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WO2014191060A1 - Procédé de régénération in situ de catalyseurs d'oxydation du méthane - Google Patents

Procédé de régénération in situ de catalyseurs d'oxydation du méthane Download PDF

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Publication number
WO2014191060A1
WO2014191060A1 PCT/EP2013/069021 EP2013069021W WO2014191060A1 WO 2014191060 A1 WO2014191060 A1 WO 2014191060A1 EP 2013069021 W EP2013069021 W EP 2013069021W WO 2014191060 A1 WO2014191060 A1 WO 2014191060A1
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WIPO (PCT)
Prior art keywords
methane
gas
reducing agent
catalyst
regeneration
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Ceased
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PCT/EP2013/069021
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English (en)
Inventor
Christophe Duwig
Niklas Bengt Jakobsson
Keld Johansen
Henrik TROLLE
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Topsoe AS
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Haldor Topsoe AS
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Publication of WO2014191060A1 publication Critical patent/WO2014191060A1/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
    • B01J23/00—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00
    • B01J23/38—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of noble metals
    • B01J23/40—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of noble metals of the platinum group metals
    • B01J23/44—Palladium
    • 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
    • B01J21/00—Catalysts comprising the elements, oxides, or hydroxides of magnesium, boron, aluminium, carbon, silicon, titanium, zirconium, or hafnium
    • B01J21/02—Boron or aluminium; Oxides or hydroxides thereof
    • B01J21/04—Alumina
    • 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
    • B01J23/00—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00
    • B01J23/38—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of noble metals
    • B01J23/54—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of noble metals combined with metals, oxides or hydroxides provided for in groups B01J23/02 - B01J23/36
    • B01J23/56—Platinum group metals
    • B01J23/63—Platinum group metals with rare earths or actinides
    • 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
    • B01J37/00—Processes, in general, for preparing catalysts; Processes, in general, for activation of catalysts
    • B01J37/0009—Use of binding agents; Moulding; Pressing; Powdering; Granulating; Addition of materials ameliorating the mechanical properties of the product catalyst
    • B01J37/0063—Granulating
    • 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
    • B01J38/00—Regeneration or reactivation of catalysts, in general
    • B01J38/02—Heat treatment
    • 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
    • B01J38/00—Regeneration or reactivation of catalysts, in general
    • B01J38/04—Gas or vapour treating; Treating by using liquids vaporisable upon contacting spent catalyst
    • B01J38/06—Gas or vapour treating; Treating by using liquids vaporisable upon contacting spent catalyst using steam
    • 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
    • B01J38/00—Regeneration or reactivation of catalysts, in general
    • B01J38/04—Gas or vapour treating; Treating by using liquids vaporisable upon contacting spent catalyst
    • B01J38/10—Gas or vapour treating; Treating by using liquids vaporisable upon contacting spent catalyst using elemental hydrogen
    • F—MECHANICAL ENGINEERING; LIGHTING; HEATING; WEAPONS; BLASTING
    • F01—MACHINES OR ENGINES IN GENERAL; ENGINE PLANTS IN GENERAL; STEAM ENGINES
