Research Papers: Fuel Combustion

Performance Degradation and Poison Build-Up of an Oxidation Catalyst in Two-Stroke Natural Gas Engine Exhaust

[+] Author and Article Information
Marc E. Baumgardner

Department of Mechanical Engineering,
Gonzaga University,
502 E. Boone Avenue,
Spokane, WA 99258
e-mail: baumgardner@gonzaga.edu

Daniel B. Olsen

Department of Mechanical Engineering,
Colorado State University,
1374 Campus Delivery,
Fort Collins, CO 80523
e-mail: Daniel.Olsen@colostate.edu

1Corresponding author.

Contributed by the Internal Combustion Engine Division of ASME for publication in the JOURNAL OF ENERGY RESOURCES TECHNOLOGY. Manuscript received December 19, 2017; final manuscript received February 15, 2018; published online March 29, 2018. Assoc. Editor: Avinash Kumar Agarwal.

J. Energy Resour. Technol 140(7), 072208 (Mar 29, 2018) (11 pages) Paper No: JERT-17-1724; doi: 10.1115/1.4039547 History: Received December 19, 2017; Revised February 15, 2018

Due to current and future exhaust emissions regulations, oxidation catalysts are increasingly being added to the exhaust streams of large-bore, two-stroke, natural gas engines. Such catalysts have a limited operational lifetime, primarily due to chemical (i.e., catalyst poisoning) and mechanical fouling resulting from the carry-over of lubrication oil from the cylinders. It is critical for users and catalyst developers to understand the nature and rate of catalyst deactivation under these circumstances. This study examines the degradation of an exhaust oxidation catalyst on a large-bore, two-stroke, lean-burn, natural gas field engine over the course of 2 years. Specifically, this work examines the process by which the catalyst was aged and tested and presents a timeline of catalyst degradation under commercially relevant circumstances. The catalyst was aged in the field for 2-month intervals in the exhaust slipstream of a GMVH-12 engine and intermittently brought back to Colorado State University for both engine testing and catalyst surface analysis. Engine testing consisted of measuring catalyst reduction efficiency as a function of temperature as well as the determination of the light-off temperature for several exhaust components. The catalyst surface was analyzed via scanning electron microscope (SEM)/energy dispersive X-ray spectroscopy (EDS) and X-ray photoelectron spectroscopy (XPS) techniques to examine the location and rate of poison deposition. After 2 years online, the catalyst light-off temperature had increased ∼55 °F (31 °C) and ∼34 wt % poisons (S, P, Zn) were built up on the catalyst surface, both of which represent significant catalyst deactivation.

