experiment in Example 9.
  • the present disclosure relates to embodiments of reformers, and associated methods, for improving efficiency and emissions of an alcohol-fueled vehicle by utilizing exhaust heat to drive an endothermic catalytic reaction of alcohols known as reforming.
  • a reformer for facilitating effective heat transfer from exhaust to the catalyst. Such effective heat transfer enables rapid reformer startup, and also enables the engine to tolerate high in-cylinder dilution, which leads to higher efficiency.
  • embodiments of the catalyst assembly inside the reformer housing comprise copper-nickel powder embedded in a heat-conducting, porous substrate that provides effective heat transfer to the catalyst.
  • the porous substrate serves as a heat-transfer medium for transferring heat to the copper-nickel powder.
  • internal filters may be disposed in the reformer housing to inhibit catalyst movement inside the reformer housing.
  • the catalyst assembly 2 includes a heat-conducting, porous catalyst substrate 4, and a powder catalyst 6 loaded on the substrate.
  • the catalyst 6 may be embedded in the porous catalyst substrate 4, as shown in FIG. 1, or otherwise applied to a surface of the substrate.
  • the catalyst substrate 4 includes one or more sheets of metal mesh or felt including heat conducting fibers. The powder catalyst 6 can be easily applied to the substrate sheets and the catalyst-loaded substrate sheets then serve as convenient catalyst carriers during assembly of the reformer, providing a catalyst bed with high catalyst density and excellent thermal conductivity.
  • the catalyst substrate 4 may include mesh, such as mesh including iron-chromium fibers (e.g., Fecralloy fibers).
  • suitable materials for the catalyst substrate 4 include G-Mat, a Fecralloy mesh product from Micron Fiber-Tech of Debary, FL and Sinterflo F and M media from Porvair of Ashland, VA.
  • the substrate 4 may comprise other materials, such as copper gauze (described in Example 4), steel wool, or loose metal fibers, or other fibrous metal.
  • the powdered catalyst 6 is loaded onto the porous catalyst substrate 4 without passivation and without the use of aggressive and time-consuming techniques such as roller mills.
  • Copper-nickel powdered catalysts particularly copper-plated nickel sponge, are weakly ferromagnetic if they have not been dried and passivated.
  • the interparticle attraction causes slurries of unpassivated catalyst to have a thick consistency similar to peanut butter, allowing a thick layer of catalyst 6 to be applied to the porous substrate 4 (e.g., metal mesh, foil, or screen) by spreading a slurry (e.g. heavy slurry including at least 50% catalyst by weight) onto one or both external surfaces of the substrate 4.
  • a magnetic force can be used to move the weakly ferromagnetic catalyst 4 into the porous substrate 4 to embed the catalyst in the porous substrate.
  • the catalyst assembly 2 may also include filters 8 disposed between adjacent sections or stages 9 of catalyst substrates.
  • the filters 8 inhibit movement of the powdered catalyst 6 within the reformer, particularly if the catalyst is arranged in the stages 9.
  • the filters 8 may comprise fibrous metal depth filter media such as Bekipor media from NV Bekaert SA, Zwevegem, -Belgium, fibrous metal depth filters from Mott Corporation, Farmington, CT, sintered metal material, or other material.
  • the filters comprise disks (or substrates) of heat transfer media between catalyst stages.
  • the heat transfer filters 8 may be metal meshes, wools, or foams that are low in nickel although carbon foams can also be used due to their high thermal conductivity.
  • suitable heat transfer media include steel and copper wool, the aforementioned metal meshes such as G-Mat and sintered metals.
  • the filters 8 promote heating and alcohol evaporation and act as a trap for trace non-volatile compounds in the fuel stream, such as tarry components of gasoline used in E85 or similar fuels.
  • a first embodiment of a reformer suitable for use with the catalyst assembly 2 for reforming an alcohol to a gaseous mixture comprising hydrogen, is generally indicated at 10.
  • the reformer 10 includes an exhaust duct, generally indicated at 12, to drive the endothermic catalytic reaction of alcohols.
