Mass spectrometric investigations on the release of inorganic species during gasification and combustion of Rhenish lignite

Abstract To reduce problems such as fouling, slagging and corrosion, which can occur during thermal utilisation of lignite, an enhanced understanding of the underlying release mechanisms for the involved Na-, K-, Cl-, and S-species is needed. Therefore basic investigations have been performed in an atmospheric tube furnace at 1400 °C under gasification and combustion like conditions in lab-scale experiments. Molecular beam mass spectrometry has been used for on-line qualitative and semi-quantitative analysis of the hot product gas. 34 H 2 S + has been formed during gasification experiments, while 64 SO 2 + has been formed during combustion experiments. 36 HCl + , 58 NaCl + , 39 K + (assumed to be partly a fragment of KCl) have been the main alkali and chlorine species and have been released mainly during pyrolysis phase. Linear correlation analysis has been undertaken to investigate the dependence of coal composition on the release of Na-, K-, Cl, and S-species. The correlations have been found to be similar for both gasification and combustion experiments. The release of 34 H 2 S + and 64 SO 2 + is in high negative correlation with the Ca/S ratio and in high positive correlation with the S-content of the coals. The release of 36 HCl + shows a negative correlation with the Na/S ratio and the Na/Si ratio of the lignite under investigation. The release of 58 NaCl + depends with negative correlation on the S/Cl ratio and the content of Al + Si of the investigated lignite. The experimental results have been compared with thermodynamic equilibrium calculations. The release of H 2 S, SO 2 , and NaCl could be predicted with sufficient accuracy, though the release of HCl and K-species could not satisfactorily be predicted.

[1]  M. P. Ketris,et al.  Chlorine in coal : A review , 2006 .

[2]  Anders Nordin,et al.  Effect of Coal Minerals on Chlorine and Alkali Metals Released during Biomass/Coal Cofiring , 1999 .

[3]  Ligang Zheng,et al.  Quantification of chlorine and alkali emissions from fluid bed combustion of coal by equilibrium calculations , 2003 .

[4]  D. Dayton,et al.  Direct Observation of Alkali Vapor Release during Biomass Combustion and Gasification. 1. Application of Molecular Beam/Mass Spectrometry to Switchgrass Combustion , 1995 .

[5]  G. Eriksson,et al.  ChemSage—A computer program for the calculation of complex chemical equilibria , 1990 .

[6]  J. Pettersson,et al.  A surface ionization instrument for on-line measurements of alkali metal components in combustion: Instrument description and applications , 2002 .

[7]  D. Dayton,et al.  The direct observation of alkali vapor species in biomass combustion and gasification , 1994 .

[8]  D. Thompson,et al.  The mobilisation of sodium and potassium during coal combustion and gasification , 1999 .

[9]  Bruce G. Miller,et al.  Chlorine in Solid Fuels Fired in Pulverized Fuel Boilers — Sources, Forms, Reactions, and Consequences: a Literature Review† , 2009 .

[10]  E. Hering,et al.  Physik für Ingenieure , 1997 .

[11]  D. Chandra,et al.  Mineral Impurities in Coal Combustion , 1986 .

[12]  A. Attar Chemistry, thermodynamics and kinetics of reactions of sulphur in coal-gas reactions: A review , 1978 .

[13]  H. Spliethoff,et al.  Alkali Metals in Circulating Fluidized Bed Combustion of Biomass and Coal: Measurements and Chemical Equilibrium Analysis , 2005 .

[14]  Michael Müller,et al.  Influence of coal composition on the release of Na-, K-, Cl-, and S-species during the combustion of brown coal , 2007 .

[15]  P. Monkhouse,et al.  On-line diagnostic methods for metal species in industrial process gas , 2002 .

[16]  F. Shadman,et al.  The kinetics and mechanism of alkali removal from flue gases by solid sorbents , 1990 .

[17]  G. A Osborn,et al.  Review of sulphur and chlorine retention in coal-fired boiler deposits , 1992 .

[18]  A. Wokaun,et al.  Qualitative Evaluation of Alkali Release during the Pyrolysis of Biomass , 2007 .

[19]  B. Bonn,et al.  In-situ study of the effect of operating conditions and additives on alkali emissions in fluidised bed combustion , 2002 .

[20]  T. Wall,et al.  Alkali-ash reactions and deposit formation in pulverized-coal-fired boilers: the thermodynamic aspects involving silica, sodium, sulphur and chlorine , 1982 .

[21]  K. Kitano,et al.  Some relationships between coal rank and chemical and mineral composition , 1996 .

[22]  Michael Müller,et al.  Release of K, Cl, and S species during co-combustion of coal and straw , 2006 .

[23]  C A Moses,et al.  Impact study on the use of biomass-derived fuels in gas turbines for power generation , 1994 .

[24]  M. Soltys,et al.  Direct mass-spectrometric studies of the pyrolysis of carbonaceous fuels: II. Qualitative observations of primary and secondary processes in biomass , 1983 .

[25]  Michael Müller,et al.  Influence of Coal Composition and Operating Conditions on the Release of Alkali Species During Combustion of Hard Coal , 2007 .

[26]  D. Pavone,et al.  Hot Fuel Gas Cleaning in IGCC at Gasification Temperature , 2009 .

[27]  Thomas A. Milne,et al.  Direct mass-spectrometric studies of the pyrolysis of carbonaceous fuels: I. A flame-pyrolysis molecular-beam sampling technique , 1983 .

[28]  P. Schenck,et al.  Development and application of very high temperature mass spectrometry. Vapor pressure determinations over liquid refractories , 2000 .