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Olsen, D. B. , Hutcherson, G. C. , Willson, B. D. , and Mitchell, C. E. , 2002, “ Development of the Tracer Gas Method for Large Bore Natural Gas Engines—Part II: Measurement of Scavenging Parameters,” ASME J. Eng. Gas Turbines Power, 124(3), pp. 686–694. [CrossRef]
Olsen, D. B. , Neuner, B. , Badrinarayanan, K. , and Arney, G. , 2013, “ Performance Characteristics of Oxidation Catalysts for Lean-Burn Natural Gas Engines,” Gas Machinery Conference, Albuquerque, NM, Oct. 6–9, pp. 1–9.
Olsen, D. B. , Luedeman, M. R. , Lanham, C. D. , and Gilbert, K. , 2014, “ Development and Testing of a Timed Power Cylinder Lube Oil Injection System,” Gas Machinery Conference, Nashville, TN, Oct. 5–8, pp. 1–11.
Olsen, D. B. , Arney, G. , Reining, A. , and Matthey, J. , 2011, “ Oxidation Catalyst Performance Considerations: Catalyst Temperature, Space Velocity, and Fouling,” Gas Machinery Conference, Nashville, TN, pp. 1–12.
Bartholomew, C. H. , 2001, “ Mechanisms of Catalyst Deactivation,” Appl. Catal. A, 212(1–2), pp. 17–60. [CrossRef]
Defoort, M. , Olsen, D. , and Wilson, B. , 2002, “ Performance Evaluation of Oxidation Catalysts for Natural Gas Reciprocating Engines,” Gas Machinery Conference, Nashville, TN.
Chen, J. , Heck, R. M. , and Farrauto, R. J. , 1992, “ Deactivation Regeneration and Poison—Resistant Catalysts: Commercial Experience in Stationary Pollution Abatement,” Catal. Today, 11(4), pp. 517–545. [CrossRef]
Mowery, D. L. , Graboski, M. S. , Ohno, T. R. , and McCormick, R. L. , 1999, “ Deactivation of PdO-Al2O3 Oxidation Catalyst in Lean-Burn Natural Gas Engine Exhaust: Aged Catalyst Characterization and Studies of Poisoning by H2O and SO2,” Appl. Catal. B: Environ., 21(3), pp. 157–169. [CrossRef]
Auvray, X. P. , and Olsson, L. , 2013, “ Sulfur Dioxide Exposure: A Way to Improve the Oxidation Catalyst Performance,” Ind. Eng. Chem. Res., 52(41), pp. 14556–14566. [CrossRef]
Bunting, B. G. , More, K. , Lewis, S. , and Toops, T. , 2005, “ Phosphorous Poisoning and Phosphorous Exhaust Chemistry with Diesel Oxidation Catalysts,” SAE Paper No. 2005–01-1758.
Eaton, S. J. , Nguyen, K. , and Bunting, B. G. , 2006, “ Deactivation of Diesel Oxidation Catalysts by Oil-Derived Phosphorus,” SAE Paper No. 2006-01-3422.
Kahandawala, M. S. P. , Graham, J. L. , and Sidhu, S. S. , 2004, “ Impact of Lubricating Oil on Particulates Formed During Combustion of Diesel Fuel—A Shock Tube Study,” Fuel, 83(13), pp. 1829–1835. [CrossRef]
Miller, A. L. , Stipe, C. B. , Habjan, M. C. , and Ahlstrand, G. G. , 2007, “ Role of Lubrication Oil in Particulate Emissions From a Hydrogen-Powered Internal Combustion Engine,” Environ. Sci. Technol., 41(19), pp. 6828–6835. [CrossRef] [PubMed]
Shinjoh, H. , 2006, “ Rare Earth Metals for Automotive Exhaust Catalysts,” J. Alloys Compd., 408–412, pp. 1061–1064. [CrossRef]
Kalantar Neyestanaki, A. , Klingstedt, F. , Salmi, T. , and Murzin, D. Y. , 2004, “ Deactivation of Postcombustion Catalysts, A Review,” Fuel, 83(4–5), pp. 395–408. [CrossRef]
Cimino, S. , and Lisi, L. , 2012, “ Impact of Sulfur Poisoning on the Catalytic Partial Oxidation of Methane on Rhodium-Based Catalysts,” Ind. Eng. Chem. Res., 51(22), pp. 7459–7466. [CrossRef]
Oudet, F. , Vejux, A. , and Courtine, P. , 1989, “ Evolution During Thermal Treatment of Pure and Lanthanum-Doped Pt/Al2O3 and Pt&z.sbnd;Rh/Al2O3automotive Exhaust Catalysts: Transmission Electron Microscopy Studies on Model Samples,” Appl. Catal., 50(1), pp. 79–86. [CrossRef]
Del Angel, G. , Torres, G. , Bertin, V. , Gómez, R. , Morán-Pineda, M. , Castillo, S. , and Fierro, J. L. G. , 2006, “ The Role of Lanthanum Oxide in the Formation of NO2 Over Pt-Pb/Al2O3-La2O3 Catalysts Under Lean-Burn Conditions,” Catal. Commun., 7(4), pp. 232–235. [CrossRef]
Bitsch-Larsen, A. , Degenstein, N. J. , and Schmidt, L. D. , 2008, “ Effect of Sulfur in Catalytic Partial Oxidation of Methane Over Rh-Ce Coated Foam Monoliths,” Appl. Catal. B, 78(3–4), pp. 364–370. [CrossRef]
Leprince, T. , Aleixo, J. , Williams, S. , and Naseri, M. , 2004, “ Regeneration of Palladium Based Catalyst for Methane Abatement,” International Council on Combustion Engines, Kyoto, Japan, Paper No. 210.
Corro, G. , Cano, C. , and Fierro, J. L. G. , 2010, “ A Study of Pt-Pd/y-Al2O3 Catalysts for Methane Oxidation Resistant to Deactivation by Sulfur Poisoning,” J. Mol. Catal. A: Chem., 315(1), pp. 35–42. [CrossRef]
Lampert, J. , Kazi, M. , and Farrauto, R. , 1997, “ Palladium Catalyst Performance for Methane Emissions Abatement From Lean Burn Natural Gas Vehicles,” Appl. Catal. B, 14(3–4), pp. 211–223. [CrossRef]