  • the exhaust duct 12 defines an exhaust plenum 13, and includes inlet and outlet ports 16, 18 for use in coupling the exhaust duct within (in line with) an exhaust system of the alcohol-fueled vehicle so that the exhaust gas flows through the exhaust plenum, as indicated by reference character Fi in FIG. 5.
  • the reformer 10 includes an alcohol (inlet) manifold assembly, generally indicated at 20, a catalytic reactor assembly, generally indicated at 22 (see also FIG. 6), and a reformate (outlet) manifold, generally indicated at 24.
  • the alcohol (inlet) manifold assembly 20 includes an inlet coupling 28, for coupling with a source of alcohol, in fluid communication with an alcohol (inlet) plenum 30.
  • the plenum 30 is defined by a cover 32 mounted on a perforated plate 34.
  • a plurality of parallel inlet tubes 36 extend through openings 38 in the perforated plate 34 such that inlets 40 of the inlet tubes are within and in fluid communication with the inlet plenum 30, and outlets 42 of the inlet tubes are outside the plenum.
  • the catalytic reactor assembly 22 includes a perforated plate 44, and a plurality of parallel reactor tubes 46 extending outward from the plate.
  • the perforated plate 44 is mounted on the exhaust duct 12 such that the reactor tubes 46 extend into the exhaust plenum 13 in thermal communication with the exhaust flow F l.
  • the reactor tubes 46 have open ends 50 (which function as outlets for reformate, as explained below), and opposite closed ends 52 in the exhaust plenum 13.
  • the reactor tubes 46 are made from heat- conducting material, and each reactor tube 46 includes a plurality of axially spaced-apart heat- conducting fins 54 extending radially outward from the exterior surface of the tube, within the exhaust plenum 13.
  • the perforated plate 34 of the alcohol (inlet) manifold assembly 20 is mounted on the perforated plate 44 of the catalytic reactor assembly 22 such that the inlet tubes 36 extend axially into the reactor tubes 46 and the outlet 42 of the inlet tubes are generally adjacent to the closed ends 52 of the reactors tubes.
  • the perforated plates 34, 44 are spaced apart to define a reformate (outlet) plenum 58 of the reformate (outlet) manifold 24 therebetween, which is in fluid communication with an outlet coupling 60.
  • the catalyst assembly 2 (or a different catalyst assembly) is disposed within the annular space 48 defined between the interior of each reactor tube 46 and the exterior of the corresponding inlet tube 36.
  • the catalyst assembly may include the catalyst stages 9 that are separated by the filters 8.
  • inlet and outlet filters 8 may be positioned at ends of the catalyst assembly 2.
  • alcohol (which may already be vaporized) flows into the alcohol (inlet) plenum 30 and into the inlet tubes 36.
  • the alcohol then enters the reactors tubes 46, via the outlets 42 of the inlet tubes 36, adjacent the closed ends of the reactor tubes, and flows axially through the catalysts assemblies 2 disposed in the annular spaces 48 defined between the reactor tubes 46 and the corresponding inlet tubes 36.
  • the reformed alcohol flows through the open ends 50 of the reactor tubes 46 and into the reformate (outlet) plenum 58 of the reformate (outlet) manifold 24.
  • the reformed alcohol exits the reformer 10 through the outlet coupling 60.
  • the individual reactor tubes 46 may be 0.5 in to 2 inches in diameter.
  • the inlet tubes 36 may be l/8-1 ⁇ 4-inch in diameter.
  • the catalyst substrate 4 and the internal filters 8 the annulus between the tubes 36, 46 may be copper mesh, gauze, or wool because of its good thermal conductivity. Also, copper is more flexible, making it easier to insert into the annulus.
  • an alcohol reformate power system such as for a vehicle, incorporating the alcohol reformer 10, is generally indicated by reference numeral 70.
  • the alcohol reformate power system includes an engine 72, and an alcohol reforming system 74. Exhaust from the engine 72 flows to the reformer 10 through a first exhaust line 76, and flows from the reformer to a vaporizer 78 through a second exhaust line 80.
