Enhanced Sulfur Fixation Efficiency of Calcium Hydroxide by Fe3+: Dual Mechanisms of Oxidation and Catalysis

doi:10.15541/jim20250348

Abstract

Abstract: Sulfur dioxide (SO₂) is a major air pollutant that poses severe hazards to the environment and human health. Currently, calcium hydroxide (Ca(OH)₂) is widely used as a common desulfurizing agent due to its simple preparation process, low cost, and relatively good desulfurization performance. However, further improving its sulfur fixation efficiency remains a key focus of research. In this study, a calcium-iron desulfurizing agent was prepared in a stepwise manner by incorporating ferric hydroxide during the hydration process of calcium oxide (CaO), and its desulfurization performance was systematically investigated. The results demonstrated that sulfur fixation efficiency of the calcium-iron desulfurizing agent was significantly enhanced, showing a 26.16% increase compared to the maximum sulfur fixation efficiency of pure Ca(OH)₂. The addition of Fe³⁺ modified the morphology of Ca(OH)₂, rendering its surface much rougher and increasing the number of pores and cracks. This morphological change provided more active sites for the desulfurization reaction. Furthermore, X-ray photoelectron spectroscopy analysis revealed that the proportion of hexavalent sulfur (S⁶⁺) in the sample after desulfurization increased from 9.71% (pure Ca(OH)₂) to 33.33% (calcium-iron desulfurizing agent). Before desulfurization, all iron in the calcium-iron desulfurizing agent was in the form of Fe³⁺. After desulfurization, Fe²⁺ accounted for 68.42% and Fe³⁺ accounted for 31.58% of the total iron. Calculations based on these data indicated that 35.56% of the sulfur was oxidized, while 64.44% was catalyzed. These findings confirmed that the oxidation and catalytic effects of iron promoted the conversion of tetravalent sulfur (S⁴⁺) to S⁶⁺, thereby further improving the sulfur fixation efficiency. This study provides an effective approach to enhance the sulfur fixation efficiency of Ca(OH)₂ and holds significant reference value for the selection of materials used in the removal of sulfur dioxide from industrial flue gas.

Key words: sulfur dioxide, calcium hydroxide, calcium iron desulfurizer, sulfur fixation efficiency, oxidation, catalysis

CLC Number:

TB321

LI Zhongyi, LIU Biao, CHEN Xi, LI Chunzhong, JIANG Haibo. Enhanced Sulfur Fixation Efficiency of Calcium Hydroxide by Fe³⁺: Dual Mechanisms of Oxidation and Catalysis[J]. Journal of Inorganic Materials, DOI: 10.15541/jim20250348.