Honkanen, M. , Kärkkäinen, M. , Viitanen, V. , Jiang, H. , Kallinen, K. , Huuhtanen, M. , Vippola, M. , Lahtinen, J. , Keiski, R. , and Lepistö, T. , 2013, “ Structural Characteristics of Natural-Gas-Vehicle-Aged Oxidation Catalyst,” Top. Catal., 56(9–10), pp. 576–585. [CrossRef]
Badrinarayanan, K. , 2012, “Performance Evaluation of Multiple Oxidation Catalysts on a Lean Burn Natural Gas Engine,” M.S. thesis, Colorado State University, Fort Collins, CO.
Hu, L. , and Williams, S. , 2007, “ Sulfur Poisoning and Regeneration of Pd Catalyst Under Simulated Emission Conditions of Natural Gas Engine,” SAE Paper No. 2007-01-4037.
Arosio, F. , Colussi, S. , Groppi, G. , and Trovarelli, A. , 2006, “ Regeneration of S-Poisoned Pd/Al2O3 Catalysts for the Combustion of Methane,” Catal. Today, 117(4), pp. 569–576. [CrossRef]
Eaton, S. J. , Bunting, B. G. , and Toops, T. J. , 2009, “ The Roles of Phosphorus and Soot on the Deactivation of Diesel Oxidation Catalysts,” SAE Paper No. 2009-01-0628.
Kakaee, A.-H. , Paykani, A. , and Ghajar, M. , 2014, “ The Influence of Fuel Composition on the Combustion and Emission Characteristics of Natural Gas Fueled Engines,” Renewable Sustainable Energy Rev., 38, pp. 64–78. [CrossRef]
Olsen, D. B. , Kohls, M. , and Arney, G. , 2010, “ Impact of Oxidation Catalysts on Exhaust NO2/NOx Ratio From Lean-Burn Natural Gas Engines,” J. Air Waste Manage. Assoc., 60(7), pp. 867–874. [CrossRef]
Thormählen, P. , Skoglundh, M. , Fridell, E. , and Andersson, B. , 1999, “ Low-Temperature CO Oxidation Over Platinum and Cobalt Oxide Catalysts,” J. Catal., 188(2), pp. 300–310. [CrossRef]
Bennett, M. R. , 2007, “Emissions From a Diesel Engine Operating With Soy-Based Biodiesel Fuel,” M.S. thesis, Colorado State University, Fort Collins, CO.
Bennett, M. , Volckens, J. , Stanglmaier, R. , McNichol, A. P. , Ellenson, W. D. , and Lewis, C. W. , 2008, “ Biodiesel Effects on Particulate Radiocarbon (14C) Emissions From a Diesel Engine,” J. Aerosol Sci., 39(8), pp. 667–678. [CrossRef]
Baumgardner, M. E. , Vaughn, T. L. , Lakshminarayanan, A. , Olsen, D. B. , Ratcliff, M. A. , McCormick, R. L. , and Marchese, A. J. , 2015, “ Combustion of Ligno-Cellulosic Biomass Based Oxygenated Components in a Compression Ignition Engine,” Energy Fuels, 29(11), pp. 7317–7326. [CrossRef]
U.S. National Archives and Records Administration, 2015, “U.S. Code of Federal Regulations. Title 40: Protection of Environment Part 60-Standards of Performance for New Stationary Sources,” U.S. National Archives and Records Administration, College Park, MD, Report No. 40CFR1.C.60.
Fisher Scientific, 2015, “Whatman™ Air Monitoring Filters No. 7592-104,” Fisher Scientific, Hampton, NH, https://www.fishersci.com/shop/products/whatman-pm-2-5-air-monitoring-filters/057175#?keyword=7592104
Muktibodh, A. S. , 2011, “Effect of Fuel Additives on Performance and Emissions From Industrial Diesel Engines,” Colorado State University, M.S. thesis, Fort Collins, CO.
Honkanen, M. , Karkkainen, M. , Kolli, T. , Heikkinen, O. , Viitanen, V. , Zeng, L. , Kallinen, K. , Huuhtanen, M. , Keiski, R. , Lahtinen, J. , Olsson, E. , and Vippola, M. , 2016, “ Accelerated Deactivation Studies of the Natural-Gas Oxidation Catalyst-Verifying the Role of Sulfur and Elevated Temperature in Catalyst Aging,” Appl. Catal. B, 182, pp. 439–448. [CrossRef]
Krocher, O. , Widmer, M. , Elsener, M. , Rothe, D. , and Ag, M. A. N. N. , 2009, “ Adsorption and Desorption of SOx on Diesel Oxidation Catalysts,” Ind. Eng. Chem. Res., 48(22), pp. 9847–9857. [CrossRef]
Winkler, A. , Ferri, D. , and Aguirre, M. , 2009, “ The Influence of Chemical and Thermal Aging on the Catalytic Activity of a Monolithic Diesel Oxidation Catalyst,” Appl. Catal. B, 93(1–2), pp. 177–184. [CrossRef]
Cho, H. M. , and He, B. Q. , 2007, “ Spark Ignition Natural Gas Engines—A Review,” Energy Convers. Manage., 48(2), pp. 608–618. [CrossRef]
Nithyanandan, K. , Zhang, J. , Li, Y. , Meng, X. , Donahue, R. , Lee, C. , and Dou, H. , 2016, “ Diesel-like Efficiency Using Compressed Natural Gas/Diesel Dual-Fuel Combustion,” ASME J. Energy Resour. Technol, 138(5), p. 052201. [CrossRef]
Mitchell, R. H. , and Olsen, D. B. , “ Extending Substitution Limits of a Diesel-Natural Gas Dual Fuel Engine,” ASME J. Energy Resour. Technol., 140(5), p. 052202. [CrossRef]
Baumgardner, M. E. , Davis, K. , and Olsen, D. B. , 2015, “Field Evaluation of Oxidation Catalyst Degradation on a 2-Stroke Lean Burn NG Engine,” Pipeline Research Council International, Chantilly, VA, Catalog No. PR-179-13205-R01.
U.S. National Archives and Records Administration, 2015, “ U.S. Code of Federal Regulations. Title 40: Protection of Environment Part 63-National Emission Standards for Hazardous Air Pollutants for Source Categories,” College Park, MD, Report No. 40CFR1.C.63.6600.


