Grantee Research Project Results

1997 Progress Report: Fundamental Study on High Temperature Chemistry of Oxygenated Hydrocarbons as Alternate Motor Fuels and Additives

EPA Grant Number: R824970C008
Subproject: this is subproject number 008 , established and managed by the Center Director under grant R824970
(EPA does not fund or establish subprojects; EPA awards and manages the overall grant for this center).
Center: Research Consortium on Ozone and Fine Particle Formation in California and in the Northeastern United States
Center Director: Seinfeld, John
Title: Fundamental Study on High Temperature Chemistry of Oxygenated Hydrocarbons as Alternate Motor Fuels and Additives
Investigators: Bozzelli, Joseph W. , Lay, Tsan
Institution: New Jersey Institute of Technology
EPA Project Officer: Hahn, Intaek
Project Period: January 1, 1992 through December 31, 1995
Project Period Covered by this Report: January 1, 1996 through December 31, 1997
Project Amount: Refer to main center abstract for funding details.
RFA: Center on Airborne Organics (1993) Recipients Lists
Research Category: Targeted Research

Objective:

Experiments and model development are performed to understand fundamental reaction processes of oxygenated hydrocarbons (OHC's) such as alcohols and ethers important to gasoline octane blending.  Detailed mechanisms are developed to allow optimization and trend prediction in engine performance and emission reduction. 

Rationale:  Oxygenates, such as dimethyl ether, methanol and ethanol, are scheduled for widespread use as additives and alternative motor fuels.  methyl tertbutyl ether (MTBE), is widely used as an anti-knock component and oxygenate additive in gasolines. Experimental data are needed for model development and validation.  A model based on fundamentals, calibrated by experimental data, will facilitate calculations of trends for future experiment testing and preferred fuel blends to reduce undesirable emissions e.g., HC's, CO, etc. while maintaining or improving engine performance. 
Approach:  Experimental:  Gas mixtures are reacted in a variable pressure, high temperature tubular flow reactor.  Reactor effluent is analyzed for products as a function of temperature, residence time, and fuel equivalence ratio.  Analysis is performed with on-line gas chromatography (GC), flame ionization detection (FID), Fourier Transform Infrared (FTIR) and GC / Mass Spectrometry. 

Modeling:  Reaction mechanisms are built from elementary reactions with rate constants based upon fundamental principles of thermochemical kinetics, statistical mechanics and transition state theory.  Quantum Rice-Ramsperger-Kassel theory for k(E), modified strong collision treatment for fall-off and thermodynamic properties are used in chemical activation and unimolecular reactions.  Ab initio and semiempirical calculations along with applications of group additivity are used to determine properties of transition states. 

Summary:  Oxidation and pyrolysis experiments on mixtures MTBE in methane / oxygen are completed at one to ten atmospheres, fuel equivalence ratios of 0.7 to 1.5.  Variable pressure experiments were initiated on dimethyl ether.  A thermodynamic data base and an initial elementary reaction mechanism has been assembled for MTBE oxidation and evaluated.  Sub-models for oxidation of neopentane, isobutane, and isobutene oxidation are developed and literature data on shown to compare well compared with experimental data. 
An initial reaction mechanism for oxidation of dimethyl ether is also developed and currently being tested by MIT. 

Key Personnel 

Graduate Students:  Ruth Wei and Takahiro Yamad 
Undergraduate Students:  Allan Petrin and Gem Pate 
Others: Rajiv Berr 
CAO Collaborators   Tim Jungkamp, John Seinfeld and Jack Howard

Supplemental Keywords:

RFA, Scientific Discipline, Air, Waste, particulate matter, mobile sources, Environmental Chemistry, Incineration/Combustion, Atmospheric Sciences, Physics, vehicle emissions, aerosols, combustion contaminants, combustion emissions, emissions, aerosol mass spectrometry, gas chromatography, mass spectrometry, MTBE, atmospheric chemistry, combustion, modeling studies, thermodynamics, combustion byproducts, high temperature reaction kinetics, fuels, motor vehicles, particulates, reaction mechanisms, automotive, ozone, high temperatuture chemistry, alternative motor fuels, modeling, automobiles, automotive exhaust, cars

Progress and Final Reports:

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Final

Main Center Abstract and Reports:

R824970    Research Consortium on Ozone and Fine Particle Formation in California and in the Northeastern United States

Subprojects under this Center: (EPA does not fund or establish subprojects; EPA awards and manages the overall grant for this center).
R824970C001 Chemical Kinetic Modeling of Formation of Products of Incomplete Combustion from Spark-ignition Engines
R824970C002 Combustion Chamber Deposit Effects on Engine Hydrocarbon Emissions
R824970C003 Atmospheric Transformation of Volatile Organic Compounds: Gas-Phase Photooxidation and Gas-to-Particle Conversion
R824970C004 Mathematical Models of the Transport and Fate of Airborne Organics
R824970C005 Elementary Reaction Mechanism and Pathways for Atmospheric Reactions of Aromatics - Benzene and Toluene
R824970C006 Simultaneous Removal of Soot and NOx from the Exhaust of Diesel Powered Vehicles
R824970C007 Modeling Gas-Phase Chemistry and Heterogeneous Reaction of Polycyclic Aromatic Compounds
R824970C008 Fundamental Study on High Temperature Chemistry of Oxygenated Hydrocarbons as Alternate Motor Fuels and Additives
R824970C009 Markers for Emissions from Combustion Sources
R824970C010 Experimental Investigation of the Evolution of the Size and Composition Distribution of Atmospheric Organic Aerosols
R824970C011 Microengineered Mass Spectrometer for in-situ Measurement of Airborne Contaminants