References

[1] LUM M M X, NG K H, LAI S Y,et al. Sulfur dioxide catalytic reduction for environmental sustainability and circular economy: a review. Process Safety and Environmental Protection, 2023, 176: 580.
[2] CHEN W C, XIANG Y H, LIU J,et al. Foreign investor and industrial pollution: evidence from sulfur dioxide emission. Finance Research Letters, 2022, 50: 103279.
[3] YANG C H, CHEN P H, YANG C S,et al. Analysis and forecasting of air pollution on nitrogen dioxide and sulfur dioxide using deep learning. IEEE Access, 2024, 12: 165236.
[4] ZHANG J Y.The mechanism of foreign direct investment on China’s sulfur dioxide emissions: evidence from partial least squares structural equation modeling.Journal of Environmental Management, 2025, 380: 124998.
[5] QIAN Y, CAO H, HUANG S M.Decoupling and decomposition analysis of industrial sulfur dioxide emissions from the industrial economy in 30 Chinese provinces.Journal of Environmental Management, 2020, 260: 110142.
[6] LI Y, GAO L H, ZHANG J H,et al. Synergetic utilization of microwave-assisted fly ash and carbide slag for simultaneous desulfurization and denitrification: high efficiency, low cost and catalytic mechanism. Chemical Engineering Journal, 2022, 437: 135488.
[7] DAI G F, ZHANG J Y, WANG X B,et al. Calcination and desulfurization characteristics of calcium carbonate in pressurized oxy-combustion. Energy, 2022, 261: 125150.
[8] KUMAR A.Desulfurization performance of sulfur dioxide and product characteristics in semi-batch bubble column and foam-bed contactor.Chemical Papers, 2019, 74: 2427.
[9] OSAKA Y, TSUIGUCHI T, KODAMA A,et al. Improvement of dry desulfurization performance using activated calcium carbonate by amorphous citric acid complex method for diesel gas purification. Journal of Material Cycles and Waste Management, 2020, 22: 470.
[10] SHIN H G, KIM H, NOH T,et al. Degradation behavior of high surface area calcium hydroxide sorbent for SO₂ removal. International Journal of Mineral Processing, 2011, 98(3/4): 145.
[11] YAN D J, HE R N, WU X Y,et al. An investigation of the surface structure of surfactants modified calcium hydroxide and enhancement of dry flue gas desulfurization performance. Research on Chemical Intermediates, 2025, 51(3): 1583.
[12] SHIN H G, KIM H, KIM Y N,et al. Preparation and characterization of high surface area calcium hydroxide sorbent for SO₂ removal. Current Applied Physics, 2009, 9(3): S276.
[13] LIU M, DING W X, CHANG J Y,et al. Pilot study on coke oven flue gas injection desulfurization using highly active modified calcium hydroxide desulfurizer. Asia-Pacific Journal of Chemical Engineering, 2025, 20(2): e3170.
[14] 熊爽, 严金生, 周洲, 等. 生石灰消化反应条件对氢氧化钙特性影响. 无机盐工业, 2023, 55(12): 50.
[15] 刘越, 郑强, 邢佳斌, 等. 石灰石干法制备高性能氢氧化钙的工艺及应用研究. 无机盐工业, 2023, 55(10): 42.
[16] RENEDO M J, FERNÁNDEZ-FERRERAS J. Characterization and behavior of modified calcium-hydroxide-based sorbents in a dry desulfurization process.Energy & Fuels, 2016, 30(8): 6350.
[17] LI Y R, QI H Y, YOU C F,et al. Kinetic model of CaO/fly ash sorbent for flue gas desulphurization at moderate temperatures. Fuel, 2007, 86(5/6): 785.
[18] FANG D X, HUANG L P, FANG Z Y,et al. Evaluation of porous calcium silicate hydrate derived from carbide slag for removing phosphate from wastewater. Chemical Engineering Journal, 2018, 354: 1.
[19] 李春花, 苏春华, 王超, 等. 草木灰促进CaO粉末高温烟气脱硫实验研究. 应用化工, 2010, 39(4): 521.
[20] SALVITTI C, ROSI M, PEPI F,et al. Reactivity of transition metal dioxide anions MO₂-(M = Co, Ni, Cu, Zn) with sulfur dioxide in the gas phase: an experimental and theoretical study. Chemical Physics Letters, 2021, 776: 138555.