    • F01N—GAS-FLOW SILENCERS OR EXHAUST APPARATUS FOR MACHINES OR ENGINES IN GENERAL; GAS-FLOW SILENCERS OR EXHAUST APPARATUS FOR INTERNAL-COMBUSTION ENGINES
    • F01N3/00—Exhaust or silencing apparatus having means for purifying, rendering innocuous, or otherwise treating exhaust
    • F01N3/08—Exhaust or silencing apparatus having means for purifying, rendering innocuous, or otherwise treating exhaust for rendering innocuous
    • F01N3/0807—Exhaust or silencing apparatus having means for purifying, rendering innocuous, or otherwise treating exhaust for rendering innocuous by using absorbents or adsorbents
    • F01N3/0871—Exhaust or silencing apparatus having means for purifying, rendering innocuous, or otherwise treating exhaust for rendering innocuous by using absorbents or adsorbents using means for controlling, e.g. purging, the absorbents or adsorbents
    • F01N3/0885—Regeneration of deteriorated absorbents or adsorbents, e.g. desulfurization of NOx traps
    • F—MECHANICAL ENGINEERING; LIGHTING; HEATING; WEAPONS; BLASTING
    • F01—MACHINES OR ENGINES IN GENERAL; ENGINE PLANTS IN GENERAL; STEAM ENGINES
    • F01N—GAS-FLOW SILENCERS OR EXHAUST APPARATUS FOR MACHINES OR ENGINES IN GENERAL; GAS-FLOW SILENCERS OR EXHAUST APPARATUS FOR INTERNAL-COMBUSTION ENGINES
    • F01N3/00—Exhaust or silencing apparatus having means for purifying, rendering innocuous, or otherwise treating exhaust
    • F01N3/08—Exhaust or silencing apparatus having means for purifying, rendering innocuous, or otherwise treating exhaust for rendering innocuous
    • F01N3/10—Exhaust or silencing apparatus having means for purifying, rendering innocuous, or otherwise treating exhaust for rendering innocuous by thermal or catalytic conversion of noxious components of exhaust
    • F01N3/103—Oxidation catalysts for HC and CO only
    • F—MECHANICAL ENGINEERING; LIGHTING; HEATING; WEAPONS; BLASTING
    • F01—MACHINES OR ENGINES IN GENERAL; ENGINE PLANTS IN GENERAL; STEAM ENGINES
    • F01N—GAS-FLOW SILENCERS OR EXHAUST APPARATUS FOR MACHINES OR ENGINES IN GENERAL; GAS-FLOW SILENCERS OR EXHAUST APPARATUS FOR INTERNAL-COMBUSTION ENGINES
    • F01N3/00—Exhaust or silencing apparatus having means for purifying, rendering innocuous, or otherwise treating exhaust
    • F01N3/08—Exhaust or silencing apparatus having means for purifying, rendering innocuous, or otherwise treating exhaust for rendering innocuous
    • F01N3/10—Exhaust or silencing apparatus having means for purifying, rendering innocuous, or otherwise treating exhaust for rendering innocuous by thermal or catalytic conversion of noxious components of exhaust
    • F01N3/18—Exhaust or silencing apparatus having means for purifying, rendering innocuous, or otherwise treating exhaust for rendering innocuous by thermal or catalytic conversion of noxious components of exhaust characterised by methods of operation; Control
    • F01N3/20—Exhaust or silencing apparatus having means for purifying, rendering innocuous, or otherwise treating exhaust for rendering innocuous by thermal or catalytic conversion of noxious components of exhaust characterised by methods of operation; Control specially adapted for catalytic conversion
    • F01N3/2053—By-passing catalytic reactors, e.g. to prevent overheating
    • F—MECHANICAL ENGINEERING; LIGHTING; HEATING; WEAPONS; BLASTING
    • F02—COMBUSTION ENGINES; HOT-GAS OR COMBUSTION-PRODUCT ENGINE PLANTS
    • F02D—CONTROLLING COMBUSTION ENGINES
    • F02D41/00—Electrical control of supply of combustible mixture or its constituents
    • F02D41/02—Circuit arrangements for generating control signals
    • F02D41/021—Introducing corrections for particular conditions exterior to the engine
