THERMAL SCIENCE

International Scientific Journal

Guoyan Chen

,

Jianing Chen

,

Anchao Zhang

,

Haoxin Deng

,

Yanyang Mei

,

Xiaoping Wen

,

Fahui Wang

,

Wei Sheng

,

Zheng Shen

,

Shuangshuang Zuo

FIRST-PRINCIPLES STUDY OF CALCIUM-BASED SULFUR FIXERS AND THEIR PRODUCTS

ABSTRACT
Calcium-based sulfur-fixing agent, as the main sulfur-fixing product, is widely used in power plant boiler systems. In order to further study the thermodynamic properties and reaction characteristics of calcium-based sulfur fixing agent and its products, the method of combining power plant experiment with theory was used. The electronic structure, thermodynamic properties and density of states of quicklime, limestone, calcium sulfate (CaSO4) and calcium sulphoaluminate have been calculated based on the first-principles ultra-soft pseudopotential plane wave method of density functional theory. The generalized gradient approximation algorithm is used to optimize the structure of various minerals to achieve the most stable state. The results show that the enthalpy, entropy, specific heat capacity at constant pressure and Gibbs free energy of calcium sulfonate vary greatly from 25-1000 K, while the change of calcium oxide (CaO) is small, and that of calcium carbonate (CaCO3) and CaSO4 are between them. It shows that calcium sulphoaluminate has strong stability and more energy is needed to destroy the molecular structure of calcium sulphoaluminate. The CaO is the most unstable and requires less energy to react. The CaCO3 and CaSO4 are in between. The variation range of CaSO4 is greater than that of CaCO3, indicating that the stability of CaSO4 is higher than that of CaCO3. The experimental results show that the desulfurization efficiency of generating calcium sulphoaluminate is much higher than that of only generating CaSO4, indicating that calcium sulphoaluminate is very stable, which is consistent with the calculated results.
KEYWORDS
First principles, Calcium-based sulfur-fixing agents, Desulfurization, Density functional theory
PAPER SUBMITTED: 2021-08-24
PAPER REVISED: 2021-10-17
PAPER ACCEPTED: 2021-10-30
PUBLISHED ONLINE: 2022-01-02
DOI REFERENCE: https://doi.org/10.2298/TSCI210824350C
CITATION EXPORT: view in browser or download as text file
THERMAL SCIENCE YEAR 2022, VOLUME 26, ISSUE Issue 5, PAGES [3843 - 3857]
REFERENCES
  1. Sarbassov, Y., et al., SO3 formation and the effect of fly ash in a bubbling fluidised bed under oxy-fuel combustion conditions, Fuel Processing Technology, 167. (2017), pp. 314-321
  2. Jin, D.S., et al., Simultaneous removal of SO2 and NO by wet scrubbing using aqueous chlorine dioxide solution, Journal of Hazardous Materials, 135. (2006), 1-3, pp. 412-417
  3. Zhou, G.M., et al., Application Research of SNCR Technology in the Pulverized-coal fired Boiler, Power System Engineering. (2010).
  4. Weirong, G.U., et al., Technology status and analysis on coal-fired flue gas denitrification, Chemical Industry and Engineering Progress. (2012).
  5. Zhang, J., et al., Control Technologies and Evaluation of Mercury in Flue Gas of Waste Incineration, Environmental Sanitation Engineering. (2012).
  6. Zhang, B., et al., Increasing oxygen functional groups of activated carbon with non-thermal plasma to enhance mercury removal efficiency for flue gases, Chemical Engineering Journal, 263. (2015), pp. 1-8
  7. Zhao, W.,Z. Wu], Simultaneous absorption of NO and SO2 by FeIIEDTA combined with Na2SO3 solution, Chemical Engineering Journal. (2007).
  8. Bricl, M.,J. Avsec, Design of thermal power plant modernization & rehabilitation model for the newmarket demands and challenges, Thermal Science. (2020), 00, pp. 188-188
  9. Shimizu, T., et al., Capture of SO2 by limestone in a 71 MWe pressurized fluidized bed boiler, Thermal Science, 7. (2003), 1, pp. 17-31
  10. Smajevic, I., et al., Co-firing Bosnian Coals with woody biomass: experimental studies on a laboratory-scale furnace and 110 MWe power unit, Thermal Science, 16. (2012), 3, pp. 789-804