[21] 高翔, 骆仲泱, 陈亚非, 等. 钙基吸收剂脱硫反应特性的研究. 燃烧科学与技术, 1998, 4(4): 369.
[22] SU M H, YANG L C.Fe/Mn-MOFs with monocarboxylic acid-induced defects enhances the catalytic oxidation of calcium sulfite in desulfurization ash.Separation and Purification Technology, 2024, 353: 128300.
[23] LATYPOVA S, ESEVA E, LEVIN I,et al. Catalytic performance of transition metal molybdates in accelerated oxidative desulfurization. Fuel, 2025, 403: 136114.
[24] CHEN X Y, ZHOU S R, WANG L Y,et al. Facile preparation of Fe-Beta zeolite-supported transition metal oxide catalysts and their catalytic performance for the simultaneous removal of NO_x and soot. Chinese Journal of Chemical Engineering, 2024, 76: 10.
[25] KIM H M, JEONG C H, CHEON B S,et al. Improving the performance of a Co-CeO₂ catalyst for hydrogen production via water gas shift reaction by addition of transition metal oxides. Energy & Fuels, 2024, 38(5): 4743.
[26] WU H D, YU B, Ni C S,et al. Enhancement of catalytic performance in Zr_0.1Ce_0.9O₂-_δ through transition metal doping and exsolution. Solid State Ionics, 2025, 425: 116868.
[27] SUN B, WANG J G, CHEN M,et al. Boosting acetone oxidation performance over mesocrystal M_xCe₁-_xO₂(M = Ni, Cu, Zn) solid solution within hollow spheres by tailoring transition-metal cations. International Materials Chemistry and Physics, 2023, 293: 126925.
[28] HE K J, SONG Q, YAN Z N,et al. Study on competitive absorption of SO₃ and SO₂ by calcium hydroxide. Fuel, 2019, 242: 355.
[29] MA X Y, WU H, CHANG L,et al. The influence of calcium hydroxide crystal morphology on the desulfurization of cement kiln flue gas. Journal of Materials Science, 2022, 57(39): 18287.
[30] DOS SANTOS V H J M, PONTIN D, PONZI G G D,et al. Application of Fourier transform infrared spectroscopy (FTIR) coupled with multivariate regression for calcium carbonate (CaCO₃) quantification in cement. Construction and Building Materials, 2021, 313: 125413.
[31] YAN D J, ZHU Y P, ZHAO J X,et al. Synthesis and utilization of polyol-modified high specific surface area Ca(OH)₂: an investigation. Environmental Science and Pollution Research International, 2024, 31(22): 32714.
[32] HUANG T K, QIN Y L, LI M C,et al. Preparation and characterization of deacetylated konjac glucomannan/pectin composite films crosslinked with calcium hydroxide. Journal of Polymer Research, 2022, 29(6): 238.
[33] ZHANG Y, TONG S R, GE M F,et al. The formation and growth of calcium sulfate crystals through oxidation of SO₂ by O₃ on size-resolved calcium carbonate. RSC Advances, 2018, 8(29): 16285.
[34] BÖKE H, AKKURT S, SERHAN Ö,et al. Quantification of CaCO₃-CaSO₃·0.5H₂O-CaSO₄·2H₂O mixtures by FTIR analysis and its ANN model. Materials Letters, 2004, 58(5): 723.
[35] FU H B, WANG X, WU H B,et al. Heterogeneous uptake and oxidation of SO₂ on iron oxides. The Journal of Physical Chemistry C, 2007, 111(16): 6077.
[36] ZHANG Y X, JIA Y.A facile solution approach for the synthesis of akaganéite (β-FeOOH) nanorods and their ion-exchange mechanism toward As(V) ions. Applied Surface Science, 2014, 290: 102.
[37] DING M, DE JONG B H W S, ROOSENDAAL S J,et al. XPS studies on the electronic structure of bonding between solid and solutes: adsorption of arsenate, chromate, phosphate, Pb²⁺, and Zn²⁺ ions on amorphous black ferric oxyhydroxide. Geochimica et Cosmochimica Acta, 2000, 64(7): 1209.
[38] LI L L, CHU Y, LIU Y, et al.Template-free synthesis and photocatalytic properties of novel Fe2O3 hollow spheres.The Journal of Physical Chemistry C, 2007, 111(5): 212.