    • F02D41/0235—Introducing corrections for particular conditions exterior to the engine in relation with the state of the exhaust gas treating apparatus
    • F02D41/027—Introducing corrections for particular conditions exterior to the engine in relation with the state of the exhaust gas treating apparatus to purge or regenerate the exhaust gas treating apparatus
    • F—MECHANICAL ENGINEERING; LIGHTING; HEATING; WEAPONS; BLASTING
    • F02—COMBUSTION ENGINES; HOT-GAS OR COMBUSTION-PRODUCT ENGINE PLANTS
    • F02M—SUPPLYING COMBUSTION ENGINES IN GENERAL WITH COMBUSTIBLE MIXTURES OR CONSTITUENTS THEREOF
    • F02M21/00—Apparatus for supplying engines with non-liquid fuels, e.g. gaseous fuels stored in liquid form
    • F02M21/02—Apparatus for supplying engines with non-liquid fuels, e.g. gaseous fuels stored in liquid form for gaseous fuels
    • F02M21/0203—Apparatus for supplying engines with non-liquid fuels, e.g. gaseous fuels stored in liquid form for gaseous fuels characterised by the type of gaseous fuel
    • F02M21/0215—Mixtures of gaseous fuels; Natural gas; Biogas; Mine gas; Landfill gas
    • F—MECHANICAL ENGINEERING; LIGHTING; HEATING; WEAPONS; BLASTING
    • F02—COMBUSTION ENGINES; HOT-GAS OR COMBUSTION-PRODUCT ENGINE PLANTS
    • F02M—SUPPLYING COMBUSTION ENGINES IN GENERAL WITH COMBUSTIBLE MIXTURES OR CONSTITUENTS THEREOF
    • F02M26/00—Engine-pertinent apparatus for adding exhaust gases to combustion-air, main fuel or fuel-air mixture, e.g. by exhaust gas recirculation [EGR] systems
    • F02M26/13—Arrangement or layout of EGR passages, e.g. in relation to specific engine parts or for incorporation of accessories
    • F02M26/14—Arrangement or layout of EGR passages, e.g. in relation to specific engine parts or for incorporation of accessories in relation to the exhaust system
    • F02M26/15—Arrangement or layout of EGR passages, e.g. in relation to specific engine parts or for incorporation of accessories in relation to the exhaust system in relation to engine exhaust purifying apparatus
    • F—MECHANICAL ENGINEERING; LIGHTING; HEATING; WEAPONS; BLASTING
    • F02—COMBUSTION ENGINES; HOT-GAS OR COMBUSTION-PRODUCT ENGINE PLANTS
    • F02M—SUPPLYING COMBUSTION ENGINES IN GENERAL WITH COMBUSTIBLE MIXTURES OR CONSTITUENTS THEREOF
    • F02M63/00—Other fuel-injection apparatus having pertinent characteristics not provided for in groups F02M39/00 - F02M57/00 or F02M67/00; Details, component parts, or accessories of fuel-injection apparatus, not provided for in, or of interest apart from, the apparatus of groups F02M39/00 - F02M61/00 or F02M67/00; Combination of fuel pump with other devices, e.g. lubricating oil pump
    • F02M63/02—Fuel-injection apparatus having several injectors fed by a common pumping element, or having several pumping elements feeding a common injector; Fuel-injection apparatus having provisions for cutting-out pumps, pumping elements, or injectors; Fuel-injection apparatus having provisions for variably interconnecting pumping elements and injectors alternatively
    • F02M63/0225—Fuel-injection apparatus having a common rail feeding several injectors ; Means for varying pressure in common rails; Pumps feeding common rails
    • 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
    • B01J21/00—Catalysts comprising the elements, oxides, or hydroxides of magnesium, boron, aluminium, carbon, silicon, titanium, zirconium, or hafnium
    • B01J21/02—Boron or aluminium; Oxides or hydroxides thereof
    • 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
    • B01J35/00—Catalysts, in general, characterised by their form or physical properties
    • B01J35/50—Catalysts, in general, characterised by their form or physical properties characterised by their shape or configuration
