丁彦博， 丰曙霞， 夏霄， 田叶顺， 吴长亮， 段广彬
济南大学 材料科学与工程学院， 山东 济南 250022
引用格式：
丁彦博， 丰曙霞， 夏霄， 等. 石灰中和复合中温煅烧制备Ⅱ型无水石膏的工艺优化［J］. 中国粉体技术， 2026， 32（2）： 1-12.
DING Yanbo， FENG Shuxia， XIA Xiao， et al. Process optimization for preparation of anhydrite-Ⅱ via lime neutralization coupled with medium‑temperature calcination［J］. China Powder Science and Technology， 2026， 32（2）： 1-12.
DOI：10.13732/j.issn.1008-5548.2026.02.017
收稿日期： 2025-02-14， 修回日期： 2025-04-11，上线日期： 2025-08-30。
基金项目： 国家自然科学基金项目，编号： 52400166；内蒙古自治区科技计划项目， 编号： 2022YFHH0118； 山东省自然科学基金，编号：ZR2024QE143、 ZR2024QE347； 国家资助博士后研究人员计划， 编号： GZC20240597。
第一作者简介： 丁彦博（2000—），男，硕士生，研究方向为磷石膏的综合利用。E-mail：13364445475@163.com。
通信作者简介： 丰曙霞（1982—），女，副教授，博士，研究方向为固废综合利用。E-mail：mse_fengsx@ujn.edu.cn。
通信作者:段广彬（1983—），男，教授，博士，硕士生导师，研究方向为固废综合利用。E-mail：mse_duangb@ujn.edu.cn。
摘要： 【目的】 为了推动磷石膏资源化利用，解决因含有磷、氟杂质及有机质导致其利用率低的问题，开发高效、低能耗的Ⅱ型无水石膏煅烧制备工艺。【方法】 采用石灰中和结合中温煅烧处理技术，研究煅烧温度及保温时间对Ⅱ型无水石膏综合性能的影响，优化磷石膏制备Ⅱ型无水石膏工艺流程及参数。【结果】 煅烧温度和保温时间对Ⅱ型无水石膏性能影响显著；煅烧温度过低、保温时间过短，煅烧磷石膏有共晶磷残留，煅烧温度过高、保温时间过长，煅烧磷石膏反应活性降低；相较于未经石灰中和处理800 ℃下煅烧2 h的Ⅱ型无水石膏，优化后的煅烧工艺中煅烧温度和保温时间分别降低38%和25%，Ⅱ型无水石膏的凝结时间缩短78%，3 d抗压强度提升55%；最佳煅烧条件为煅烧温度500 ℃、保温1.5 h。【结论】 石灰中和复合中温煅烧技术可有效去除磷石膏中有害共晶磷杂质，获得性能优良的Ⅱ型无水石膏。
关键词： 磷石膏； Ⅱ型无水石膏； 共晶磷； 煅烧温度
Abstract
Objective Phosphogypsum（PG） is one of the predominant solid wastes generated by the phosphorus chemical industry. It contains harmful components， including phosphorus compounds， sulfates， fluoride， organic matter， trace metals， and radioactive substances， posing severe environmental threats by contaminating soil， surface water， and groundwater. Therefore， the resource utilization of PG is an urgent environmental challenge. Anhydrite II （AⅡ）， a gypsum-based cementitious material with superior properties， is primarily produced through high-temperature calcination to remove crystallization water. This method offers advantages such as reasonable costs and controllable processing， making it widely applicable in the building industry.However， such traditional processes have significant limitations， as the required high temperatures cause high energy consumption and costs and reduce the reactivity of anhydrous gypsum， thereby impairing its hydration rate and application performance.To address these issues， this study aims to optimize the calcination process of AⅡ and explore a technical approach for producing high-performance AⅡ at moderate temperatures. By lowering the calcination temperature and shortening the holding time， this study achieves the dual goal of reducingenergy consumption and enhancing product performance.This provides a scientific foundation and technical support for the efficient utilization of PG.
Methods A combined approach of lime neutralization and medium-temperature calcination was adopted.Lime neutralization was employed to eliminate soluble phosphorus and fluorine， thereby reducing firing temperature. Medium-temperature calcination was utilized to remove organic matter.First， AⅡ was synthesized at various calcination temperatures. The synthesized samples were characterized using aseries of advanced analytical techniques， including X-ray diffraction （XRD）， X-ray fluorescence spectroscopy （XRF）， scanning electron microscopy （SEM）， and Fourier-transform infrared spectroscopy （FTIR）. Phase composition， microstructure， water requirement for normal consistency， setting time， compressive strength， and eutectic phosphorus content were comprehensively evaluated.The impact of calcination temperature on the mineral composition， morphology， performance， and mechanical properties of AⅡ was systematically analyzed to determine the optimal calcination temperature. Subsequently， the influence of different holding times on the properties of AⅡ was investigated， and the optimal duration was identified.
Results and Discussion As the calcination temperature increased， the phase composition of the calcined product transitioned from hemihydrates to anhydrous gypsum. At 450 ℃， XRD patterns revealed no diffraction peak in hemihydrate gypsum. At 500 ℃， the microstructure evolved from grains with distinct boundaries into a denser plate-like form.This transition was accompanied by a gradual reduction in water requirement and an extended setting time， correlating with the increasing proportion of AⅡ in the system. The 3-day compressive strength initially increased， peaking at 500 ℃， but then declined when AⅡ became the dominant.This reduction in strength at higher temperatures was due to the decreased reactivity of the material.In the FTIR spectrum， the absorption peak of eutectic phosphorus gradually faded and disappeared at 500 ℃， indicating its complete decomposition.As the holding time increased， the phase composition of the calcined products remained as anhydrous gypsum. After 1.5 hours of calcination， the microstructure transformed into a plate-like form. The water requirement for normal consistency initially decreased and then increased， while the 3-day compressive strength first increased and then decreased， both reaching their respective lowest and highest values at 1.5 hours of calcination. These changes were attributed to the complete decomposition of eutectic phosphorus at 1.5 hours， eliminating its suppression of hydration. The FTIR analysis further validated the process， showing a significant reduction in phosphorus absorption peaks after 1.5 hours. Experiments showed that the optimal calcination temperature for AⅡ preparation was 500 ℃， and the ideal holding time was 1.5 hours. Compared to traditional processes， this optimized method reduced the calcination temperature by 38% and the holding time by 25%. Additionally， the setting time was reduced by 78%， and the 3-day compressive strength was enhanced by 55%， demonstrating significant improvements in both energy efficiency and material performance.
Conclusion Both calcination temperature and holding time significantly influence the properties of AⅡ. Insufficient temperatures or duration result in the incomplete decomposition of eutectic phosphorus，causing impurities. Conversely， excessive temperatures or prolonged holding time reduce the reactivity of the material， thereby compromising its application potential. The combination of lime neutralization and medium-temperature calcination can effectively remove harmful eutectic phosphorus impurities from PG， yielding high-performance AⅡ. The optimal calcination conditions are determined to be 500 ℃ with a holding time of 1.5 hours.
Keywords： phosphogypsum； anhydrite II； eutectic phosphorus； calcination temperature
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