Hoesterey, BL
1988-1987
Prediction and Modeling of Coal Conversion Reactions by Pyrolysis Mass Spectrometry and Multivariate Statistical Analysis
Meuzelaar, H.L.C.; Hoesterey, B.L.; Windig, W. and Hill, G.R.
Fuel Processing Technology, l5, 59-70, 1987. 11 pgs. Funded by Electric Power Research Institute and US Department of Energy.
Report on the use of Curie-point pyrolysis MS as a microscale modeling technique for the conversion of four Western US coals into pyrolytic tars and for the production of SO2 during the combustion of l6 Gulf Province lignites.
Investigation of Structure/Property Relationships of Selected C5 to C10 Hydrocarbons Using Canonical Correlation Analysis of Multisource Data
Hoesterey, B.L.; Meuzelaar, H.L.C. and Pugmire, R.J.
Submitted to Anal. Chem., 1988. 28 pgs. Funded by ACERC (National Science Foundation and Associates and Affiliates).
Twelve physico-chemical and thermodynamic properties including molecular weight, boiling point, flash point, density, refractive index, volumetric, gravimetric, and molar heats of combustion, atomic H/C, carbon number, hydrogen number and the fuel-related threshold sooting index for 47 C5 to C10 hydrocarbons were subjected to factor analysis. Two factors with eigenvalues greater than 1.0 were found, accounting for 95% of the variance. The major groups of variables were interpreted as arising from either molecular size (boiling point, flash point, molar heat of combustion, molecular weight and carbon number) or degree of unsaturation (density, refractive index, volumetric heat of combustion, threshold sooting index, H/C and gravimetric heat of combustion). When three factors from the physicochemical and thermodynamic properties factor space were used for canonical correlation analysis with the Wiener topological index, molecular size related papers were found to correlate with it. Canonical correlation analysis of the properties factor space with mass spectrometry/Kavats retention index data showed that characteristic mass spectral variables correlated closely with the degree of unsaturation by differentiating aliphatic from aromatic compounds. The Kovats retention index variable, not unexpectedly, modeled molecular size related parameters such as carbon number.
Effects of Low Temperature Air Oxidation (Weathering) Reactions on the Pyrolysis of Mass Spectra of US Coals
Jakab, E.; Hoesterey, B.L.; Windig, W.; Gill, G.R. and Meuzelaar, H.L.C.
Fuel, 67, (1), 73-79, 1988. 6 pgs. Funded by US Department of Energy and Utah Power and Light.
Two high volatile bituminous coals (Upper Freeport and Hiawatha seams), a subbituminous coal (Adaville seam) were used to investigate the effect of low temperature air oxidation ("weathering") on the yield and composition of vacuum pyrolysis products. Fresh coal samples were exposed to air at 80º and 100ºC for up to 10 days under controlled laboratory conditions. Curie-point pyrolysis mass spectrometry combined with computerized data analysis was applied to study the weathering induced changes in a series of samples weathered for various lengths of time. It was found that the abundance of small oxygen-containing molecules such as carbon monoxide, carbon dioxide and aliphatic carboxylic acids increased in the pyrolysate of all samples, whereas phenols and dihydroxybenzenes showed decreased yields, especially in the two lowest rank coals. Besides phenols, alkylnaphthalenes and alkyltetralins showed decreased abundances in the pyrolysis mass spectra of the two high volatile bituminous coals. An attempt is made to explain the difference in pyrolysis patterns observed before and after weathering experiments in terms of underlying structural changes.
An Integrated Spectroscopic Approach to the Chemical Characterization of Pyrolysis Oils
Hoesterey, B.L.; Windig, W.; Meuzelaar, H.L.C.; Eyring, E.M.; Grant, D.M. and Pugmire, R.J.
Processing of Pyrolysis Oils, 1988, E.J., Soltes (ed.) ACS Symp. Series, in press. Funded by Consortium for Fossil Fuel Liquefaction Science and US Department of Energy.