    • B01J35/56—Foraminous structures having flow-through passages or channels, e.g. grids or three-dimensional monoliths
    • F—MECHANICAL ENGINEERING; LIGHTING; HEATING; WEAPONS; BLASTING
    • F01—MACHINES OR ENGINES IN GENERAL; ENGINE PLANTS IN GENERAL; STEAM ENGINES
    • F01N—GAS-FLOW SILENCERS OR EXHAUST APPARATUS FOR MACHINES OR ENGINES IN GENERAL; GAS-FLOW SILENCERS OR EXHAUST APPARATUS FOR INTERNAL-COMBUSTION ENGINES
    • F01N2240/00—Combination or association of two or more different exhaust treating devices, or of at least one such device with an auxiliary device, not covered by indexing codes F01N2230/00 or F01N2250/00, one of the devices being
    • F01N2240/14—Combination or association of two or more different exhaust treating devices, or of at least one such device with an auxiliary device, not covered by indexing codes F01N2230/00 or F01N2250/00, one of the devices being a fuel burner
    • F—MECHANICAL ENGINEERING; LIGHTING; HEATING; WEAPONS; BLASTING
    • F01—MACHINES OR ENGINES IN GENERAL; ENGINE PLANTS IN GENERAL; STEAM ENGINES
    • F01N—GAS-FLOW SILENCERS OR EXHAUST APPARATUS FOR MACHINES OR ENGINES IN GENERAL; GAS-FLOW SILENCERS OR EXHAUST APPARATUS FOR INTERNAL-COMBUSTION ENGINES
    • F01N2240/00—Combination or association of two or more different exhaust treating devices, or of at least one such device with an auxiliary device, not covered by indexing codes F01N2230/00 or F01N2250/00, one of the devices being
    • F01N2240/30—Combination or association of two or more different exhaust treating devices, or of at least one such device with an auxiliary device, not covered by indexing codes F01N2230/00 or F01N2250/00, one of the devices being a fuel reformer
    • F—MECHANICAL ENGINEERING; LIGHTING; HEATING; WEAPONS; BLASTING
    • F01—MACHINES OR ENGINES IN GENERAL; ENGINE PLANTS IN GENERAL; STEAM ENGINES
    • F01N—GAS-FLOW SILENCERS OR EXHAUST APPARATUS FOR MACHINES OR ENGINES IN GENERAL; GAS-FLOW SILENCERS OR EXHAUST APPARATUS FOR INTERNAL-COMBUSTION ENGINES
    • F01N2410/00—By-passing, at least partially, exhaust from inlet to outlet of apparatus, to atmosphere or to other device
    • F01N2410/04—By-passing, at least partially, exhaust from inlet to outlet of apparatus, to atmosphere or to other device during regeneration period, e.g. of particle filter
    • F—MECHANICAL ENGINEERING; LIGHTING; HEATING; WEAPONS; BLASTING
    • F01—MACHINES OR ENGINES IN GENERAL; ENGINE PLANTS IN GENERAL; STEAM ENGINES
    • F01N—GAS-FLOW SILENCERS OR EXHAUST APPARATUS FOR MACHINES OR ENGINES IN GENERAL; GAS-FLOW SILENCERS OR EXHAUST APPARATUS FOR INTERNAL-COMBUSTION ENGINES
    • F01N2610/00—Adding substances to exhaust gases
    • F01N2610/04—Adding substances to exhaust gases the substance being hydrogen
    • 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
    • Y02T—CLIMATE CHANGE MITIGATION TECHNOLOGIES RELATED TO TRANSPORTATION
    • Y02T10/00—Road transport of goods or passengers
    • Y02T10/10—Internal combustion engine [ICE] based vehicles
    • Y02T10/12—Improving ICE efficiencies
    • 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
    • Y02T—CLIMATE CHANGE MITIGATION TECHNOLOGIES RELATED TO TRANSPORTATION
    • Y02T10/00—Road transport of goods or passengers
    • Y02T10/10—Internal combustion engine [ICE] based vehicles
    • Y02T10/30—Use of alternative fuels, e.g. biofuels

Definitions

  • the present invention is directed towards a method of re-generating deactivated methane oxidation catalysts, in par ⁇ ticular methane oxidation catalysts employed cleaning of exhaust gas from lean burn gas engines at reduced tempera ⁇ tures .
  • Natural gas (compressed or liquefied) is a clean and af ⁇ fordable fuel.