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Fig. 1

Catalyst used in the present study: (a) photos of the catalyst units and (b) dimensions of corrugated stainless steel layers where H = 1 mm and W = 2 mm. The locations where the sheets physically touch are the “base” areas where no catalyst material is deposited. Catalyst material is, thus, located in the open regions.

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Fig. 2

Catalyst surface analysis diagram. At left is the general surface analysis schematic going from actual catalyst sample to SEM image. At right are examples of the SEM/EDS results and how the catalyst phase and the base phase differ in their location and elemental makeup. The relative scales on the plots are representative of the two phases but meant for illustrative purposes only. Note the two phases correspond to the “valley” and “hill” areas of the corrugation: (i) the catalyst phase (Al–O–La) thick in low sections, site of poison deposition (P, Zn, and S), little to no steel base (Fe–Cr) evident, and (ii) base phase in high sections where sheet contacts adjacent sheet, catalyst layer thinned and steel support is evident, significant poison deposition not evident.

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Fig. 3

(a) Laboratory and (b) field engines

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Fig. 4

Schematic of laboratory slipstream. Note the catalyst was placed in the small catalyst housing for laboratory testing.

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Fig. 5

Schematic of field slipstream

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Fig. 6

Reduction efficiency of CO versus temperature

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Fig. 7

Reduction efficiency of ethylene versus temperature

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Fig. 8

Reduction efficiency of formaldehyde versus temperature

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Fig. 9

Reduction efficiency of VOC versus temperature

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Fig. 10

Catalyst light-off temperatures for exhaust emissions of primary interest

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Fig. 11

Catalyst surface poison buildup as a function of time. Units are wt % of surface material as determined via XPS: (a) individual traces of sulfur, phosphorus, and zinc and (b) accumulative poison level.

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Fig. 12

Poison deposition location. Images are of the leading edge of the test four catalyst sample.

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Fig. 13

Front (leading) versus back (trailing) surface buildup of catalyst poisons: (a) surface sulfur buildup, (b) surface phosphorus buildup, and (c) surface zinc buildup

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Fig. 14

Surface poison build-up as a function of PM passing over the catalyst




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