On 14C-based methods for measuring the biogenic carbon fraction

University of Groningen
On 14C-based methods for measuring the biogenic carbon fraction in fuels and flue
gases
Palstra, Sanne
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Palstra, S. W. L. (2016). On 14C-based methods for measuring the biogenic carbon fraction in fuels and
flue gases [Groningen]: University of Groningen
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On 14C-‐based methods for measuring the biogenic carbon fraction in fuels and flue gases Sanne W.L. Palstra 14
On C-‐based methods for measuring the biogenic carbon fraction in fuels and flue gases Sanne W.L. Palstra PhD thesis, 2016 University of Groningen The Netherlands ISBN: 978-‐90-‐367-‐8553-‐2 ISBN, electronic version: 978-‐90-‐367-‐8552-‐5 Printing: Ridderprint BV, Ridderkerk The research described in this thesis was performed at the Centre for Isotope Research (CIO), part of the Energy and Sustainability Research Institute Groningen (ESRIG), University of Groningen. The research of chapter 2 was partly funded by energy company Essent (RWE). The research described in chapters 3 and 4 was partly funded by a grant of the Energy Delta Gas Research (EDGaR) program. EDGaR is co-‐financed by the Northern Netherlands Provinces, the European Fund for Regional Development, the Ministry of Economic Affairs and the Province of Groningen. On 14C-‐based methods for measuring the biogenic carbon fraction in fuels and flue gases Proefschrift ter verkrijging van de graad van doctor aan de Rijksuniversiteit Groningen op gezag van de rector magnificus prof. dr. E. Sterken en volgens besluit van het College voor Promoties. De openbare verdediging zal plaatsvinden op vrijdag 19 februari 2016 om 14.30 uur door Sanne Waltje Lieze Palstra geboren op 15 december 1975 te Stadskanaal Promotor Prof. dr. H.A.J. Meijer Beoordelingscommissie Prof. dr. G.T. Cook Prof. M.A. Herber Prof. dr. H.J. Heeres Contents Chapter 1 – Introduction 14
C-‐based methods for measuring the biogenic carbon fraction in fuels and flue gases 9 1.1 A global interest to distinguish biogenic from fossil carbon . . . . . . . . . . . . 10 14
1.2 C as tracer for biogenic and fossil carbon fractions. . . . . . . . . . . . . . . . 15 14
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1.3 Determination of Csample and Cbio . . . . . . . . . . . . . . . . . . . . . . . . . 16 14
1.3.1 C measurement. . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 16 14
1.3.2 Calculation of C values . . . . . . . . . . . . . . . . . . . . . . . . . . . 19 14
1.3.3 Definition of 0% biogenic carbon and determination of Csample 14
and Cbio . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 23 14
1.4 Application of C-‐based methods for fuels and flue gases . . . . . . . . . . . . 25 Chapter 2 Carbon-‐14 based determination of the biogenic fraction of industrial CO2 emissions – Application and validation 27 Abstract . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 27 2.1 Introduction . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 28 2.2 Materials and Methods . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 30 2.2.1 Sampling . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 30 14
2.2.2 C measurement . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 32 14
2.2.3 C-‐based quantification of the biogenic fuel-‐derived CO2 fraction . . . . 32 2.2.4 Calculation of fCO2_air . . . . . . . . . . . . . . . . . . . . . . . . . . . . 34 2.2.5 Mass data method . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 36 2.3 Results . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 37 2.4 Discussion . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 46 2.4.1 Reliability of flue gas CO2 sampling . . . . . . . . . . . . . . . . . . . . . 46 14
2.4.2 Reliability of sample pre-‐treatment and C analysis . . . . . . . . . . . 48 14
2.4.3 Reliability of the calculated C-‐based biogenic fuel-‐derived CO2 fraction 49 2.5 Conclusions . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 51 Acknowledgements. . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 51 Chapter 3 14
Biogenic carbon fraction of biogas and natural gas fuel mixtures determined with C 53 Abstract . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 53 3.1 Introduction . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 54 3.2 Experimental methods . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 56 3.2.1 Biogas and natural gas samples. . . . . . . . . . . . . . . . . . . . . . . 56 3.2.2 Gas sample pre-‐treatment . . . . . . . . . . . . . . . . . . . . . . . . . 56 3.2.3 Gas sample combustion . . . . . . . . . . . . . . . . . . . . . . . . . . . 57 13