  • the discovery of large amounts of shale gas as well as the large natural resources has contributed to make natural gas a competitor of traditional oil products. Unlike oil, natural gas prices have been stable the past decade which make it a competitive alternative. In addi ⁇ tion, natural gas has very low sulphur content and offers opportunities for complying with most stringent emission regulations. It is today a serious candidate for powering engine - so-called gas engines.
  • methane slip results from incomplete combus ⁇ tion of the fuel injected in the pre-chamber or cylinders of the engine. The remaining methane in the exhaust is therefore up to several thousand of ppm.
  • the high activity of the catalyst at low temperature is vi ⁇ tal. However, it makes the catalyst prone to adsorb a wide range of poisons. If the natural gas is mostly free from poisons, lubrication oils and other oil used in the engine are still sources of potential poisons. The most critical are sulphur oxides formed from sulphur compounds. The sul ⁇ phur level originating from the mechanical oil is far below legislation limits, typically resulting in ppm or ppb levels of SOx in the flue gas. It is, however, sufficient for reducing the life time of the catalyst significantly. Deac ⁇ tivation of the catalyst by sulphur adsorption, allows the operation of the catalyst only within a given activity range. When deactivation has proceeded to the limit of this range, the catalyst must be replaced or reactivated.
  • Essentially suitable temperature levels for regeneration would be from 150°C to 750°C.
  • the invention provides a method for the regeneration of a deactivated methane oxidation catalyst comprising the step of bringing the deactivated catalyst in contact with a reducing agent, selected from the group of methanol, natu ⁇ ral gas, very low sulphur diesel, alcohols, ethers, hydro ⁇ gen, carbon monoxide and ammonia or mixtures thereof.
  • a reducing agent selected from the group of methanol, natu ⁇ ral gas, very low sulphur diesel, alcohols, ethers, hydro ⁇ gen, carbon monoxide and ammonia or mixtures thereof.
  • the catalysts will normally be in the oxidised state or be poisoned by sulphur oxides forming sulphate or sulphite compounds on the catalyst surface that further can migrate to the carrier oxides.
  • the reducing agent enables removal of the sulphur oxides, sulphates and sulphites as gaseous hydrogen sulphide and sulphur dioxide.
  • the reducing agent can be generated in a methane or natural gas burner running rich at lambda below 1.00 where CO, H2 and reactive hydrocarbons can be formed.
  • a preferred reducing agent is hydrogen and/or carbon monoxide.
  • the hydrogen reducing agent can also be prepared by one of methane or hydrocarbon reforming, methanol reforming or cracking, or ammonia cracking.
  • Reducing conditions may also be accomplished by utilizing the thermal inertia in the methane oxidation reactor and catalyst.
  • the reducing agent such as methanol, other alcohols, ethers, ammonia or mixtures thereof are fed into the methane oxidation reactor and the thermal inertia is used to convert the reducing agent into H2 and CO which then regenerate the catalyst.
  • the formation of H2 and CO from other reducing agents is catalysed by the methane oxi ⁇ dation catalyst or a separate catalyst also placed in the methane oxidation rector.
  • methane containing flue gas is by-passed the deactivated methane oxidation catalyst during the regeneration and brought into contact with a regenerat ⁇ ed methane oxidation catalyst
  • the H2 and/or CO reducing agent is prepared by burning natural gas at lambda below 1.00, typi ⁇ cally between 0.85 and 0.97.
  • Suitable methane oxidation catalysts comprise palladium and/or platinum and/or rhodium.
  • Preferred catalysts comprise palladium on yttria and/or lanthanum stabilized alumina, optionally coated on cordier- ite or corrugated metal sheets.
  • the oxidation catalyst can be arranged in the methane oxidation reactor in form of a monolith with a plurality of straight channels.
  • a part of the channels can under re ⁇ generation with the reducing agent, while the remaining channels are active in the oxidation of methane. It may be preferred that the reducing agent is passed in counter current flow direction to the flow direction of a methane containing gas .
  • off gas from the regeneration of the deactivated methane oxidation catalyst is recycled and mixed with the engine exhaust gas and passed to a regener ⁇ ated methane oxidation catalyst.
