Kelemen, SR
1998
Nitrogen Transformation in Coal During Pyrolysis
Kelemen, S.R.; Gorbaty, M.L.; Kwiatek, P.J.; Fletcher, T.H.; Watt, M.; Solum, M.S. and Pugmire, R.J.
Energy & Fuels, 12:159-73 (1998).
X-ray photoelectron spectroscopy (XPS) was used to identify and quantify the changes in organically bound nitrogen forms present in the tars and chars of coals after pyrolysis. For fresh coal, pyrrolic nitrogen is the most abundant form of organically bound nitrogen, followed by pyridinic, quaternary, and amino types. Some of the quaternary nitrogen species initially present in coal are lost upon mild pyrolysis, prior to hydrocarbon devolatilization. These quaternary species are attributed to pyridinic or basic nitrogen species associated with hydroxyl groups from carboxylic acids or phenols. A portion of the quaternary nitrogen species is lost at the very earliest stage of pyrolysis. Upon devolatilization, the resultant tar and char contain mostly pyrrolic and pyridinic forms; however, a portion of the quaternary nitrogen initially present in the coal appears in the coal char and tar. The relatively strong bonding interactions associated with these quaternary species suggests that there may be other quaternary nitrogen, in addition to protonated pyridines, in low-rank coal. For low-rank coal, amino groups are preferentially released and concentrate in the tar. XPS analysis of chars and tars produced during rapid heat-up (10^14 deg/s) pyrolysis show similar trends. However, severe pyrolysis of the devolatilized char results in the appearance of an asymmetric carbon (1s) line shape indicative of very large polynuclear "graphitic-like" units. This transformation is accompanied by a rise in the relative number of quaternary nitrogen forms and occurs over a relatively narrow temperature range. Quaternary and pyridinic nitrogen forms become the dominant forms in severely pyrolyzed chars. The relatively low level of quaternary nitrogen in the rapid heat-up chars indicates that very large polynuclear aromatic structures are not fully developed under these pyrolysis conditions.
1997
Nitrogen Transformations in Coal During Pyrolysis
Kelemen, S.R.; Gorbaty, M.L.; Kwiatek, P.J.; Fletcher, T.H.; Watt, M.; Solum, M.S. and Pugmire, R.J.
Energy & Fuels, 12:159-72(1997). Funded by ACERC, Exxon and Federal Energy Technology Center.
X-ray photoelectron spectroscopy (XPS) was used to identify and quantify the changes in organically bound nitrogen forms present in the tars and chars of coal after pyrolysis. For fresh coal, pyrrolic nitrogen is the most abundant form of organically bound nitrogen, followed by pyridinic, quaternary, and amino types. Some of the quaternary nitrogen species initially present in coal are lost upon mild pyrolysis, prior to hydrocarbon devolatilization. These quaternary species are attributed to pyridinic or basic nitrogen species associated with hydroxyl groups from carboxylic acids or phenols. A portion of the quaternary nitrogen species is lost at the very earliest stage of pyrolysis. Upon devolatilization, the resultant tar and char contain mostly pyrrolic and pyridinic forms; however, a portion of the quaternary nitrogen initially present in the coal appears in the coal char and tar. The relatively strong bonding interactions associated with theses quaternary species suggests that there may be other quaternary nitrogen, in addition to protonated pyridines, in low-rank coal. For low-rank coal, amino groups are preferentially released and concentrate in the tar. XPS analysis of chars and tars produced during rapid heat-up (104 deg/s) pyrolysis show similar trends. However, sever pyrolysis of the devolatilized char results in the appearance of asymmetric carbon (1s) line shape indicative of very large polynuclear "graphitic-like" units. This transformation is accompanied by a rise in the relative number of quaternary nitrogen forms and occurs over a relatively narrow temperature range. Quaternary and pyridinic nitrogen forms become the dominant forms in severely pyrolyzed chars. The relatively low level of quaternary nitrogen in the rapid heat up chars indicates that very large polynuclear aromatic structures are not fully developed under these pyrolysis conditions.
N-15 CPMAS NMR of the Argonne Premium Coals
Solum, M.S.; Pugmire, R.J; Grant, D.M.; Kelemen, S.R.; Gorbaty, M.L. and Wind, R.A.
Energy & Fuels, 11:491-94(1997). Funded by ACERC and US Department of Energy.
N-15 NMR data are reported for the Argonne Premium Coals. Arguments are presented to explain discrepancies between observations and conclusions obtained from NMR experiments and those obtained by XPS and XANES techniques. Delectability of different types of nitrogens is discussed in terms of cross-polarization dynamics together with effects of the large chemical shift anisotropy that is found in different types of nitrogen functional groups. Data on acid-treated coals confirm the presence of pyridinic type nitrogens that were not observed in a previous N-15 NMR study of coals.