The hydrocarbon ("oil") fraction of a coal pyrolysis tar prepared by open-column liquid chromatography (LC) was separated into l6 subfractions by a second LC procedure. Low voltage mass spectrometry (MS), infrared spectroscopy (1R), and proton (PMR) as well as carbon-13 nuclear magnetic resonance spectrometry (CMR) were performed on the first 13 subfractions. Computerized multivariate analysis procedures such as factor analysis followed by canonical correlation techniques were used to extract the overlapping information from the analytical data. Subsequent evaluation of the integrated analytical data revealed chemical information that could not have been obtained readily from the individual spectroscopic techniques. The approach described is generally applicable to multisource analytical data on pyrolysis oils and other complex mixtures.
Attempted Development of a "Weathering Index" for Argonne PCSP Coals
Yun, Y.; Hoesterey, B.L.; Meuzelaar, H.L.C. and Hill, G.R.
ACS Preprints, 32, 4, 1987, New Orleans. Funded by US Department of Energy.
In order to develop a reliable, simple procedure for determining the oxidation status ("weathering index") of a coal sample, several candidate methods were tested with all eight coals from the Argonne Premium Coal Sample Program after air oxidation under relatively mild, controlled environmental conditions. Twenty-five gram aliquots of all eight PCSP coals were exposed to a 10-ml/min dry airflow at 100ºC in all-glass reactors for eight days. Weight changes and O2, CO2, and H2O exchange rates were recorded. Among the various characterization methods tested were FSI, slurry pH, Zeta potential and thermogravimetry. Pyrolysis mass spectrometry and Fourier transform IR spectroscopy were used to monitor structural changes. Results obtained to data show that FSI is a good indicator of oxidation state for low-to-medium caking coals of bituminous rank whereas slurry pH appeared to be less useful for most coals. Although Zeta potential and thermogravimetry tests are still underway, it is becoming quite clear that a reliable, generally useful "weathering index" may have to be based on a fairly comprehensive battery of tests rather than on a single technique.
Hoesterey, BL
1988-1987
Prediction and Modeling of Coal Conversion Reactions by Pyrolysis Mass Spectrometry and Multivariate Statistical Analysis
Meuzelaar, H.L.C.; Hoesterey, B.L.; Windig, W. and Hill, G.R.
Fuel Processing Technology, l5, 59-70, 1987. 11 pgs. Funded by Electric Power Research Institute and US Department of Energy.
Report on the use of Curie-point pyrolysis MS as a microscale modeling technique for the conversion of four Western US coals into pyrolytic tars and for the production of SO2 during the combustion of l6 Gulf Province lignites.
Investigation of Structure/Property Relationships of Selected C5 to C10 Hydrocarbons Using Canonical Correlation Analysis of Multisource Data
Hoesterey, B.L.; Meuzelaar, H.L.C. and Pugmire, R.J.
Submitted to Anal. Chem., 1988. 28 pgs. Funded by ACERC (National Science Foundation and Associates and Affiliates).
Twelve physico-chemical and thermodynamic properties including molecular weight, boiling point, flash point, density, refractive index, volumetric, gravimetric, and molar heats of combustion, atomic H/C, carbon number, hydrogen number and the fuel-related threshold sooting index for 47 C5 to C10 hydrocarbons were subjected to factor analysis. Two factors with eigenvalues greater than 1.0 were found, accounting for 95% of the variance. The major groups of variables were interpreted as arising from either molecular size (boiling point, flash point, molar heat of combustion, molecular weight and carbon number) or degree of unsaturation (density, refractive index, volumetric heat of combustion, threshold sooting index, H/C and gravimetric heat of combustion). When three factors from the physicochemical and thermodynamic properties factor space were used for canonical correlation analysis with the Wiener topological index, molecular size related papers were found to correlate with it. Canonical correlation analysis of the properties factor space with mass spectrometry/Kavats retention index data showed that characteristic mass spectral variables correlated closely with the degree of unsaturation by differentiating aliphatic from aromatic compounds. The Kovats retention index variable, not unexpectedly, modeled molecular size related parameters such as carbon number.
