Abstract
Ca(OH)2, a widely available and low-cost calcium-based desulfurizer, needs further improvement in calcium utilization in flue gas desulfurization. In this experiment, Ca(OH)2 crystals with different morphologies were prepared by do** impurity ions including SO42− and SiO32− by precipitation method, which played directing role in the process of crystal growth. The prepared Ca(OH)2 crystals were applied to cement kiln flue gas desulfurization environment to investigate the effect of crystal morphology on flue gas desulfurization. The observed results illustrated that Ca(OH)2 prepared by SO42− as impurity ion in hexagonal plate shape presents the best desulfurization performance with desulfurization efficiency up to 93%. The structural characterization of Ca(OH)2 crystals by XRD and SEM, and the investigation of the reasons for desulfurization by BET, EDS, and XPS showed that the hexagonal plate-shaped Ca(OH)2 crystals increased the specific surface area and had the highest elemental sulfur content of 5.04% on the (100) crystal plane, and the high surface energy on the (100) plane led to the high reactivity. This confirms the guiding significance of hexagonal plate-like morphology for improving the desulfurization performance of Ca(OH)2.
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References
National Bureau of Statistics. http://www.stats.gov.cn/
Renedo MJ, Fernández-Ferreras J (2016) Characterization and behavior of modified calcium-hydroxide-based sorbents in a dry desulfurization process. Energy Fuel 30(8):6350–6354. https://doi.org/10.1021/acs.energyfuels.6b01106
Chang J, Tian HJ, Jiang JG, Zhang C, Guo QJ (2016) Simulation and experimental study on the desulfurization for smelter off-gas using a recycling ca-based desulfurizer. Chem Eng J 291:225–237. https://doi.org/10.1016/j.cej.2015.12.064
Li Y, Masateru SM (1999) High calcium utilization and gypsum formation for dry desulfurization process. Energy Fuel 13(5):1015–1020. https://doi.org/10.1021/ef9802781
Zhao RF, Liu HD, Ye SF, Chen YF (2006) Ca-based sorbents modified with humic acid for flue gas desulfurization. Ind Eng Chem Res 45(21):7120–7125. https://doi.org/10.1021/ie051253
Shin HG, Kim H, Kim YN, Lee HS (2009) Preparation and characterization of high surface area calcium hydroxide sorbent for SO2 removal. Curr Appl Phys 9(3):S276–S279. https://doi.org/10.1016/j.cap.2009.01.036
Osaka Y, Tsujiguchi T, Kodama A, Huang HY (2020) Improvement of dry desulfurization performance using activated calcium carbonate by amorphous citric acid complex method for diesel gas purification. J Mater Cycles Waste 22(2):470–478. https://doi.org/10.1007/s10163-019-00942-1
Ruiz-Alsop RN, Rochelle GT (1986) Effect of deliquescent salt additives on the reaction of SO2 with Ca(OH)2. ACS Symp Ser 319:208–222. https://doi.org/10.1021/bk-1986-0319.ch017
Galmarini S, Aimable A, Ruffray N, Bowen P (2011) Changes in portlandite morphology with solvent composition: atomistic simulations and experiment. Cem Concr Res 41(12):1330–1338. https://doi.org/10.1016/j.cemconres.2011.04.009
Shen YS, Tang ML, Shen XD (2016) Growth Habit of Portlandite Crystal in Cement Paste. J Chin Ceram Soc 44(02):232–238. https://doi.org/10.14062/j.issn.0454-5648.2016.02.08
Iizuka A, Morishita Y, Shibata E, Takatoh C, Cho H (2020) Basic study of the reaction of calcium hydroxide with hydrogen chloride using single crystals. Ind Eng Chem Res 59(20):9699–9704. https://doi.org/10.1021/acs.iecr.9b06967
