Systematically reduced chemical mechanisms for sulfur oxidation and pyrolysis

被引:72
作者
Cerru, F. G. [1 ]
Kronenburg, A. [1 ]
Lindstedt, R. P. [1 ]
机构
[1] Univ London Imperial Coll Sci Technol & Med, Dept Mech Engn, London SW7 2AZ, England
基金
英国工程与自然科学研究理事会;
关键词
sulfur chemistry; chemical kinetics; reduced chemical mechanisms; pollutant formation and oxidation;
D O I
10.1016/j.combustflame.2006.05.005
中图分类号
O414.1 [热力学];
学科分类号
摘要
Recent research on sulfur chemistry has predominantly focused on the high-temperature chemistry typical of flames. The present work initially assesses the ability of a sulfur submechanism featuring 12 sulfur-containing species and 70 reversible reactions to reproduce measured data. The functionality includes the pyrolysis and oxidation of hydrogen sulfide as well as the chemistry of sulfur dioxide. The sensitivity of reaction paths to alternative rate determinations has been analyzed. In particular, the consumption paths of sulfanyl and the rates of the reactions involved in the SO2-catalyzed radical recombination highlight existing uncertainties. Despite these difficulties, the detailed mechanism generally produces good agreement with experimental data. Most industrial combustion processes are turbulent and turbulence-chemistry interactions cannot be included through high-Damkohler-number limit approximations. Accordingly, chemical kinetic effects need to be accounted for and the implementation of systematically reduced mechanisms has the potential to increase the computational efficiency. The detailed reaction mechanism is thus subsequently reduced to six independent scalars with HSO, HOSO, HOSO2, HSSH, and S in steady state. The reduced mechanism provides good agreement over the range of conditions studied. Further simplifications are made in the context of oxides of sulfur and a two-step mechanism involving SO, SO2, and SO3 is derived and shown to retain good agreement with the experimental data for a more limited set of conditions. (c) 2006 The Combustion Institute. Published by Elsevier Inc. All rights reserved.
引用
收藏
页码:437 / 455
页数:19
相关论文
共 65 条
[1]   THERMOLYSIS OF HYDROGEN-SULFIDE IN AN OPEN-TUBULAR REACTOR [J].
ADESINA, AA ;
MEEYOO, V ;
FOULDS, G .
INTERNATIONAL JOURNAL OF HYDROGEN ENERGY, 1995, 20 (10) :777-783
[2]   Inhibition and sensitization of fuel oxidation by SO2 [J].
Alzueta, MU ;
Bilbao, R ;
Glarborg, P .
COMBUSTION AND FLAME, 2001, 127 (04) :2234-2251
[3]  
[Anonymous], 1973, J PHYS CHEM REF DATA, DOI DOI 10.1063/1.3253112
[4]   KINETICS OF REACTION O(P-3) + SO2 + M-]SO3 + M OVER TEMPERATURE-RANGE OF 299-DEGREES-440-DEGREESK [J].
ATKINSON, R ;
PITTS, JN .
INTERNATIONAL JOURNAL OF CHEMICAL KINETICS, 1978, 10 (10) :1081-1090
[5]   Evaluated kinetic and photochemical data for atmospheric chemistry:: Volume I -: gas phase reactions of Ox, HOx, NOx and SOx species [J].
Atkinson, R ;
Baulch, DL ;
Cox, RA ;
Crowley, JN ;
Hampson, RF ;
Hynes, RG ;
Jenkin, ME ;
Rossi, MJ ;
Troe, J .
ATMOSPHERIC CHEMISTRY AND PHYSICS, 2004, 4 :1461-1738
[6]   Evaluated kinetic and photochemical data for atmospheric chemistry: Supplement VI - IUPAC subcommittee on gas kinetic data evaluation for atmospheric chemistry [J].
Atkinson, R ;
Baulch, DL ;
Cox, RA ;
Hampson, RF ;
Kerr, JA ;
Rossi, MJ ;
Troe, J .
JOURNAL OF PHYSICAL AND CHEMICAL REFERENCE DATA, 1997, 26 (06) :1329-1499
[7]  
BAUER SH, 1971, P COMBUST INST, V13, P417
[8]   EVALUATED KINETIC DATA FOR COMBUSTION MODELING [J].
BAULCH, DL ;
COBOS, CJ ;
COX, RA ;
ESSER, C ;
FRANK, P ;
JUST, T ;
KERR, JA ;
PILLING, MJ ;
TROE, J ;
WALKER, RW ;
WARNATZ, J .
JOURNAL OF PHYSICAL AND CHEMICAL REFERENCE DATA, 1992, 21 (03) :411-734
[9]   EVALUATED KINETIC DATA FOR COMBUSTION MODELING SUPPLEMENT-I [J].
BAULCH, DL ;
COBOS, CJ ;
COX, RA ;
FRANK, P ;
HAYMAN, G ;
JUST, T ;
KERR, JA ;
MURRELLS, T ;
PILLING, MJ ;
TROE, J ;
WALKER, RW ;
WARNATZ, J .
JOURNAL OF PHYSICAL AND CHEMICAL REFERENCE DATA, 1994, 23 (06) :847-1033
[10]   Determination of the high-pressure limiting rate coefficient and the enthalpy of reaction for OH+SO2 [J].
Blitz, MA ;
Hughes, KJ ;
Pilling, MJ .
JOURNAL OF PHYSICAL CHEMISTRY A, 2003, 107 (12) :1971-1978