  • the off gas can be recycled to a gas engine connected to the methane oxidation reactor.
  • a reducing agent is injected upstream of the methane slip catalyst and the flow over the catalyst re ⁇ moves sulphur poisoning as 3 ⁇ 4S or SO 2 .
  • the sulphur contami ⁇ nated reducing agent is mixed with the flue gas and exits through the turbo-charger.
  • Fig. 2 shows a system with two parallel methane slip cata ⁇ lyst units for ensuring that slip is always removed. One of the units is in operation and the other is under regenera ⁇ tion.
  • Fig. 3 presents a system where the additional fuel is con ⁇ verted catalytically to hydrogen prior to injection as re ⁇ ducing agent, instead of expensive storage of hydrogen. This conversion could be methane or hydrocarbon reforming, methanol reforming or cracking or ammonia cracking.
  • a fraction of flue agent form the engine is passed to the catalyst unit during regeneration for combus- tion of a fraction of the additional fuel ( methane or nat ⁇ ural gas) in a burner, thereby increasing the temperature during regeneration.
  • This enables to increase/ control the temperature during the regeneration phase.
  • some oxygen containing flue gas is injected during the regenera- tion phase, the regeneration occurs in reducing atmosphere, hence the reducing agent is in excess compared to oxygen to maintain fuel rich conditions.
  • the reducing agent can be gener ⁇ ated in a methane or natural gas burner running rich at lambda ⁇ 1.0 where CO, H2 and reactive hydrocarbons can be formed. This embodiment is shown in Fig.5
  • Fig. 6 shows a further alternative, wherein an oxidation reactor is divided in two or more compartments where the reducing gas is directed to one compartment while the other compartments are used for methane oxidation.
  • Simple dampen- ers can be used to control the flow. Due to the fact that the required reducing gas volume to regenerate the catalyst is modest, the emissions of residual CO and H2 are kept to a minimum.
  • the reducing gas can be redirected to the main gas flow at the catalyst inlet using flaps also at the catalyst outlet and a recycle, as shown in Fig.7.
  • Fig. 8 shows a device moving across the catalyst surface injecting reducing gas and thus continuously regenerating one catalyst segment at the time. Due to the fact that the required reducing gas volume to regenerate the catalyst is modest, the emissions of residual CO and H2 are kept to a minimum. Ceiling flaps can be used to avoid mixing reducing and oxidizing gas close to the catalyst surface. Openings in the distributor top segment can be used to direct excess reducing agent away from the catalyst surface.
  • the reducing gas can be collected at the catalyst outlet and returned to the main flow where the reducing agent H2 and CO will be oxidized when passing the catalyst bed together with the oxygen rich main flow as shown in Fig.9.
  • the collector follows the movement of the regenera- tive gas distributor.
  • the reducing agent can be injected in counter current direction towards the main gas flow.
  • the reducing gas will have to be injected a high ⁇ er pressure level compared to the main flow.
  • Reducing gas will in this layout (not shown) automatically mix with oxy- gen rich gas at the main flow inlet and oxidize when pass ⁇ ing the catalyst in the direction of the main gas flow of methane containing gas .
  • Fig. 10 shows a rotating methane oxidation reactor.
  • the re- ducing agent can be collected at outlet of reactor and dis ⁇ tributed into methane containing bulk gas flow (not shown) .
  • the reducing agent can in this layout also be injected in counter current direction towards the main gas flow of me ⁇ thane containing gas .
  • a two-rector layout as shown in Fig. 11 for example a gas engine operating with two parallel rectors, one reactor can be bypassed during regeneration.
  • Burner off gas from rich (lambda below 1.00) combustion of methane containing the H2 and CO reducing agent is fed counter current to the engine exhaust gas flow into the reactor with the catalyst that shall be regenerated.
  • the regeneration off gas is subsequently passed to the other reactor that is in normal engine exhaust methane slip operation. This re- quires that the burner is operating at higher pressure than the pressure of the main gas flow of methane containing gas .
