By analyzing process samples full and pilot scale gasifiers, the main influences affecting their slag are identified. Based on this knowledge as well as the current literature, the effect of crystallization was identified as crucial for understanding slag behavior and is analyzed during cooldown. Finally, the emerging interest in sewage sludge upcycling via gasification necessitated an investigation on the influence of adding P2O5 as slag constituent. All conclusions concerning the full scale gasifier slags were based on XRF, XRD, and SEM-EDX analyses coupled with thermodynamic equilibrium calculations via FactSage. The subsequently presented research on crystallization and the effect of P2O5 was centered on conducting slag viscosity measurements, recreating the conditions of said measurement in a quench oven, and analyzing the resulting quench samples via the mentioned analysis methods. Special focus was put on the phase evolution, its governing factors, and the effect on slag viscosity.:1. INTRODUCTION 1
2. FUNDAMENTALS IN SLAG BEHAVIOR CHARACTERIZATION 3
2.1. BASE TO ACID RATIO AS KEY FIGURE FOR SLAG CHARACTERIZATION 7
2.2. VISCOSITY ALTERING SECONDARY PHASES IN SLAGS 9
2.2.1. The effect of crystallization on slag flow 10
2.2.2. Modelling and measuring crystallization in slags 11
2.3. CRITICAL VISCOSITY 13
2.4. PHOSPHOROUS OXIDE IN SLAGS 15
2.4.1. Behavior of P2O5 within slags 16
2.4.2. Phase separation in melts containing P2O5 17
2.4.3. Effect on slag viscosity 22
3. ANALYTICAL METHODS 26
3.1. SAMPLE PRETREATMENT 26
3.2. ASH FUSION TEMPERATURE 28
3.3. X-RAY FLUORESCENCE MEASUREMENT (XRF) 30
3.4. X-RAY DIFFRACTION 31
3.5. VISCOSITY MEASUREMENT 32
3.6. DIFFERENTIAL THERMAL ANALYSIS (DTA) 36
3.7. QUENCH APPARATUS 37
3.8. SEM-EDX 39
3.9. THERMODYNAMIC EQUILIBRIUM CALCULATIONS 40
4. CHARACTERIZATION OF SLAGS FROM FULL OR PILOT SCALE GASIFIERS 42
4.1. SLAG FROM GENERAL ELECTRICS GASIFIER IN TAMPA 43
4.1.1. Analysis of the suspending main phase 45
4.1.2. Analysis of the silica phase 50
4.1.3. Analysis of the metal enclosures 51
4.1.4. Analysis of the vanadium-rich particles 53
4.1.5. Summary of the analysis of the General Electrics gasifier slag 55
4.2. SLAG FROM GSP GASIFIER 57
4.2.1. NCPP slag 57
4.2.2. Huainan Anhui slag 64
4.2.3. Genesee slag 70
4.2.4. Hambach-Garzweiler 50:50 slag 75
4.2.5. Summary of the analysis of the GSP slags 86
4.3. SLAG FROM BRITISH GAS/LURGI (BGL) GASIFIER 88
4.3.1. Summary and conclusions of the analysis of the BGL slag 99
5. CHARACTERIZING CRYSTALLIZATION DURING SLAG VISCOSITY MEASUREMENTS 102
5.1. EXPERIMENTAL PROCEDURE 103
5.1.1. Sample preparation 107
5.1.2. Viscosity measurement 108
5.1.3. Differential thermal analysis (DTA) 108
5.1.4. Quench oven 108
5.1.5. XRD, XRF, SEM-EDX, and FactSage calculations 109
5.2. RESULTS AND DISCUSSION 109
5.2.1. Slag 1 (CO/CO2 atmosphere) 110
5.2.2. Slag 2 (CO/CO2 atmosphere) 112
5.2.3. Slag 3 (air atmosphere) 116
5.2.4. Slag 3 (CO/CO2 atmosphere) 119
5.3. CONCLUSION AND SUMMARY OF THE STUDY OF CRYSTALLIZATION IN SLAGS DURING COOLDOWN 122
6. THE EFFECT OF PHOSPHOROUS OXIDE ON SLAGS 125
6.1. PRELIMINARY SEWAGE SLUDGE SLAG INVESTIGATION 126
6.1.1. Conclusion and summary sewage slag investigation 136
6.2. EXPERIMENTAL PROCEDURE FOR PARAMETRIC STUDY 139
6.3. PARAMETRIC STUDY 141
6.3.1. HKN with 15% sand (HKNS) 142
6.3.2. HKNS with low P2O5 addition (HKNS5P) 147
6.3.3. HKNS with medium low P2O5 addition (HKNS10P) 153
6.3.4. HKNS with medium high P2O5 addition (HKNS15P) 158
6.3.5. HKNS with high P2O5 addition (HKNS20P) 163
6.3.6. P2O5 distribution 169
6.3.7. Effect of P2O5 on viscosity 174
6.4. SUMMARY ON THE INVESTIGATION OF P2O5 IN SLAGS 179
7. CONCLUSION AND OUTLOOK 185
8. REFERENCES 190
9. APPENDIX A: DIFFERENCE IN PREDICTION OF SEWAGE SLUDGE ELEMENTAL DISTRIBUTION 213
10. APPENDIX B COMPARISON OF XRF ANALYSES OF HKNS-P2O5 MIXTURES 215
11. APPENDIX C EDX MAPS OF THE QUENCH SAMPLES IN THE PARAMETRIC PHOSPHORUS ADDITION STUDY 218
12. APPENDIX D SUMMARY OF PHASE COMPOSITION OF THE EDX MAPS 239
13. APPENDIX E ENRICHMENT FACTORS FOR THE QUENCH SAMPLES IN THE PARAMETRIC PHOSPHORUS ADDITION STUDY 242
| Identifer | oai:union.ndltd.org:DRESDEN/oai:qucosa:de:qucosa:78168 |
| Date | 09 March 2022 |
| Creators | Schwitalla, Daniel |
| Contributors | Meyer, Bernd, Volkova, Olena, Technische Universität Bergakademie Freiberg |
| Source Sets | Hochschulschriftenserver (HSSS) der SLUB Dresden |
| Language | English |
| Detected Language | English |
| Type | info:eu-repo/semantics/publishedVersion, doc-type:doctoralThesis, info:eu-repo/semantics/doctoralThesis, doc-type:Text |
| Rights | info:eu-repo/semantics/openAccess |
| Relation | 10.1016/j.fuproc.2021.106833, 10.1016/j.fuel.2017.04.092, 10.1016/j.fuel.2021.121501 |
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