  • the first exhaust line 76 couples to the inlet port 16 of the exhaust duct 12 in FIGS. 4 and 5.
  • the alcohol is pumped, via pump 82, from a tank 84 (e.g., a source) through a reformate cooler 86 and a vaporizer 88 before flowing through the reformer 10 via an alcohol inlet line 90 which is coupled to the inlet coupling 28.
  • a tank 84 e.g., a source
  • the reformed alcohol flows through an alcohol outlet line 92, which is coupled to the outlet coupling 60, to the reformate cooler 86, and then to the engine for combustion.
  • a modified version of the first embodiment of the reformer is generally indicated at 1 10.
  • This reformer 110 is similar to the first reformer 10, with like components indicated by corresponding reference numeral plus 100.
  • the main difference between the first reformer 10 and the modified reformer 1 10 is that the modified reformer includes an electrical heating system 193 for delivering electrical current to the reformer to heat the reformer.
  • the electrical heating system 193 includes an electrical power source 194 (e.g., a battery) and electrical lead 195 electrically connected to the inlet tubes 136.
  • the reformer 1 10 is grounded for safety.
  • the inlet tubes 136 have lateral inlet openings 140 through which the alcohol enters the tubes.
  • the inlet tubes 136 are electrically isolated through the use of swaged connections with insulating ferrules 197 or by similar components. VespelTM may be used for the insulating ferrules 197 as it can withstand temperatures up to 350°C.
  • the internal filters 108 of the catalyst assemblies 102 may be electrically non-conductive.
  • the internal filters may be glass wool or other electrically non-conductive material.
  • a glass cylinder 198 retains an upper internal filter in the reactor tube 146. Electrical startup is achieved by passing either direct or alternating current through the inlet tubes 136.
  • the power source 194 may be the battery or the alternator of the vehicle. Preferably, current is not passed through the reformer 1 10 until exhaust temperature entering the reformer is at least 200°C. Otherwise, the exhaust will cool the catalyst assembly 102.
  • a third embodiment of a reformer for reforming an alcohol to a gaseous mixture comprising hydrogen is generally indicated at 210.
  • This reformer 210 includes a generally cylindrical, rolled reformer housing, generally indicated at 12, and a catalyst assembly 14.
  • the reformer housing 12 includes opposing metal layers or sheets 16 defining a catalyst chamber 18 therebetween, in which the catalyst assembly 14 is disposed.
  • the metal sheets 16 are rolled and a spacer 20 is provided between adjacent turns of the rolled reformer housing 12.
  • the metal sheets 16 serve to transfer heat from exhaust to catalyst assembly 14, and are preferably no thicker than required in order to withstand maximum reformer pressure and are formed from alloys which are stable to hot exhaust and ethanol.
  • the metal sheets may be formed from stainless steels and/or copper-rich alloys such as Monel.
  • the spacer 20 may be in the form of a sheet including a plurality of channels extending longitudinally with respect to the housing 12. Thus, the spacer 20 at least partially defines a plurality of exhaust plenums 22 extending along the reformer housing, and through which exhaust flows in thermal contact with the metal sheets.
  • the catalyst chamber 18 is generally at higher pressure than exhaust plenums 22, so the spacer 20 provides mechanical support for the exhaust plenums, without creating significant exhaust backpressure, to inhibit collapse of the exhaust plenums 22.
  • the spacer may comprise a plurality of structures spaced apart along the turns of the rolled reformer housing 12 to define the plurality of exhaust plenums 22 extending along the reformer housing.
  • Inlet and outlet headers 24, 26, respectively, for introducing ethanol into and withdrawing reformate from the catalyst chamber 18, extend longitudinally at the outer circumference of the housing 12 and the inner circumference of the housing, respectively, in fluid communication with the catalyst chamber 18. It is understood that the locations of the inlet and outlet headers 24, 26, respectively, can be reversed. Opposite longitudinal edges 28 of the metal sheets 16 are sealed, such as by laser welding, furnace brazing or other ways, so as to seal the catalyst assembly 14 in the catalyst chamber 18 and prevent exhaust from entering the catalyst chamber.
