Modeling Oxidation and Hydrolysis Reactions in Supercritical Water—free Radical Elementary Reaction Networks and Their Applications

Ploeger, Jason M.; Bielenberg, Patricia A.; Dinaro-Blanchard, J. L.; Lachance, Russell P.; Taylor, Joshua P.; Green, William; Tester, Jefferson W.

doi:10.1080/00102200500287209

Cited by 18 publications

(9 citation statements)

References 65 publications

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“…As temperature increases, N 2 O yield decreases to 30–40% at T = 700°C. Previous studies have shown that matching product distributions is the most reliable method for validating elementary reaction rate mechanisms,26 so the N 2 O yield data will be key to the development of an ammonia–ethanol cooxidation model.…”

Section: Resultsmentioning

confidence: 99%

Cooxidation of ammonia and ethanol in supercritical water, part 1: Experimental results

2007

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in Wiley InterScience (www.interscience.wiley.com).The cooxidative effect of ethanol on ammonia oxidation in supercritical water was studied for a range of temperatures (655-7058C), initial ammonia (1-3 mM), ethanol (0-1.0 mM), and oxygen concentrations (0.7-5.0 mM), corresponding to fuel equivalence ratios ranging from 0.9 to 2.2 for the complete combustion of both organic species. With a stoichiometric amount of oxygen available for complete oxidation, the addition of ethanol on an equivalent molar basis was found to increase ammonia conversion from 20 to 65% at initial concentrations of 1 mM for each reactant, T ¼ 7008C, P ¼ 246 bar, and t ¼ 2.5 s. Nitrous oxide was produced in much larger quantities for ammonia-ethanol cooxidation than for ammonia oxidation. Based on fractional yields of nitrogen product, this amounted to 40-75% for co-oxidation with ethanol versus 4-13% without ethanol present.

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Section: Resultsmentioning

confidence: 99%

Cooxidation of ammonia and ethanol in supercritical water, part 1: Experimental results

2007

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“…A number of works that study in depth the organic reactions in SCW, focusing on the influence of the properties of water and in the kinetics modeling, has been developed over the last few years. [61][62][63][64] Thus, in this work, only a few remarks about the SCWO reactions and their kinetics modeling from an engineering perspective are presented.…”

Section: Oxidation Reactions In Supercritical Watermentioning

confidence: 99%

Supercritical water oxidation: A technical review

2006

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Supercritical water oxidation (SCWO) technology presents important environmental advantages for the treatment of industrial wastes and sludges. The homogeneous reaction that takes place between the oxidizable materials and oxygen, at temperatures and pressures above the critical point of the water (647.3 K and 22.12 MPa), is well known. Specific equations of state for water and aqueous mixtures, gases, and organics have been developed. The process is not having the expected industrial development. Some new plants have been closed by corrosion and operational problems related with high temperature, high pressure, and oxidative atmosphere inside of the equipments. To overcome these technical difficulties more research focused on solving operational problems is necessary. This article presents an overview of the technical aspects of the supercritical water oxidation process. Reactors design, construction materials, corrosion, salts precipitation problems, and industrial applications are discussed. © 2006 American Institute of Chemical Engineers AIChE J, 2006

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“…• 2 [26]. H 2 NNO x may rearrange and react to form products with different overall rates and branching ratios than the low-pressure literature values.…”

Section: Figurementioning

confidence: 80%

“…The predicted N 2 O yields are much closer to experimentally observed values and reproduce the experimental trend of decreasing yield with increasing temperature. Since matching experimental channel yields is the most reliable method of validating elementary reaction rate mechanisms [26], we interpret the improved N 2 O yield predictions as confirmation that the updated ammoniaethanol mechanism more accurately models the co-oxidation reaction. Figure 5 also shows that the ammonia conversion can be considered constant with respect to temperature because the three ammonia conversion profiles are within the ±2% experimental error of each other.…”

Section: Updated Ammonia-ethanol Mechanismmentioning

confidence: 85%

Co‐oxidation of ammonia and ethanol in supercritical water, part 2: Modeling demonstrates the importance ofH₂NNO_x

Ploeger

Green

Tester

2008

Int J of Chemical Kinetics

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A co-oxidation model was constructed from available submechanisms for ammonia and ethanol oxidation. The ammonia submechanism validated for combustion at atmospheric pressure conditions was modified for the higher densities and lower temperatures (655-700 • C) of supercritical water. The ethanol submechanism had previously been tested and validated at supercritical water conditions. The initial model poorly reproduced experimental ammonia conversion data and was not able to consistently match nitrous oxide production as a function of temperature over a range from 655-700 • C at 246 bar. To improve model predictions, the low-pressure NH 2 + NO x submechanism was replaced with a submechanism that included the H 2 NNO x adduct species that are expected to be stabilized in the high-pressure supercritical water environment. Thermochemical and kinetic parameters for the adduct species were estimated with quantum chemical calculations using Gaussian 98 with

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Modeling Oxidation and Hydrolysis Reactions in Supercritical Water—free Radical Elementary Reaction Networks and Their Applications

Cited by 18 publications

References 65 publications

Cooxidation of ammonia and ethanol in supercritical water, part 1: Experimental results

Cooxidation of ammonia and ethanol in supercritical water, part 1: Experimental results

Supercritical water oxidation: A technical review

Co‐oxidation of ammonia and ethanol in supercritical water, part 2: Modeling demonstrates the importance ofH₂NNO_x

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Modeling Oxidation and Hydrolysis Reactions in Supercritical Water—free Radical Elementary Reaction Networks and Their Applications

Cited by 18 publications

References 65 publications

Cooxidation of ammonia and ethanol in supercritical water, part 1: Experimental results

Cooxidation of ammonia and ethanol in supercritical water, part 1: Experimental results

Supercritical water oxidation: A technical review

Co‐oxidation of ammonia and ethanol in supercritical water, part 2: Modeling demonstrates the importance ofH2NNOx

Contact Info

Product

Resources

About

Co‐oxidation of ammonia and ethanol in supercritical water, part 2: Modeling demonstrates the importance ofH₂NNO_x