Performance and Regeneration of Methane Oxidation Catalyst for LNG Ships

Liquefied natural gas (LNG) use as marine fuel is increasing. Switching diesel to LNG in ships significantly reduces air pollutants but the methane slip from gas engines can in the worst case outweigh the CO2 decrease with an unintended effect on climate. In this study, a methane oxidation catalyst (MOC) is investigated with engine experiments in lean-burn conditions. Since the highly efficient catalyst needed to oxidize methane is very sensitive to sulfur poisoning a regeneration using stoichiometric conditions was studied to reactivate the catalyst. In addition, the effect of a special sulfur trap to protect the MOC and ensure long-term performance for methane oxidation was studied. MOC was found to decrease the methane emission up to 70–80% at the exhaust temperature of 550 degrees. This efficiency decreased within time, but the regeneration done once a day was found to recover the efficiency. Moreover, the sulfur trap studied with MOC was shown to protect the MOC against sulfur poisoning to some extent. These results give indication of the possible use of MOC in LNG ships to control methane slip emissions

Effect of periodic lean/rich switch on methane conversion over a Pd/Rh-based three way catalyst in the exhausts of natural gas vehicles

The behavior of a commercial Ce–Zr promoted Pd-Rh/Al2O3 catalyst for the abatement of methane from the exhausts of natural gas vehicles (NGVs) is studied in presence of large amounts of water under both stationary conditions and by periodically switching from lean to rich feed. Under stationary conditions with both stoichiometric (λ = 1.00) and lean (λ = 1.02) feed catalyst deactivation is observed after prolonged exposure to the reaction mixture. Periodic rich pulses in a constant lean feed gas result in the stabilization of catalytic performances.A higher methane conversion than those obtained with stoichiometric and lean feed mixtures is observed under rich conditions, during an experiment carried out by performing lean pulses (λ = 1.02) in a constant rich feed gas (λ = 0.98). The analysis of reactants conversion and products distribution suggests that different chemistries are involved under lean and rich conditions. Only reactions of complete oxidation of H2, CO, CH4 and NO occur under excess of oxygen, whereas under rich conditions NO reduction, CH4 steam reforming and water gas shift also occur.The effect of symmetric oscillation of the exhausts composition around stoichiometry is also addressed by periodically switching from slightly rich to slightly lean composition with different oscillation amplitudes (Δλ = \ub10.01, \ub10.02 and \ub10.03). Higher and more stable methane conversion performances are obtained than those observed under constant λ operations. The presence of a more active PdO/Pd0 state is suggested to explain the enhancement of catalytic performances

Effect of periodic lean/rich switch on methane conversion over a Pd/Rh-based three way catalyst in the exhausts of natural gas vehicles

The behavior of a commercial Ce–Zr promoted Pd-Rh/Al2O3 catalyst for the abatement of methane from the exhausts of natural gas vehicles (NGVs) is studied in presence of large amounts of water under both stationary conditions and by periodically switching from lean to rich feed. Under stationary conditions with both stoichiometric (λ = 1.00) and lean (λ = 1.02) feed catalyst deactivation is observed after prolonged exposure to the reaction mixture. Periodic rich pulses in a constant lean feed gas result in the stabilization of catalytic performances.A higher methane conversion than those obtained with stoichiometric and lean feed mixtures is observed under rich conditions, during an experiment carried out by performing lean pulses (λ = 1.02) in a constant rich feed gas (λ = 0.98). The analysis of reactants conversion and products distribution suggests that different chemistries are involved under lean and rich conditions. Only reactions of complete oxidation of H2, CO, CH4 and NO occur under excess of oxygen, whereas under rich conditions NO reduction, CH4 steam reforming and water gas shift also occur.The effect of symmetric oscillation of the exhausts composition around stoichiometry is also addressed by periodically switching from slightly rich to slightly lean composition with different oscillation amplitudes (Δλ = \ub10.01, \ub10.02 and \ub10.03). Higher and more stable methane conversion performances are obtained than those observed under constant λ operations. The presence of a more active PdO/Pd0 state is suggested to explain the enhancement of catalytic performances