  11. Zhao, Y., et al., Experimental study on simultaneous desulfurization and denitrification based on highly active absorbent, Journal of environmental sciences, 18. (2006), 2, pp. 281-286
  12. Chiu, C.H., et al., Multipollutant control of Hg/SO2/NO from coal-combustion flue gases using transition metal oxide-impregnated SCR catalysts, Catalysis Today, 245. (2015), pp. 2-9
  13. Zhang, S., et al., Integrated removal of NO and mercury from coal combustion flue gas using manganese oxides supported on TiO2, Journal of Environmental Sciences, 53. (2017), 003, pp. 141-150
  14. ShiboZhang, et al., Enhancement of CeO2 modified commercial SCR catalyst for synergistic mercury removal from coal combustion flue gas, RSC Advances, 10.
  15. Guo, S., et al., Simultaneous removal of SO2 and NOx with ammonia combined with gas-phase oxidation of NO using ozone, Chemical Industry and Chemical Engineering Quarterly, 21. (2015), 2, pp. 305-310
  16. Zheng, Y., et al., Review of technologies for mercury removal from flue gas from cement production processes, Progress in energy and combustion science. (2012).
  17. Guilin, L.U., et al., First-Principles Calculation of Thermodynamic Properties of XCO3(X=Ca,Mg), Materials Review. (2012).
  18. Sousa, J., et al., Catalytic oxidation of NO to NO2 on N-doped activated carbons, Catalysis Today, 176. (2011), 1, pp. 383-387
  19. Jeguirim, M., et al., Interaction mechanism of NO2 with carbon black: Effect of surface oxygen complexes, Journal of Analytical & Applied Pyrolysis, 72. (2004), 1, pp. 171-181
  20. Zhang, W.J., et al., Study of NO adsorption on activated carbons, Applied Catalysis B Environmental, 83. (2008), 1-2, pp. 63-71
  21. Liu, D., et al., Utilization of waste concrete powder with different particle size as absorbents for SO2 reduction, Construction and Building Materials, 266. (2021), p. 121005
  22. Yu, H., et al., Dynamic modeling for SO2-NOx emission concentration of circulating fluidized bed units based on quantum genetic algorithm-Extreme learning machine, Journal of Cleaner Production. (2021), p. 129170
  23. Wang, X., et al., Simultaneous SO2 and NO removal by pellets made of carbide slag and coal char in a bubbling fluidized-bed reactor, Process Safety and Environmental Protection, 134. (2020), pp. 83-94
  24. Morselli, G.R.,R.A. Ando, SO2 Capture by Tricyanomethanide Ionic Liquids: Unraveling Anion-Gas Interactions by Resonance Raman Spectroscopy, Chemical Physics Letters. (2021), p. 139106
  25. YAN, Y.-g., et al., Simultaneous removal of SO2, NOx and Hg0 by O3 oxidation integrated with bio-charcoal adsorption, Journal of Fuel Chemistry and Technology, 48. (2020), 12, pp. 1452-1460
  26. Ng, K.H., et al., A review on dry-based and wet-based catalytic sulphur dioxide (SO2) reduction technologies, Journal of Hazardous Materials, 423. (2022), p. 127061
  27. Li, B.,C. Ma, Study on the mechanism of SO2 removal by activated carbon, Energy Procedia, 153. (2018), pp. 471-477
  28. Ying, Z., et al., First-Principle Theory Calculation of Electronic Structures of Scheelite,Fluorite and Calcite, Chinese Journal of Rare Metals. (2014).
  29. Wang, Z.H., et al., Experimental Research for the Simultaneous Removal of NOx and SO2 in Flue Gas by O3, Zhongguo Dianji Gongcheng Xuebao/Proceedings of the Chinese Society of Electrical Engineering, 27. (2007), 11, pp. 1-5
  30. Zhang, B., et al., Study on NO adsorptive removal on modified activated carbon, New Chemical Materials. (2015)
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First-principles study of calcium-based sulfur fixers and their products

© 2024 Society of Thermal Engineers of Serbia. Published by the Vinča Institute of Nuclear Sciences, National Institute of the Republic of Serbia, Belgrade, Serbia. This article is an open access article distributed under the terms and conditions of the Creative Commons Attribution-NonCommercial-NoDerivs 4.0 International licence