Subscriber access provided by Fudan University
Article
Investigating Secondary Pyrolysis Reactions of Coal Tar via Mass Spectrometry Techniques Jeffrey LeBlanc, John F. Quanci, and Marco J. Castaldi Energy Fuels, Just Accepted Manuscript • DOI: 10.1021/acs.energyfuels.6b02543 • Publication Date (Web): 30 Dec 2016 Downloaded from http://pubs.acs.org on January 1, 2017
Just Accepted “Just Accepted” manuscripts have been peer-reviewed and accepted for publication. They are posted online prior to technical editing, formatting for publication and author proofing. The American Chemical Society provides “Just Accepted” as a free service to the research community to expedite the dissemination of scientific material as soon as possible after acceptance. “Just Accepted” manuscripts appear in full in PDF format accompanied by an HTML abstract. “Just Accepted” manuscripts have been fully peer reviewed, but should not be considered the official version of record. They are accessible to all readers and citable by the Digital Object Identifier (DOI®). “Just Accepted” is an optional service offered to authors. Therefore, the “Just Accepted” Web site may not include all articles that will be published in the journal. After a manuscript is technically edited and formatted, it will be removed from the “Just Accepted” Web site and published as an ASAP article. Note that technical editing may introduce minor changes to the manuscript text and/or graphics which could affect content, and all legal disclaimers and ethical guidelines that apply to the journal pertain. ACS cannot be held responsible for errors or consequences arising from the use of information contained in these “Just Accepted” manuscripts.
Energy & Fuels is published by the American Chemical Society. 1155 Sixteenth Street N.W., Washington, DC 20036 Published by American Chemical Society. Copyright © American Chemical Society. However, no copyright claim is made to original U.S. Government works, or works produced by employees of any Commonwealth realm Crown government in the course of their duties.
Page 1 of 21
1 2 3 4 5 6 7 8 9 10 11 12 13 14 15 16 17 18 19 20 21 22 23 24 25 26 27 28 29 30 31 32 33 34 35 36 37 38 39 40 41 42 43 44 45 46 47 48 49 50 51 52 53 54 55 56 57 58 59 60
Energy & Fuels
1
Investigating Secondary Pyrolysis Reactions of Coal Tar
2
via Mass Spectrometry Techniques
3
Jeffrey LeBlanca, John Quancib, Marco J. Castaldi*,a
4 5 6 7 8
a
Combustion and Catalysis Laboratory, Department of Chemical Engineering, The City College of New York, City University of New York, New York, NY 10030 b
Suncoke Energy Inc., 1011 Warrenville Road, 6th Floor, Lisle, IL 60532 USA *Corresponding author fax: (212) 650-6660, phone: (212) 650-6679, email:
[email protected] 9 10 11 12 13 14 15 16 17 18 19 20 21 22 23 24
ACS Paragon Plus Environment
1
Energy & Fuels
1 2 3 4 5 6 7 8 9 10 11 12 13 14 15 16 17 18 19 20 21 22 23 24 25 26 27 28 29 30 31 32 33 34 35 36 37 38 39 40 41 42 43 44 45 46 47 48 49 50 51 52 53 54 55 56 57 58 59 60
Page 2 of 21
25
Abstract
26
Coal pyrolysis tars produced from a United States bituminous coal in two reaction confinements of
27
different aspect ratio (0.11:1.0 and 2.0:1.0), and at heating rates of 1, 3, and 10 ºC min-1 were analyzed
28
by laser desorption/ionization-time-of-flight mass spectrometry (LDI-TOF), thermogravimetric-gas
29
chromatography (TG-GC) and gas chromatography-mass spectrometry (GC-MS). The reaction
30
confinement served to extend the volatile residence time in the pyrolysis environment by 350
31
milliseconds. The goal of this study was to determine the effect of extended residence times on the tar
32
product distribution. LDI-TOF and GC-MS analysis combined suggest that tars exposed to extended
33
residence time in the pyrolysis environment were lower in average molecular weight, had a lower H/C
34
ratio, and produced more expansive speciation of nitrogen and sulfur species. The heating rates were
35
able to vary the average tar molecular by 15-32 amu which is, at least in part, attributed to variations in
36
volatile residence time between 110 milliseconds to 1 second. These findings are evidence of tar
37
cracking during the extended residence times of nominally 350 milliseconds. TG-GC of coal tar shows
38
that 78 % of the remaining tar products vaporize before 400 ºC while the remaining 22 % of the tar
39
decomposes by 1000 ºC producing secondary tar products and without producing secondary gas or coke
40
products. The thermally treated tar was collected from a condenser system and analyzed by LDI-TOF
41
which suggested the secondary tar had an overall lower average molecular weight but, a higher presence
42
of both light (100 amu) and heaver (>267 amu,