  • FIG. 12 another embodiment of a reformer for reforming an alcohol to a gaseous mixture comprising hydrogen is generally indicated at 310.
  • the reformer is generally of a shell and tube design, wherein the reformer includes tubes 312 for receiving exhaust that are disposed within a shell or housing 314 for receiving alcohol.
  • the exhaust tubes 312 may be constructed from stainless steels and copper-rich alloys such as Monel.
  • Inlet and outlet couplings 316, 318, respectively, for coupling with the exhaust line are in fluid communication with the exhaust tubes 312.
  • Alcohol inlet and outlet ports 320, 322, respectively, are in fluid communication with the interior of the shell 314.
  • the catalyst assembly 302 is received in the shell 314.
  • the catalyst assembly 302 may be similar to the catalyst assemblies 2, 102, 202, and may include catalyst stages 308 separated by internal filters 309, as illustrated.
  • the catalyst substrates 304 and internal filters 309 have openings 324, 326, respectively, through which the exhaust tubes 312 extend in thermal contact with the substrates and filters.
  • the reformer 310 also includes baffles 328 for directing the flow of alcohol through the catalyst assembly 302.
  • the baffles 328 also include openings 330 through which the exhaust tubes 312 extend, and cutouts 332 through which the alcohol flows. Heat from the exhaust flowing through the exhaust tubes 312 is transferred to the thermally conductive substrates 304 and filters 309 to heat the powdered catalysts 306 on the substrates and the alcohol flowing through the catalyst substrates.
  • a copper-nickel catalyst is impregnated onto Fecralloy mesh disks 304 which are perforated with the holes 324 to accommodate the exhaust tubes 312.
  • Multiple catalyst stages 308 composed of stacks of such disks 304 followed by a similarly perforated layer of fibrous metal depth filter material 309. Accordingly, catalyst zones 308 and catalyst free zones 309 alternate to facilitate reheating of the alcohol-reformate stream in the shell 314.
  • the reformer be a lightweight plate-and-frame design into which rectangular pieces of catalyst substrate 4 coated with copper-plated nickel sponge 6 are inserted.
  • a suitable reformer housing is a heat exchanger, marketed as the "Catacel ® " by fuel cell materials.com and described in patent publication US 2008/0072425, the entirety of which is hereby incorporated by reference.
  • This Example describes the preparation of copper-plated nickel sponge.
  • the product is a wet catalyst slurry which can be applied directly to fibrous metal supports such as G-Mat.
  • This Example describes preparation of copper-plated nickel sponge by the method of Example 1 followed by drying and passivation with air.
  • the brown catalyst was rinsed twice with three liters of deionized water.
  • the catalyst was dried overnight under vacuum at 120°C with nitrogen purge.
  • the dry catalyst (851 g) was allowed to cool in the oven under nitrogen, and then poured out in portions into a lasagna pan in the sink, with running water keeping the outside of the pan cool and continuous stirring of the powder with a spatula.
  • a little water (a few ml each time) was added every few minutes to control the temperature and mixed thoroughly with the catalyst by stirring. Some sparking was seen initially. The process took ten minutes. The pan then sat out for another hour to complete oxidation before re-drying the catalyst under the same conditions. 912 g of passivated dry catalyst was recovered.
  • This Example describes a simple reformer built to determine the heat transfer properties of powder beds of copper-plated nickel sponge.
  • a large reformer was fabricated out of Monel with a cylindrical catalyst chamber, two inches in diameter. Surrounding the catalyst chamber through which hot nitrogen passed as a simulant of automotive exhaust. The bottom of the reactor was packed with glass wool supported on a metal screen with holes in it. Nine 1/16" thermocouples were fed through the bottom to different depths and in several radial positions. The depth of the chamber from the flange to the glass wool was five inches with no catalyst in the reformer.