Kelemen, SR
1998
Nitrogen Transformation in Coal During Pyrolysis
Kelemen, S.R.; Gorbaty, M.L.; Kwiatek, P.J.; Fletcher, T.H.; Watt, M.; Solum, M.S. and Pugmire, R.J.
Energy & Fuels, 12:159-73 (1998).
X-ray photoelectron spectroscopy (XPS) was used to identify and quantify the changes in organically bound nitrogen forms present in the tars and chars of coals after pyrolysis. For fresh coal, pyrrolic nitrogen is the most abundant form of organically bound nitrogen, followed by pyridinic, quaternary, and amino types. Some of the quaternary nitrogen species initially present in coal are lost upon mild pyrolysis, prior to hydrocarbon devolatilization. These quaternary species are attributed to pyridinic or basic nitrogen species associated with hydroxyl groups from carboxylic acids or phenols. A portion of the quaternary nitrogen species is lost at the very earliest stage of pyrolysis. Upon devolatilization, the resultant tar and char contain mostly pyrrolic and pyridinic forms; however, a portion of the quaternary nitrogen initially present in the coal appears in the coal char and tar. The relatively strong bonding interactions associated with these quaternary species suggests that there may be other quaternary nitrogen, in addition to protonated pyridines, in low-rank coal. For low-rank coal, amino groups are preferentially released and concentrate in the tar. XPS analysis of chars and tars produced during rapid heat-up (10^14 deg/s) pyrolysis show similar trends. However, severe pyrolysis of the devolatilized char results in the appearance of an asymmetric carbon (1s) line shape indicative of very large polynuclear "graphitic-like" units. This transformation is accompanied by a rise in the relative number of quaternary nitrogen forms and occurs over a relatively narrow temperature range. Quaternary and pyridinic nitrogen forms become the dominant forms in severely pyrolyzed chars. The relatively low level of quaternary nitrogen in the rapid heat-up chars indicates that very large polynuclear aromatic structures are not fully developed under these pyrolysis conditions.
1997
Nitrogen Transformations in Coal During Pyrolysis
Kelemen, S.R.; Gorbaty, M.L.; Kwiatek, P.J.; Fletcher, T.H.; Watt, M.; Solum, M.S. and Pugmire, R.J.
Energy & Fuels, 12:159-72(1997). Funded by ACERC, Exxon and Federal Energy Technology Center.
X-ray photoelectron spectroscopy (XPS) was used to identify and quantify the changes in organically bound nitrogen forms present in the tars and chars of coal after pyrolysis. For fresh coal, pyrrolic nitrogen is the most abundant form of organically bound nitrogen, followed by pyridinic, quaternary, and amino types. Some of the quaternary nitrogen species initially present in coal are lost upon mild pyrolysis, prior to hydrocarbon devolatilization. These quaternary species are attributed to pyridinic or basic nitrogen species associated with hydroxyl groups from carboxylic acids or phenols. A portion of the quaternary nitrogen species is lost at the very earliest stage of pyrolysis. Upon devolatilization, the resultant tar and char contain mostly pyrrolic and pyridinic forms; however, a portion of the quaternary nitrogen initially present in the coal appears in the coal char and tar. The relatively strong bonding interactions associated with theses quaternary species suggests that there may be other quaternary nitrogen, in addition to protonated pyridines, in low-rank coal. For low-rank coal, amino groups are preferentially released and concentrate in the tar. XPS analysis of chars and tars produced during rapid heat-up (104 deg/s) pyrolysis show similar trends. However, sever pyrolysis of the devolatilized char results in the appearance of asymmetric carbon (1s) line shape indicative of very large polynuclear "graphitic-like" units. This transformation is accompanied by a rise in the relative number of quaternary nitrogen forms and occurs over a relatively narrow temperature range. Quaternary and pyridinic nitrogen forms become the dominant forms in severely pyrolyzed chars. The relatively low level of quaternary nitrogen in the rapid heat up chars indicates that very large polynuclear aromatic structures are not fully developed under these pyrolysis conditions.
N-15 CPMAS NMR of the Argonne Premium Coals
Solum, M.S.; Pugmire, R.J; Grant, D.M.; Kelemen, S.R.; Gorbaty, M.L. and Wind, R.A.
Energy & Fuels, 11:491-94(1997). Funded by ACERC and US Department of Energy.
N-15 NMR data are reported for the Argonne Premium Coals. Arguments are presented to explain discrepancies between observations and conclusions obtained from NMR experiments and those obtained by XPS and XANES techniques. Delectability of different types of nitrogens is discussed in terms of cross-polarization dynamics together with effects of the large chemical shift anisotropy that is found in different types of nitrogen functional groups. Data on acid-treated coals confirm the presence of pyridinic type nitrogens that were not observed in a previous N-15 NMR study of coals.