  • Fig.12 shows a possible layout for gas engine applications operating with only one reactor.
  • the methane oxidation reactor is bypassed during the regeneration of the methane oxidation catalyst (CH4 slip cat.) and burner off gas con ⁇ taining the H2 and CO containing reducing agent to the tur- bocharger air inlet after passing the methane oxidation catalyst.
  • the reducing gas is thus redirected back to the engine .
  • Fig.13 shows a layout suitable for gas engine applications operating with two reactors.
  • one methane ox ⁇ idation reactor is regenerated while the methane containing engine exhaust gas is passed to the other reactor.
  • Flue gas containing H2 and CO reducing agent from a burner operating at lambda below 1.00 is passed to a turbocharger air inlet after having passed through the methane oxidation catalyst for regeneration and is thus redirected back to the engine.
  • a quartz U-tube reactor with an inner diameter of 4 mm was filled with 200 mg of a catalyst consisting of 2 wt% Pd on La-promoted alumina, which was granulated to a size range of 150-300 ym.
  • the reactor exit gas was determined by on- line infrared spectrometry, using a GasmetDX4000 FTIR spec ⁇ trometer.
  • the catalyst was heated in a mixture containing 880 ppm CH 4 , 10% 0 2 , and 5% H 2 0 in inert gas to 600 °C for 1 h, without added S02 to the feed gas.
  • Table 1 lists the measured CH 4 conversion levels at differ ⁇ ent times on stream after initial heating to 600 °C, and additional 1 h heating to 600 °C, after the conversion had dropped to about 66%. It is clear that heating to 600 °C after deactivation restores a catalytic activity for a short period, but after about 3 h after the regeneration, the conversion level is already below the level measured immediately before the regeneration, which indicates that no stable activity is obtained after heating to 600 °C.
  • Table 2 lists the measured con- versions of methane after 1 h heating at 600 °C; both the heating treatment and the activity measurements were done using the feed gas as mentioned in Example 1 without S O2 added to the feed. After heating, the methane conversion is increased for a short period of time. After only 1.5 hours, the conversion level is almost back to the level it had be- fore the heating, indicating that heating to 600 °C does not result in a stable regeneration.
  • a Pd catalyst can be regenerated in a gas containing 3 ⁇ 4 and CO, corresponding to the product gas of a fuel-rich combustion of methane.
  • 10 ppm SO 2 was added to the feed once again and the methane conversion was reduced to about 35%.
  • the conversion remained constant after removal of the SO 2 from the feed gas.
  • the catalyst was then exposed to a gas mixture consisting of 3% 3 ⁇ 4, 3% CO, 8.5% C0 2 , 20% H 2 0 in N 2 (65.5%) - the estimated composi ⁇ tion of the exhaust gas from a fuel-rich combustion of natural gas at about 10% air deficiency (A «0.9) [ North
  • This example shows that the regeneration by exposure to the fuel-rich exhaust gas can be repeated without affecting the catalyst performance.
  • the flow of the 880 ppm CH 4 /10% 0 2 ,/5% 3 ⁇ 40/inert gas mixture was increased to 300 Nml/min.
  • the catalyst was deactivated by adding 10 ppm S O2 and 20 ppm S O2 to the feed, and regenerated after each deactivation by exposure to a fuel-rich exhaust gas with the composition given in Example 3.
  • table 4 it is seen that the conversion of methane is restored after regenera ⁇ tion, and that the performance of the catalyst does not de ⁇ teriorate after repeated cycles of deactivation and regen- eration.

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Abstract

L'invention concerne la régénération in situ d'un catalyseur d'oxydation du méthane désactivé comprenant l'étape de mise du catalyseur désactivé en contact avec un agent réducteur, choisi dans l'ensemble constitué de gaz naturel, de diesel à très faible teneur en soufre, d'alcools, d'éthers, d'hydrogène, de monoxyde de carbone et d'ammoniac ou de mélanges de ceux-ci.