  • Absolute ethanol was fed from the top after preheating in an evaporator and using a heat exchanger which exchanges heat between nitrogen exiting the reformer and incoming steam or ethanol. Reformate composition was monitored using a Micro-GC from Agilent.
  • Catalyst temperature is reported as a function of radius, representing an average of a group of thermocouples near the catalyst chamber wall, on the midline and a group at intermediate positions.
  • This Example demonstrates the substantial temperature gradients that develop in beds of copper-plated Raney nickel and the use of a fibrous metal medium to largely eliminate the gradient.
  • Example 3 The reactor system and catalyst bed of Example 3 was operated using a 5 ml/min feed rate of ethanol.
  • the ethanol and nitrogen flowrates and nitrogen temperatures are given in Table 1 below.
  • the catalyst was removed from the reformer and then re-loaded mixed with 28 2-inch disks formed from copper gauze. (Copper Knitted Wire Industrial Cleaning Mesh). 28 of the disks weighing a total of 17.92 g were placed in the reformer along with the catalyst. The stack of disks extended to near the top of the catalyst bed, but did not quite reach the upper surface of it. When the catalyst was removed from the reactor it was gray in color and not pyrophoric or self-heating. [0062] As originally prepared, the catalyst bed had cracks which disappeared over several hours of operation with occasional tapping on the reformer wall. The experiment in Table 1 was then repeated. Temperature profiles without and with copper gauze are shown in Figs. 14A and 14B, respectively. As seen in Figs. 14A and 14B, the copper gauze greatly reduced the temperature gradient across the radius of the reactor particularly between the wall and intermediate thermocouples.
  • Results showed a dramatic increase in methane formation relative to other permanent gases (H2 and CO) after the decrease in ethanol flow from 4 to 2 ml/min at 310 minute experiment time. Catalyst temperatures were about 390°C at this point. A smaller increase in methanation is apparent at the previous flow change at 250 minutes with catalyst temperatures about 380°C. Table 2: Reactor conditions used in Example 5.
  • This example describes the use of dry, passivated copper-plated nickel sponge prepared by the method of Example 2 impregnated into Fecralloy mesh in an HEP or "Catacel" plate-and-frame reformer described above.
  • the reformer had multiple (9) rectangular flow channels for the engine exhaust sandwiched between similar number of flow channels for the ethanol-reformate.
  • a commercial Flat Plate heat exchanger was used for reformate cooling; a finned pipe heat exchanger was used as a vaporizer; and a catalytic hydrogen burner was used to generate hot stream of exhaust simulant.
  • the configuration is shown in Fig. 16.
  • the HEP reformer had about 0.165 sq meter heat transfer area and weighed less than 500 g without flanges.
  • Nine strips (23 cm L x 4 cm W x 0.16 mm thick) of a porous metal felt (G-Mat from Micron Fiber-Tech) were oxidized in air at 800°C for 16 hr and then cooled down naturally. The oxidized strips were compressed and inserted into the nine HEP channels.
  • An aqueous slurry of copper-plated nickel sponge that had been dried and air-passivated by the procedure of Example 2 were loaded onto HEP channels and the porous felt strips were soaked for several minutes. The slurry solution was then drained out.
  • the HEP loaded with wet catalyst was put into the furnace filled with N2 and dried at 120°C. The soaking and drying procedures were repeated for three times. The HEP was weighed before and after catalyst loading to obtain the amount of catalyst loading.
  • the typical catalyst weight value by this method is 95 g.
  • the vaporizer a finned tube, was placed coaxially inside the hot exhaust pipeline after the HEP.
  • the total heat transfer area of the vaporizer was 0.137 m 2 .
  • Heat was introduced into the reaction chambers by the catalytic combustion of hydrogen in the burner.
  • the heat of combustion (LHV) was about 1.4 kW while the 3 ⁇ 4 feed rate to the burner was ⁇ 8.4 slpm during the test.
  • the flow rate of the air to the burner was set to 141 slpm.
