Surface characterization of alkali-treated coals

Baltrus, John P.; Diehl, J. Rodney; D'Este, Joseph R.; Ladner, Edward P.

doi:10.1016/0016-2361(90)90267-t

Cited by 10 publications

(1 citation statement)

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“…The development and application of direct analytical tools for quantifying heteroatom functionalities in complex solid and nonvolatile carbonaceous systems has been the focus of much research. − X-ray photoelectron spectroscopy (XPS) 13-17,20,27-29,36 and X-ray absorption near edge structure (XANES) 6-8 studies have established that pyrrolic and pyridinic forms are the most abundant nitrogen forms present in fresh coal. There have been several XPS and XANES studies which have characterized nitrogen in petroleum and coal derived products, ,− kerogen, , and crude oil asphaltenes. , These nondestructive techniques along with 15 N NMR 37,38 are being developed to yield complementary new information about nitrogen functionalities in carbonaceous materials.…”

Section: Introductionmentioning

confidence: 99%

Nitrogen Transformations in Coal during Pyrolysis

Kelemen¹,

Gorbaty²,

Kwiatek³

et al. 1998

Energy Fuels

108

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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 (104 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.

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