PCT/EP2013/069021 2013-05-30 2013-09-13 Procédé de régénération in situ de catalyseurs d'oxydation du méthane Ceased WO2014191060A1 (fr)

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CN105715345A (zh) * 2014-12-19 2016-06-29 罗伯特·博世有限公司 用于监控甲烷氧化催化剂的方法
CN105715337A (zh) * 2014-12-19 2016-06-29 罗伯特·博世有限公司 用于运行甲烷氧化催化剂的方法和废气后处理系统
CN110296009A (zh) * 2019-05-05 2019-10-01 浙江吉利控股集团有限公司 一种醇氢发动机系统及其控制方法
CN111097514A (zh) * 2018-10-29 2020-05-05 中国石油化工股份有限公司 一种低活性加氢改质降凝催化剂活性恢复的方法
CN112916053A (zh) * 2019-12-06 2021-06-08 中国科学院大连化学物理研究所 一种催化剂的再生方法
WO2022122182A1 (fr) * 2020-12-10 2022-06-16 Caterpillar Energy Solutions Gmbh Procédé et appareil de régénération d'un catalyseur des gaz d'échappement dans un moteur à gaz
EP4204668A4 (fr) * 2020-09-24 2024-11-06 Miratech Group, LLC Appareil, système et procédé d'oxydation du méthane dans un échappement de moteur à mélange pauvre
WO2025017074A1 (fr) 2023-07-19 2025-01-23 Daphne Technology SA Procédés de régénération d'un catalyseur d'oxydation de méthane
US12415158B2 (en) 2020-07-07 2025-09-16 Daphne Technology SA Apparatus and method for electron irradiation scrubbing

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Cited By (14)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN105715345B (zh) * 2014-12-19 2020-06-16 罗伯特·博世有限公司 用于监控甲烷氧化催化剂的方法
CN105715337A (zh) * 2014-12-19 2016-06-29 罗伯特·博世有限公司 用于运行甲烷氧化催化剂的方法和废气后处理系统
CN105715337B (zh) * 2014-12-19 2021-08-27 罗伯特·博世有限公司 用于运行甲烷氧化催化剂的方法和废气后处理系统
CN105715345A (zh) * 2014-12-19 2016-06-29 罗伯特·博世有限公司 用于监控甲烷氧化催化剂的方法
CN111097514A (zh) * 2018-10-29 2020-05-05 中国石油化工股份有限公司 一种低活性加氢改质降凝催化剂活性恢复的方法
CN111097514B (zh) * 2018-10-29 2022-03-08 中国石油化工股份有限公司 一种低活性加氢改质降凝催化剂活性恢复的方法
CN110296009A (zh) * 2019-05-05 2019-10-01 浙江吉利控股集团有限公司 一种醇氢发动机系统及其控制方法
CN110296009B (zh) * 2019-05-05 2022-03-22 浙江吉利控股集团有限公司 一种醇氢发动机系统及其控制方法
CN112916053A (zh) * 2019-12-06 2021-06-08 中国科学院大连化学物理研究所 一种催化剂的再生方法
US12415158B2 (en) 2020-07-07 2025-09-16 Daphne Technology SA Apparatus and method for electron irradiation scrubbing
EP4204668A4 (fr) * 2020-09-24 2024-11-06 Miratech Group, LLC Appareil, système et procédé d'oxydation du méthane dans un échappement de moteur à mélange pauvre
WO2022122182A1 (fr) * 2020-12-10 2022-06-16 Caterpillar Energy Solutions Gmbh Procédé et appareil de régénération d'un catalyseur des gaz d'échappement dans un moteur à gaz
GB2601799B (en) * 2020-12-10 2023-06-28 Caterpillar Energy Solutions Gmbh Method and apparatus for regenerating an exhaust gas catalyst in a gas engine
WO2025017074A1 (fr) 2023-07-19 2025-01-23 Daphne Technology SA Procédés de régénération d'un catalyseur d'oxydation de méthane

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