Fundamentals of Sulfate Species in Methane Combustion Catalyst Operation and Regeneration—A Simulated Exhaust Gas Study

Emission regulations and legislation inside the European Union (EU) have a target to reduce tailpipe emissions in the transportation sector. Exhaust gas aftertreatment systems play a key role in low emission vehicles, particularly when natural gas or bio-methane is used as the fuel. The main question for methane operating vehicles is the durability of the palladium-rich aftertreatment system. To improve the durability of the catalysts, a regeneration method involving an efficient removal of sulfur species needs to be developed and implemented on the vehicle. This paper tackles the topic and its issues from a fundamental point of view. This study showed that Al2(SO4)3 over Al2O3 support material inhibits re-oxidation of Pd to PdO, and thus hinders the formation of the low-temperature active phase, PdOx. The presence of Al2(SO4)3 increases light-off temperature, which may be due to a blocking of active sites. Overall, this study showed that research should also focus on support material development, not only active phase inspection. An active catalyst can always be developed, but the catalyst should have the ability to be regenerated

Decomposition of Al₂O₃-Supported PdSO₄ and Al₂(SO₄)₃ in the Regeneration of Methane Combustion Catalyst: A Model Catalyst Study

Exhaust gas aftertreatment systems play a key role in controlling transportation greenhouse gas emissions. Modern aftertreatment systems, often based on Pd metal supported on aluminum oxide, provide high catalytic activity but are vulnerable to sulfur poisoning due to formation of inactive sulfate species. This paper focuses on regeneration of Pd-based catalyst via the decomposition of alumina-supported aluminum and palladium sulfates existing both individually and in combination. Decomposition experiments were carried out under hydrogen (10% H2/Ar), helium (He), low oxygen (0.1% O2/He), and excess oxygen (10% O2/He). The structure and composition of the model catalysts were examined before and after the decomposition reactions via powder X-ray diffraction and elemental sulfur analysis. The study revealed that individual alumina-supported aluminum sulfate decomposed at a higher temperature compared to individual alumina-supported palladium sulfate. The simultaneous presence of aluminum and palladium sulfates on the alumina support decreased their decomposition temperatures and led to a higher amount of metallic palladium than in the corresponding case of individual supported palladium sulfate. From a fundamental point of view, the lowest decomposition temperature was achieved in the presence of hydrogen gas, which is the optimal decomposition atmosphere among the studied conditions. In summary, aluminum sulfate has a two-fold role in the regeneration of a catalyst—it decreases the Pd sulfate decomposition temperature and hinders re-oxidation of less-active metallic palladium to active palladium oxide

The Effect of Phosphorus Exposure on Diesel Oxidation Catalysts-Part II : Characterization of Structural Changes by Transmission Electron Microscopy

Phosphorus poisoning and its effect on the diesel oxidation catalysts morphology was studied by transmission electron microscopy (TEM). The studied catalyst samples were PtPd or Pt supported on the alumina-based washcoat including additives. The laboratory-scale phosphorus exposures were carried out with two different phosphorus concentrations. The cross-sectional TEM samples were prepared from the fresh and phosphorus-treated catalysts. After phosphorus exposures, significant structural changes were observed compared to the fresh catalysts. The shape of the noble metal particles had changed from irregular to more spherical-shaped particles. In addition, phosphorus was detected throughout the catalyst TEM samples but the amount varied depending on the local composition of the support. Phosphorus accumulated mainly in the alumina-containing areas of the support and indications of dense and amorphous aluminium phosphates were found. Based on the results gained, cross-sectional TEM characterization is essential to observe these kinds of morphological changes in the catalysts caused e.g. by phosphorus exposures. In addition, cross-sectional TEM samples are needed to study the effect of local variation in the support composition on the phosphorus accumulation.acceptedVersionPeer reviewe