钱大益, 王艳, 叶凯航, 邢奕, 苏伟, 段淑雅. 钢铁行业钙基半干法脱硫灰渣资源化利用进展[J]. 工程科学学报, 2024, 46(3): 567-579. DOI: 10.13374/j.issn2095-9389.2022.12.23.002
引用本文: 钱大益, 王艳, 叶凯航, 邢奕, 苏伟, 段淑雅. 钢铁行业钙基半干法脱硫灰渣资源化利用进展[J]. 工程科学学报, 2024, 46(3): 567-579. DOI: 10.13374/j.issn2095-9389.2022.12.23.002
QIAN Dayi, WANG Yan, YE Kaihang, XING Yi, SU Wei, DUAN Shuya. Progress in the resource utilization of calcium-based semi-dry desulfurized ash in the iron and steel industry[J]. Chinese Journal of Engineering, 2024, 46(3): 567-579. DOI: 10.13374/j.issn2095-9389.2022.12.23.002
Citation: QIAN Dayi, WANG Yan, YE Kaihang, XING Yi, SU Wei, DUAN Shuya. Progress in the resource utilization of calcium-based semi-dry desulfurized ash in the iron and steel industry[J]. Chinese Journal of Engineering, 2024, 46(3): 567-579. DOI: 10.13374/j.issn2095-9389.2022.12.23.002

钢铁行业钙基半干法脱硫灰渣资源化利用进展

Progress in the resource utilization of calcium-based semi-dry desulfurized ash in the iron and steel industry

  • 摘要: 对首钢和唐钢循环流化床(CFB)、密相塔(DFA)烟气脱硫灰氧化改性进行了深入研究,脱硫灰分的矿物相组成主要包括CaSO3·0.5H2O、CaSO4、CaCO3、Ca(OH)2,平均粒径为7.252 μm、中位粒径(D50)为4.521 μm、80%的粒子粒径处于1.039~16.162 μm、比表面积为2.25 m2·g–1,比表面积相对较大,且喷雾干燥(SDA)法脱硫灰粒径明显大于CFB与DFA法;脱硫灰含水率0.02%~0.36%,体积密度0.85~1.0 t·m–3,容积密度0.55~1.0 t·m–3,真密度2.25~2.69 t·m–3,压实密度为1.4 t·m–3;脱硫灰粒大小不一,形状多为不规则的小类球体且孔道直径在0.1~0.2 μm. 结合半干法脱硫灰理化性质系统表征、改性与工业化应用等成果,系统分析目前钢铁企业及其他半干法脱硫灰资源化利用研究的主要方向和进展情况,提出利用半干法脱硫灰制备多种新型材料实现半干法脱硫灰资源化利用.

     

    Abstract: With the introduction of an ultralow emission policy for the steel industry, nearly 70% of the steel enterprises in China have integrated desulfurization, denitrification, dust removal, and collaborative treatment transformation. The semi-dry desulfurization process, which mostly uses CaO or Ca(OH)2 as the desulfurization absorber, has produced large amounts of desulfurization byproducts—desulfurized ash—which is difficult to resource. Relevant data show that China annually produces approximately 20 million tons of semi-dry desulfurized ash, which is the third largest solid waste in China. At present, the treatment of semidry desulfurized ash is mainly based on stockpiling, leading to increased land occupation. Semidry desulfurized ash has the characteristics of slow hydration reaction, strong alkalinity, and high content of metal impurities, and long-term stockpiling also causes environmental pollution; therefore, the resource utilization of semidry desulfurization byproducts has become a hot research and practical issue in the environmental field. This research team conducted in-depth research on the oxidative modification of flue gas desulfurized ash from Shougang and Tanggang circular fluidized bed (CFB) and dense phase tower (DFA). The mineral phase composition of the desulfurized ash mainly includes CaSO3·0.5H2O, CaSO4, CaCO3, and Ca(OH)2, which are slightly different from those of the wet desulfurized ash (the main composition is CaSO4·2H2O). The average particle size of the desulfurized ash is 7.252 μm, with a median particle size (D50) of 4.521 μm, and 80% of the particles are in the range of 1.039–16.162 μm. The specific surface area is 2.25 m2·g−1, the specific surface area is relatively large, and the particle size of desulfurized ash by the spray drying absorption method is significantly larger than that of the CFB and DFA methods. The main physical characteristics of the desulfurized ash are as follows: water content, 0.02%–0.36%; bulk density, 0.85–1.0 t·m−3; bulk density, 0.55–1.0 t·m−3; true density, 2.25–2.69 t·m−3; and compacted density, 1.4 t·m−3. The desulfurized ash particles are of various sizes and mostly irregularly shaped small spheroids with many pores and pore diameters in the region of 0.1–0.2 μm. This article presents the results of systematic characterization of the physical and chemical properties of semidry desulfurized ash, modification, and industrial application; systematically analyses the main directions and progress of research on the resource utilization of semidry desulfurized ash in iron and steel enterprises and other semidry desulfurized ashes; and proposes that the modification of desulfurized ash, such as the oxidation of CaSO3·1/2H2O to CaSO4, is one of the important means to achieve resource utilization. In addition, the use of semi-dry desulfurized ash to prepare various new materials can facilitate resource utilization.

     

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