《工程科学学报》录用稿，htps:/doi.org/10.13374/i,issn2095-9389.2021.03.30.003©北京科技大学2020 基于温度效应的半水磷石膏水化反应热动力学模型 王贻明)，王志凯区，吴爱祥)，彭青松)，李剑秋2) (1.北京科技大学土木与资源工程学院，北京100083：2.贵州大学化学与化工学院，贵阳550025) ☒通信作者，E-mail:ustbwzk@163.com 摘要为扩大半水磷石膏(HPG)作为充填胶凝材料的工业应用半径，实现HPG资源化利用技术新突破。本文寻求一种在堆 存过程中HPG水化反应放热量变化的模型，以了解其胶凝性能的变化情况。通过对初始温度为3540、60和80℃的HPG堆 体进行自由水含量和温度监测，发现HPG自由水含量变化规律符合一级反应动力学模型，之后基热力学和化学反应动力 学基本理论，提出了一种关于堆存温度与时间关系的HPG水化反应热动力学模型。最后/采角COMSOL Multiphysics数值模 拟软件，将HPG水化反应热动力学方程嵌入传热和ODE模块，对HPG堆体温度进行数值模拟 模拟堆体温度变化曲线与 试验结果较为吻合，验证了所提出模型的可靠性。 关键词半水磷石膏：初始堆存温度：自由水含量：一级反应动力学：热动力学：数值模抄 分类号TD853 Thermodynamic Model of Hydration Reaction of hemihydrate phosphogypsum Based on Temperature Effect WANG Yi-ming",WANG Zhi-kai,WU Ai-xiang,PENG. ong,LI Jian-giu) 1)School of Civil and Resource Engineering,University of Science and Technology Betjing,Beijing 100083,China; School of Chemistry Engineering,Guizhou University,Guiyang Corresponding author,E-mail:ustbwzk@163.com ABSTACT Hemihydrate phosphogypsum (HPG).as a cementing material for mine filling,will spontaneously transform into phosphogypsum (PG)in the state of stockpiling The gelling activity decreases and it is difficult to meet the requirements of mechanical properties required for long-distance mine filling.To expand the industrial application radius of HPG as filling cementitious material,the key measure is to prevent the spontaneous conversion of HPG to PG.In-depth research on the conversion process of HPGin the storage stateachieve anew breakthrough in HPG resourceutilizaion technology In the process of storage,the HPG chemical reaction will release the heat of hydration,which will cause the temperature field and the chemical field in the system to interact with each other and promote the conversion of HPG to PG.Therefore,the HPG hydration heat release process is accurately calculated,analyzed and simulated.It is the prerequisite to effectively inhibit the conversion of HPG.This article seeks a model of the heat release of HPG hydration reaction during the storage process to understand the change of its gelation performance and guide on-site industrial applications.First,by monitoring the free water content and temperature of HPG stacks with initial temperatures of 35,40,60,and 80 C,it is found that the HPG free water content change law conforms to the first-order reaction kinetic model.Based on thermodynamics and chemical reaction kinetics,a thermal kinetic model of HPG hydration reaction on the' relationship between storage temperature and time is proposed.Finally,using the COMSOL Multiphysics numerical simulation software,the HPG hydration reaction thermokinetic equation was embedded in the heat transfer and ODE modules,and the HPG reactor temperature was numerically simulated.The simulated reactor temperature curve was more consistent with the experimental results.The reliability of the proposed model is verified.This model can provide model guidance for the later design of delaying HPG conversion plan,and has very important practical significance for the promotion and application of HPG. 收藕日期：2021-03-30 基金项目：国家自然科学基金重点项目资助(51834001)基于温度效应的半水磷石膏水化反应热动力学模型 王贻明 1)，王志凯 1)，吴爱祥 1)，彭青松 1)，李剑秋 2) (1. 北京科技大学 土木与资源工程学院，北京 100083； 2. 贵州大学 化学与化工学院，贵阳 550025) 通信作者, E-mail: ustbwzk@163.com 摘 要 为扩大半水磷石膏（HPG）作为充填胶凝材料的工业应用半径，实现 HPG 资源化利用技术新突破。本文寻求一种在堆 存过程中 HPG 水化反应放热量变化的模型，以了解其胶凝性能的变化情况。通过对初始温度为 35、40、60 和 80 ℃的 HPG 堆 体进行自由水含量和温度监测，发现 HPG 自由水含量变化规律符合一级反应动力学模型，之后基于热力学和化学反应动力 学基本理论，提出了一种关于堆存温度与时间关系的 HPG 水化反应热动力学模型。最后，采用 COMSOL Multiphysics 数值模 拟软件，将 HPG 水化反应热动力学方程嵌入传热和 ODE 模块，对 HPG 堆体温度进行数值模拟，模拟堆体温度变化曲线与 试验结果较为吻合，验证了所提出模型的可靠性。 关键词 半水磷石膏；初始堆存温度；自由水含量；一级反应动力学；热动力学；数值模拟 分类号 TD853 Thermodynamic Model of Hydration Reaction of hemihydrate phosphogypsum Based on Temperature Effect WANG Yi-ming1) , WANG Zhi-kai1), WU Ai-xiang1), PENG Qing-song1) , LI Jian-qiu2) 1) School of Civil and Resource Engineering, University of Science and Technology Beijing, Beijing 100083, China; 2) School of Chemistry Engineering, Guizhou University, Guiyang 550025, China) Corresponding author, E-mail: ustbwzk@163.com ABSTACT Hemihydrate phosphogypsum (HPG), as a cementing material for mine filling, will spontaneously transform into phosphogypsum (PG) in the state of stockpiling. The gelling activity decreases and it is difficult to meet the requirements of mechanical properties required for long-distance mine filling. To expand the industrial application radius of HPG as filling cementitious material, the key measure is to prevent the spontaneous conversion of HPG to PG. In-depth research on the conversion process of HPG in the storage state is required to achieve a new breakthrough in HPG resource utilization technology. In the process of storage, the HPG chemical reaction will release the heat of hydration, which will cause the temperature field and the chemical field in the system to interact with each other and promote the conversion of HPG to PG. Therefore, the HPG hydration heat release process is accurately calculated, analyzed and simulated. It is the prerequisite to effectively inhibit the conversion of HPG. This article seeks a model of the heat release of HPG hydration reaction during the storage process to understand the change of its gelation performance and guide on-site industrial applications. First, by monitoring the free water content and temperature of HPG stacks with initial temperatures of 35, 40, 60, and 80 , it is found that the HPG free water content change law conforms to the first-order reaction ℃ kinetic model. Based on thermodynamics and chemical reaction kinetics, a thermal kinetic model of HPG hydration reaction on the 1 relationship between storage temperature and time is proposed. Finally, using the COMSOL Multiphysics numerical simulation software, the HPG hydration reaction thermokinetic equation was embedded in the heat transfer and ODE modules, and the HPG reactor temperature was numerically simulated. The simulated reactor temperature curve was more consistent with the experimental results. The reliability of the proposed model is verified. This model can provide model guidance for the later design of delaying HPG conversion plan, and has very important practical significance for the promotion and application of HPG. 1收稿日期:2021-03-30 基金项目:国家自然科学基金重点项目资助(51834001) 《工程科学学报》录用稿，https://doi.org/10.13374/j.issn2095-9389.2021.03.30.003 ©北京科技大学 2020 录用稿件，非最终出版稿