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3.2.4 C and C analyses of CO2 samples . . . . . . . . . . . . . . . . . . . . 58 3.2.5 Bio-‐fossil CO2 mixtures . . . . . . . . . . . . . . . . . . . . . . . . . . . . 58 3.3 Calculation methods . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 59 3.3.1 Isotope fractionation correction . . . . . . . . . . . . . . . . . . . . . . 59 3.3.2 Calculation of the deviation in the bioC fraction . . . . . . . . . . . . . 60 3.4 Results and discussion . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 63 3.4.1 Origin and composition of the investigated gases . . . . . . . . . . . . 63 13
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3.4.2 C and C measurement results biogas and natural gas . . . . . . . . 64 13
3.4.3 δ C values . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 66 14
3.4.4 C values of biogas . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 67 14
3.4.5 C reference value for 100% biogenic carbon. . . . . . . . . . . . . . . 70 3.4.6 Deviations in the bioC fraction related to isotope fractionation correction 75 14
3.4.7 Accuracy of the C method for biogas/natural gas fuel mixtures . . . . 79 3.5 Conclusions and recommendations . . . . . . . . . . . . . . . . . . . . . . . . 82 Acknowledgements . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 83 Chapter 4 Radiocarbon-‐based determination of biogenic and fossil carbon partitioning in the production of synthetic natural gas 85 Abstract . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 85 4.1 Introduction . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 86 4.2 Methods . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 88 4.2.1 SNG sample information . . . . . . . . . . . . . . . . . . . . . . . . . . . 88 14
4.2.2 Applied C method. . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 90 4.2.3 Determination of bio-‐fossil carbon partitioning of solid input materials 91 4.3 Results and discussion. . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 93 4.3.1 Biogenic carbon fraction of flue gas CO2 and raw SNG . . . . . . . . . . 93 4.3.2 Biogenic carbon fraction of mixed solid input materials . . . . . . . . . 93 4.3.3 Bio-‐fossil carbon partitioning . . . . . . . . . . . . . . . . . . . . . . . . 96 4.4 Conclusions . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 99 Acknowledgements . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 99 Appendix A.4 Applied method for separation of CO2 and CH4 fractions in gases and combustion of CH4 . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 100 A.4.1 Introduction . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 100 A.4.2 Separation and combustion system (SCS) and applied method . . 100 A.4.2.1 Separation of the CO2 fraction. . . . . . . . . . . . . . . . 101 A.4.2.2 Combustion of the CH4 fraction. . . . . . . . . . . . . . . 102 13
Appendix B.4 δ C IRMS measurement results of the investigated flue gas and SNG samples. . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 103 B.4.1 Introduction. . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 103 B.4.2 Measurement results . . . . . . . . . . . . . . . . . . . . . . . . . 103 B.4.3 Discussion about the separation of CO2 and CH4 with the new 13
SCS system based on the measured IRMS δ C values . . . . . . . 105 B.4.4 Conclusions . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 107 Chapter 5 14
Application of C-‐based methods for fuels, flue gases and bio-‐based materials – An overview with discussion & outlook 109 5.1 Introduction. . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 110 14
5.2 Application of C-‐based methods for fuels, flue gases and bio-‐based materials 111 14
5.3 Insights in an accurate and reliable application of C-‐based methods . . . . . 116 14
5.3.1 Cases in which C-‐based methods cannot be applied . . . . . . . . . . 116 5.3.2 Selection of representative carbon . . . . . . . . . . . . . . . . . . . . 117 14
5.3.3 Reliable determination of Csample. . . . . . . . . . . . . . . . . . . . . 119 14
5.3.4 Representative determination of Cbio . . . . . . . . . . . . . . . . . . 122 14
5.3.5 C-‐based biogenic carbon fraction . . . . . . . . . . . . . . . . . . . . 125 14
5.4 Future use of C-‐based methods for fuels, flue gases and bio-‐based materials 126 14
5.5 Future research of C-‐based methods to distinguish biogenic and fossil carbon sources . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 129 References 131 Summary 139
Samenvatting 145 Dankwoord 153
Curriculum Vitae 157

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