Daud FDM, Vignesh K, Sreekantan S, Mohamed AR, Kang M, Kwak BS (2016) Ca(OH)2 nano-pods: investigation on the effect of solvent ratio on morphology and CO2 adsorption capacity. RSC Adv 6(42):3631–3638. https://doi.org/10.1039/c5ra27771j
Shen YS (2016) Growth habit of Portlandite crystal in coprecipitation and cementitious systems. MEng Dissertation, Nan**g University of Technology, China
Harutyunyan VS (2012) Adsorption energy of stoichiometric molecules and surface energy at morphologically important facets of a Ca(OH)2 crystal. Mater Chem Phys 134(1):200–213. https://doi.org/10.1016/j.matchemphys.2012.02.052
Schnelle KB Jr, Dunn RF, Ternes ME (2015) Air pollution control technology handbook. CRC Press, Los Angeles
Shen P, Meng H (2012) Material chemistry. Sun Yat-sen University, China
Sangwal K (1993) Effect of impurities on the processes of crystal growth. J Cryst Growth 128(1–4):1236–1244. https://doi.org/10.1016/S0022-0248(07)80129-1
Lahav M, Leiserowitz L (2001) The effect of solvent on crystal growth and morphology. Chem Eng Sci 56(7):2245–2253. https://doi.org/10.1016/S0009-2509(00)00459-0
Liu F, Garofalini SH, King-Smith RD, Vanderbilt D (1993) Structural and electronic properties of sodium metasilicate. Chem Phys Lett 215(4):401–404. https://doi.org/10.1016/0009-2614(93)85736-8
Yang QZ, Gao XT, Fang L, Zhang SB, Cheng FQ (2021) Controllable crystal growth of Mg(OH)2 hexagonal flakes and their surface modification using graft polymerization. Adv Powder Technol 32(7):2634–2644. https://doi.org/10.1016/j.apt.2021.05.036
Yang J, Hou DS, Ding QJ (2018) Ionic hydration structure, dynamics and adsorption mechanism of sulfate and sodium ions in the surface of calcium silicate hydrate gel: a molecular dynamics study. Appl Surf Sci 448:559–570. https://doi.org/10.1016/j.apsusc.2018.04.071
Brunet F, Bertani P, Charpentier T, Nonat A, Virlet J (2004) Application of 29Si homonuclear and 1h–29Si heteronuclear NMR correlation to structural studies of calcium silicate hydrates. J Phys Chem B 108(40):15494–15502. https://doi.org/10.1021/jp031174g
Fernández I, Garea A, Irabien A (1998) SO2 reaction with Ca(OH)2 at medium temperatures (300–425°C): kinetic behaviour. Chem Eng Sci 53(10):1869–1881. https://doi.org/10.1016/S0009-2509(98)00029-3
Chiarello G, Lumachi A, Parmigiani F, Ghetti P, Michele GD (1990) An XPS study of SO2 on a CaO surface derived from Ca(OH)2. J Electron Spectrosc Relat Phenom 50(2):229–237. https://doi.org/10.1016/0368-2048(90)87067-X
Ho CS, Shih SM, Lee CD (1996) Influence of CO2 and O2 on the reaction of Ca(OH)2 under spray-drying flue gas desulfurization conditions. Ind Eng Chem Res 35:3915–3919. https://doi.org/10.1016/0368-2048(90)87067-X
Shih SM, Ho CS, Song YS, Lin JP (1999) Kinetics of the reaction of Ca(OH)2 with CO2 at low temperature. Ind Eng Chem R es 38:1316–1322. https://doi.org/10.1021/ie980508z
Ho CS, Shih SM, Liu CF, Chu HM, Lee CD (2002) Kinetics of the sulfation of Ca(OH)2 at low temperatures. Ind Eng Chem Res 41(14):3357–3364. https://doi.org/10.1021/ie010887n
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This study was funded by Bei**g Natural Science Foundation-Education Commission joint program, grant number KZ202010005013.
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Ma, X., Wu, H., Chang, L. et al. The influence of calcium hydroxide crystal morphology on the desulfurization of cement kiln flue gas. J Mater Sci 57, 18287–18297 (2022). https://doi.org/10.1007/s10853-022-07801-9
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DOI: https://doi.org/10.1007/s10853-022-07801-9