Enhanced Sulfur Fixation Efficiency of Calcium Hydroxide by Fe³⁺: Dual Mechanisms of Oxidation and Catalysis

PDF (PC)

Knowledge

Abstract

Cite this article

share this article

References

Related Articles 15

Recommended Articles

Metrics

Comments

[1]	LIU Jiangping, GUAN Xin, TANG Zhenjie, ZHU Wenjie, LUO Yongming. Research Progress on Catalytic Oxidation of Nitrogen-containing Volatile Organic Compounds [J]. Journal of Inorganic Materials, 2025, 40(9): 933-943.
[2]	ZHU Wenjie, TANG Lu, LU Jichang, LIU Jiangping, LUO Yongming. Research Progress on Catalytic Oxidation of Volatile Organic Compounds by Perovskite Oxides [J]. Journal of Inorganic Materials, 2025, 40(7): 735-746.
[3]	FAN Xiaoxuan, ZHENG Yonggui, XU Lirong, YAO Zimin, CAO Shuo, WANG Kexin, WANG Jiwei. Organic Pollutant Fenton Degradation Driven by Self-activated Afterglow from Oxygen-vacancy-rich LiYScGeO₄: Bi³⁺ Long Afterglow Phosphor [J]. Journal of Inorganic Materials, 2025, 40(5): 481-488.
[4]	LI Jianjun, CHEN Fangming, ZHANG Lili, WANG Lei, ZHANG Liting, CHEN Huiwen, XUE Changguo, XU Liangji. Peroxymonosulfate Activation by CoFe₂O₄/MgAl-LDH Catalyst for the Boosted Degradation of Antibiotic [J]. Journal of Inorganic Materials, 2025, 40(4): 440-448.
[5]	JIA Xianghua, ZHANG Huixia, LIU Yanfeng, ZUO Guihong. Cu₂O/Cu Hollow Spherical Heterojunction Photocatalysts Prepared by Wet Chemical Approach [J]. Journal of Inorganic Materials, 2025, 40(4): 397-404.
[6]	MU Shuang, MA Qin, ZHANG Yu, SHEN Xu, YANG Jinshan, DONG Shaoming. Oxidation Behavior of Yb₂Si₂O₇ Modified SiC/SiC Mini-composites [J]. Journal of Inorganic Materials, 2025, 40(3): 323-328.
[7]	LI Wei, XU Zhiming, GOU Yanzi, YIN Senhu, YU Yiping, WANG Song. Preparation and Performance of Sintered SiC Fiber-bonded Ceramics [J]. Journal of Inorganic Materials, 2025, 40(2): 177-183.
[8]	LI Xiaoxuan, FU Qiangang, WEN Zihao, YANG Jinshan, NI Dewei, ZHANG Jie, CHENG Yuan, LIU Yuxuan, CHU Yanhui, CAI Feiyan, WANG Jingyang, ZHANG Xinghong. Research Progress on Ultra-high Temperature Ceramic Structural Materials for Extreme Environments [J]. Journal of Inorganic Materials, 2025, 40(10): 1045-1078.
[9]	ZHANG Li, GUAN Haoyang, ZHENG Qining, HONG Zhiliang, WANG Jiaxuan, XING Ning, LI Mei, LIU Yongsheng, ZHANG Chengyu. Creep Properties and Damage Mechanisms of SiC_f/SiC-SiYBC Prepared by Melt Infiltration [J]. Journal of Inorganic Materials, 2025, 40(1): 23-30.
[10]	WANG Wenting, XU Jingjun, MA Ke, LI Meishuan, LI Xingchao, LI Tongqi. Oxidation Behavior at 1000-1300 ℃ in air of Ti₂AlC-20TiB₂ Synthesized by in-situ Reaction/Hot Pressing [J]. Journal of Inorganic Materials, 2025, 40(1): 31-38.
[11]	YANG Xin, HAN Chunqiu, CAO Yuehan, HE Zhen, ZHOU Ying. Recent Advances in Electrocatalytic Nitrate Reduction to Ammonia Using Metal Oxides [J]. Journal of Inorganic Materials, 2024, 39(9): 979-991.
[12]	QUAN Wenxin, YU Yiping, FANG Bing, LI Wei, WANG Song. Oxidation Behavior and Meso-macro Model of Tubular C/SiC Composites in High-temperature Environment [J]. Journal of Inorganic Materials, 2024, 39(8): 920-928.
[13]	TAN Min, CHEN Xiaowu, YANG Jinshan, ZHANG Xiangyu, KAN Yanmei, ZHOU Haijun, XUE Yudong, DONG Shaoming. Microstructure and Oxidation Behavior of ZrB₂-SiC Ceramics Fabricated by Tape Casting and Reactive Melt Infiltration [J]. Journal of Inorganic Materials, 2024, 39(8): 955-964.
[14]	MA Binbin, ZHONG Wanling, HAN Jian, CHEN Liangyu, SUN Jingjing, LEI Caixia. ZIF-8/TiO₂ Composite Mesocrystals: Preparation and Photocatalytic Activity [J]. Journal of Inorganic Materials, 2024, 39(8): 937-944.
[15]	JIANG Lingyi, PANG Shengyang, YANG Chao, ZHANG Yue, HU Chenglong, TANG Sufang. Preparation and Oxidation Behaviors of C/SiC-BN Composites [J]. Journal of Inorganic Materials, 2024, 39(7): 779-786.