  • Synasol 190 An ethanol-rich fuel known as Synasol 190 was used as the feed. Its composition was 83% ethanol, 6.8% water, 3.5% methanol; 5.0% ethyl acetate and ⁇ 1% other impurities). This fuel was fed parallel (co-current) to the simulated exhaust with the HEP reformer in a horizontal orientation. No internal filters were used. Some catalyst blew out of the reformer over the course of the experiment as a result. Synasol 190 flowrates of 12 and 24 ml/min were tested. The results are shown in Table 3. Conversions were about 50%, likely due to channeling in the catalyst bed which in turn is due to the lack of internal filters.
  • Table 3 Tem erature and conversion data for the late-and- frame reformer in Exam le 6.
  • This Example describes the construction of a shell-and-tube reformer with multiple catalyst stages.
  • the catalyst was copper-plated Raney nickel 4200 prepared without catalyst drying by the procedure of Example 1.
  • the shell was a 24-inch length of Schedule 10, type 304 stainless steel pipe with an internal diameter of 6.32 inches. 24-inch lengths of 1 ⁇ 4-inch i.d. stainless steel tubes were used for the exhaust.
  • the first step in reformer assembly was forming a stack of the internals.
  • a tube sheet was placed on the work table and six tubes inserted symmetrically around the periphery to hold and align the stack.
  • the reformer internals were threaded onto the six tubes, taking care to maintain correct alignment.
  • the sequence of internals is shown in Table 4.
  • Table 4 Stack of reformer internals for the shell-and-tube reformer of Example 7.
  • Catalyst Stage 5 45 G-Mat (6 disks) w/ catalyst
  • the reformer was fitted with a shroud which was coupled to the exhaust cones. A fraction of the exhaust passes around the reformer between the shell and the shroud, accelerating heatup and thermal expansion of the shell. This was intended to prevent the exhaust tubes from heating up faster than the shell, creating thermal stress.
  • 5/32" welding rod was welded to the shell in the longitudinal direction serving as a spacer.
  • Sheet metal (18-gauge stainless steel) was cut in a rectangular shape and holes punched in order to accommodate the thermocouple ports. The sheet metal was creased between each port to allow for thermal expansion of the shroud. The shroud was then wrapped around the welding rods and welded to each of the thermocouple ports, creating a 5/32-inch channel for bypassed exhaust.
  • too much exhaust would be diverted around the reformer, since the cross section of the aperture created by the shroud is about 30% of the total cross sectional area of the reformer exhaust tubes.
  • This Example describes the modification of a Ford 5.4-liter 8-cylinder engine for operation with the alcohol reformer of Example 7 and E85 fuel.
  • the engine had three valves per cylinder with dual equal cam retard capability.
  • the compression ratio was increased to 12: 1 by increasing the piston height while maintaining a completely flat piston crown.
  • E85 or gasoline was injected through port fuel injectors.
  • Hydrogen gaseous fuel injectors manufactured by Quantum (P/N 1 10764-001) were used to introduce reformate fuel just upstream of the liquid fuel in the intake ports.
  • Table 5 Engine specifications for an eight-cylinder engine operated using ethanol reformate and E85 fuel.
  • Valve Configuration SOHC 2 Intake - 1 Exhaust -
  • the reformer was inserted in the exhaust train downstream of the catalytic converters.
  • a diverter valve placed in the exhaust stream controlled the amount of exhaust flow directed into the reformer.
  • This Example describes the performance of the engine and reformer of Examples 7 and 8 when operating at 5.41 bar BMEP, 1500 rpm on certified E85 fuel.

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  • Chemical & Material Sciences (AREA)
  • Organic Chemistry (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Health & Medical Sciences (AREA)
  • General Health & Medical Sciences (AREA)
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  • Combustion & Propulsion (AREA)
  • Inorganic Chemistry (AREA)
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Abstract

L'invention concerne des conceptions de reformeur pour le reformage d'un alcool en un mélange de reformat gazeux comportant de l'hydrogène, pour la combustion dans un moteur. L'invention concerne également un ensemble catalyseur pour le reformage d'un alcool en un mélange de reformat gazeux comportant de l'hydrogène, pour la combustion dans un moteur. L'ensemble catalyseur comprend un substrat de catalyseur poreux, conducteur de la chaleur, et un catalyseur pulvérulent cuivre-nickel, non passivé, chargé sur le substrat, pour le reformage d'un alcool en mélange de reformat gazeux comportant de l'hydrogène.