Effects of Low Temperature Air Oxidation (Weathering) Reactions on the Pyrolysis of Mass Spectra of US Coals
Jakab, E.; Hoesterey, B.L.; Windig, W.; Gill, G.R. and Meuzelaar, H.L.C.
Fuel, 67, (1), 73-79, 1988. 6 pgs. Funded by US Department of Energy and Utah Power and Light.
Two high volatile bituminous coals (Upper Freeport and Hiawatha seams), a subbituminous coal (Adaville seam) were used to investigate the effect of low temperature air oxidation ("weathering") on the yield and composition of vacuum pyrolysis products. Fresh coal samples were exposed to air at 80º and 100ºC for up to 10 days under controlled laboratory conditions. Curie-point pyrolysis mass spectrometry combined with computerized data analysis was applied to study the weathering induced changes in a series of samples weathered for various lengths of time. It was found that the abundance of small oxygen-containing molecules such as carbon monoxide, carbon dioxide and aliphatic carboxylic acids increased in the pyrolysate of all samples, whereas phenols and dihydroxybenzenes showed decreased yields, especially in the two lowest rank coals. Besides phenols, alkylnaphthalenes and alkyltetralins showed decreased abundances in the pyrolysis mass spectra of the two high volatile bituminous coals. An attempt is made to explain the difference in pyrolysis patterns observed before and after weathering experiments in terms of underlying structural changes.
An Integrated Spectroscopic Approach to the Chemical Characterization of Pyrolysis Oils
Hoesterey, B.L.; Windig, W.; Meuzelaar, H.L.C.; Eyring, E.M.; Grant, D.M. and Pugmire, R.J.
Processing of Pyrolysis Oils, 1988, E.J., Soltes (ed.) ACS Symp. Series, in press. Funded by Consortium for Fossil Fuel Liquefaction Science and US Department of Energy.
The hydrocarbon ("oil") fraction of a coal pyrolysis tar prepared by open-column liquid chromatography (LC) was separated into l6 subfractions by a second LC procedure. Low voltage mass spectrometry (MS), infrared spectroscopy (1R), and proton (PMR) as well as carbon-13 nuclear magnetic resonance spectrometry (CMR) were performed on the first 13 subfractions. Computerized multivariate analysis procedures such as factor analysis followed by canonical correlation techniques were used to extract the overlapping information from the analytical data. Subsequent evaluation of the integrated analytical data revealed chemical information that could not have been obtained readily from the individual spectroscopic techniques. The approach described is generally applicable to multisource analytical data on pyrolysis oils and other complex mixtures.
Attempted Development of a "Weathering Index" for Argonne PCSP Coals
Yun, Y.; Hoesterey, B.L.; Meuzelaar, H.L.C. and Hill, G.R.
ACS Preprints, 32, 4, 1987, New Orleans. Funded by US Department of Energy.
In order to develop a reliable, simple procedure for determining the oxidation status ("weathering index") of a coal sample, several candidate methods were tested with all eight coals from the Argonne Premium Coal Sample Program after air oxidation under relatively mild, controlled environmental conditions. Twenty-five gram aliquots of all eight PCSP coals were exposed to a 10-ml/min dry airflow at 100ºC in all-glass reactors for eight days. Weight changes and O2, CO2, and H2O exchange rates were recorded. Among the various characterization methods tested were FSI, slurry pH, Zeta potential and thermogravimetry. Pyrolysis mass spectrometry and Fourier transform IR spectroscopy were used to monitor structural changes. Results obtained to data show that FSI is a good indicator of oxidation state for low-to-medium caking coals of bituminous rank whereas slurry pH appeared to be less useful for most coals. Although Zeta potential and thermogravimetry tests are still underway, it is becoming quite clear that a reliable, generally useful "weathering index" may have to be based on a fairly comprehensive battery of tests rather than on a single technique.