MINERAL SEQUESTRATION OF CO 2 BY REACTION WITH ALKALINE RESIDUES Dissertation zur Erlangung des Grades Doktor der Naturwissenschaften (Dr. rer. nat.) An der Fakultät Biologie/Chemie/Geowissenschaften vorgelegt von Martin Back geb. am 25.02.1977 in Ludwigshafen Die Arbeiten zur vorliegenden Dissertation wurden im Zeitraum von März 2005 bis Februar 2008 am Lehrstuhl für Hydrologie der Universität Bayreuth unter Betreuung von Herrn Prof. Dr. Stefan Peiffer durchgeführt. Vollständiger Abdruck der von der Fakultät für Biologie, Chemie und Geowissenschaften der Universität Bayreuth genehmigten Dissertation zur Erlangung des akademischen Grades eines Doktors der Naturwissenschaften (Dr. rer. nat.). Dissertation eingereicht am: 10.10.2011 Zulassung durch die Prüfungskommission: 19.10.2011 Wissenschaftliches Kolloquium: 31.05.2012 Amtierender Dekan: Prof. Dr. Beate Lohnert Prüfungsausschauss: Prof. Dr. Stefan Peiffer (Erstgutachter) Prof. Dr. Christoph Clauser (Zweitgutachter) Prof. Dr. Klaus Bitzer (Vorsitz) Prof. Dr. Britta Planer-Friedrich Prof. Dr. Egbert Matzner Table of Contents TABLE OF CONTENTS TABLE OF CONTENTS ...................................................................................................................... I LIST OF FIGURES ........................................................................................................................... IV LIST OF TABLES ............................................................................................................................. IX SUMMARY ........................................................................................................................................ X ZUSAMMENFASSUNG................................................................................................................ XIII INTRODUCTION AND OUTLINE OF THESIS ............................................................................... 1 CLIMATE CHANGE AND ATMOSPHERIC INCREASE OF ANTHROPOGENIC CO 2 ...................................... 1 THE ROLE OF CARBON CAPTURE AND STORAGE (CCS) ...................................................................... 1 MINERAL CARBONATION ................................................................................................................... 3 USING OF ALKALINE RESIDUES FOR CO 2 SEQUESTRATION ................................................................. 5 OBJECTIVE OF THE DISSERTATION ..................................................................................................... 6 CONTRIBUTIONS TO DIFFERENT STUDIES ............................................................................... 9 1 REACTIVITY OF ALKALINE LIGNITE FLY ASHES TOWARDS CO 2 IN WATER ........ 13 1.1 INTRODUCTION ................................................................................................................... 14 1.2 EXPERIMENTAL SECTION ..................................................................................................... 15 Sample characterisation ............................................................................................................ 15 Experiments ................................................................................................................................ 15 1.3 RESULTS AND DISCUSSION .................................................................................................. 17 Composition of fly ashes ............................................................................................................ 17 Reaction between fly ash and water ........................................................................................... 18 Reaction between CO 2 and fly ash ............................................................................................. 19 Effect of process variables on CO 2 uptake ................................................................................. 22 1.4 IMPLICATIONS FOR A TECHNICAL REALIZATION .................................................................. 26 Acknowledgement....................................................................................................................... 27 1.5 SUPPORTING INFORMATIONS ............................................................................................... 28 Section A: Experimental setup ................................................................................................... 28 Section B: Accuracy of the methods used for determination of the total uptake of CO 2, TDIC and carbonate precipitation ....................................................................................................... 28 Section C: SEM-pictures of lignite fly ash ................................................................................. 31 Section D: Grain size analysis ................................................................................................... 32 I Table of Contents Section E: Mineralogical composition (XRD, Rietveld analysis) .............................................. 32 2 SEQUESTRATION OF CO 2 AFTER REACTION WITH ALKALINE EARTH METAL OXIDES CAO AND MGO ................................................................................................................ 35 2.1 INTRODUCTION ................................................................................................................... 36 2.2 MATERIALS AND METHODS ................................................................................................. 38 Experimental setup ..................................................................................................................... 38 Measurements and calculations ................................................................................................. 39 Sets of experiments ..................................................................................................................... 41 2.3 RESULTS AND DISCUSSION .................................................................................................. 43 Reaction of CaO/Ca(OH) 2 suspensions with CO 2 ..................................................................... 43 Reaction of MgO suspensions with CO 2 .................................................................................... 45 Controls on CO 2 transfer to the water phase ............................................................................. 53 2.4 CONCLUSIONS ..................................................................................................................... 58 Acknowledgements ..................................................................................................................... 60 3 APPLICATION OF A PHREEQC BASED KINETIC MODEL TO SIMULATE PROCESS AND DYNAMICS OF THE CARBONATION OF ALKALINE MATERIALS BY GAS PHASE DERIVED CO 2 IN AQUEOUS SYSTEMS ...................................................................................... 63 ABSTRACT ...................................................................................................................................... 63 3.1 INTRODUCTION ................................................................................................................... 65 3.2 MATERIALS AND METHODS ................................................................................................. 68 Experimental section .................................................................................................................. 68 CO 2 uptake (carbonation) experiments by alkaline materials ................................................... 70 Modelling section ....................................................................................................................... 70 3.3 RESULTS AND DISCUSSION .................................................................................................. 72 Determination of rate constants and model setup ..................................................................... 72 SIMULATION OF THE CARBONATION IN SYSTEMS WITH MULTIPLE MINERAL PHASES ....................... 80 Simulation of lignite fly ash carbonation ................................................................................... 87 3.4 CONCLUSIONS ..................................................................................................................... 91 Acknowledgements ..................................................................................................................... 92 SUPPORTING INFORMATIONS ........................................................................................................... 92 4 MINERAL TRAPPING OF CO 2 IN OPERATED HYDROGEOTHERMAL RESERVOIRS.... .................................................................................................................................................... 96 4.1 INTRODUCTION ................................................................................................................... 97 II Table of Contents 4.2 SUITABLE GEOTHERMAL RESERVOIRS ................................................................................. 98 4.3 TRANSFORMATION OF ANHYDRITE INTO CALCITE ............................................................. 100 4.4 CORE FLOODING EXPERIMENT ........................................................................................... 102 4.5 SUITABLE SOURCES OF ALKALINITY .................................................................................. 104 In-situ alkalinity source 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