PCT/US2012/031382 2011-03-30 2012-03-30 Appareil et procédés pour le reformage d'éthanol à basse température à l'aide de catalyseurs pulvérulents WO2012135583A1 (fr)

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Cited By (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US9347386B2 (en) 2012-03-30 2016-05-24 Monsanto Technology Llc Alcohol reforming system for internal combustion engine
EP2922783A4 (fr) * 2012-11-15 2016-08-24 Phillips 66 Co Catalyseurs pour une production d'hydrogène renouvelable à partir de charges d'alimentation oxygénées
US10450193B2 (en) 2012-03-30 2019-10-22 Monsanto Technology Llc Alcohol reformer for reforming alcohol to mixture of gas including hydrogen

Citations (6)

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Publication number Priority date Publication date Assignee Title
DE10346267A1 (de) * 2003-10-06 2005-04-28 Daimler Chrysler Ag Vorrichtung zur Dampfreformierung eines Ausgangsstoffes
WO2006045744A1 (fr) * 2004-10-20 2006-05-04 Shell Internationale Research Maatschappij B.V. Procede pour le reformage de vapeur et/ou de co2 d'une matiere premiere hydrocarbonee
US20070028860A1 (en) * 2005-08-08 2007-02-08 Utilization Technology Development, Nfp Recuperative reforming reactor
WO2007118950A1 (fr) * 2006-03-17 2007-10-25 Ifp Reacteur echangeur a combustion interne pour reaction endothermique en lit fixe
US20080072425A1 (en) 2005-09-13 2008-03-27 Catacel Corp. High-temperature heat exchanger
US20100254891A1 (en) * 2007-07-20 2010-10-07 Ifp Bayonet tube exchanger-reactor allowing operation with pressure differences of the order of 100 bars between the tube side and the shell side

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* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
DE10346267A1 (de) * 2003-10-06 2005-04-28 Daimler Chrysler Ag Vorrichtung zur Dampfreformierung eines Ausgangsstoffes
WO2006045744A1 (fr) * 2004-10-20 2006-05-04 Shell Internationale Research Maatschappij B.V. Procede pour le reformage de vapeur et/ou de co2 d'une matiere premiere hydrocarbonee
US20070028860A1 (en) * 2005-08-08 2007-02-08 Utilization Technology Development, Nfp Recuperative reforming reactor
US20080072425A1 (en) 2005-09-13 2008-03-27 Catacel Corp. High-temperature heat exchanger
WO2007118950A1 (fr) * 2006-03-17 2007-10-25 Ifp Reacteur echangeur a combustion interne pour reaction endothermique en lit fixe
US20100254891A1 (en) * 2007-07-20 2010-10-07 Ifp Bayonet tube exchanger-reactor allowing operation with pressure differences of the order of 100 bars between the tube side and the shell side

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T. HIROTA: "Study of the Methanol-Reformed Gas Engine", JSAE REV., vol. 4, 1981, pages 7 - 13
T.G. ADAMS: "A Comparison of Engine Performance Using Methanol or Dissociated Methanol as the Fuel", SAE PAPER 845128, 1984

Cited By (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US9347386B2 (en) 2012-03-30 2016-05-24 Monsanto Technology Llc Alcohol reforming system for internal combustion engine
US10450193B2 (en) 2012-03-30 2019-10-22 Monsanto Technology Llc Alcohol reformer for reforming alcohol to mixture of gas including hydrogen
EP2922783A4 (fr) * 2012-11-15 2016-08-24 Phillips 66 Co Catalyseurs pour une production d'hydrogène renouvelable à partir de charges d'alimentation oxygénées

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