Effect of storage temperature on the cementitious property of hemihydrate phosphogypsum
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摘要: 半水磷石膏（HPG）長時間堆存狀態下會出現固結現象，其膠凝性能也相應下降。以室內HPG結晶水檢測和單軸壓縮試驗為基礎，通過設定4種不同堆存溫度，分別為20，40，60和80 ℃，探究不同堆存溫度作用下HPG試樣結晶水質量分數變化和堆存后制備的充填膠凝材料（HCM）抗壓強度發展規律，并采用掃描電鏡等微觀分析手段研究堆存溫度對其強度影響機制。結果表明，堆存溫度對HPG膠凝性能影響顯著，高的堆存溫度會加快HPG試樣中的自由水轉變為結晶水速率，而且會抑制堆存后制備的HCM強度發展。采用數據標準化對不同堆存溫度作用后的試樣抗壓強度作出預測，被證實與實測值較吻合。微觀分析發現，堆存溫度主要影響體系的過飽和度，而使不同堆存溫度作用后制備的HCM微觀形態表現差異。Abstract: Whether domestic or foreign, the utilization of phosphogypsum (PG) resources is not satisfactory. A chemical plant in Guizhou produces phosphoric acid through a semi-aqueous process to obtain the byproduct hemihydrate phosphogypsum (HPG), which has a certain gelling activity. If this feature of HPG can be fully utilized, it can replace cement as a cementing material to prepare mine-filling materials. Utilizing HPG for goaf filling can not only reduce the environmental protection problems caused by the surface discharge of PG but also eliminate the hidden safety hazards in the goaf. At present, when HPG is used to prepare mine-filling cementitious materials, HPG will be consolidated into a block and lose its gelling activity when it is stacked for a certain period of time. The gelling performance of the HPG in the storage state appears to decline. Based on the indoor HPG crystal water detection and uniaxial compression test and setting four different storage temperatures (20 ℃, 40 ℃, 60 ℃, and 80 ℃), this study explored the changes in the mass fraction of the crystal water of HPG samples under different storage temperatures. The compressive strength development law of HCM prepared after storage and microscopic analysis methods, such as scanning electron microscopy, were used to study the influence mechanism of the storage temperature on its strength. Results show that the stacking temperature has a significant effect on the gelling performance of HPG. A high stacking temperature will speed up the conversion of free water in the HPG sample to crystal water and inhibit the strength development of the HCM prepared after stacking. Data standardization was used to predict the compressive strength of samples after storage at different temperatures, which is confirmed to be in good agreement with the measured values. The microscopic analysis found that the storage temperature mainly affects the supersaturation of the system, and the microscopic morphology of the HCM prepared after storage at different temperatures is different.
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圖 1 HPG的礦物組成和微觀形貌分析。（a）HPG的X射線衍射圖；（b）HPG的微觀結構圖
Figure 1. Mineral composition and micromorphology analysis of HPG: (a) X-ray diffraction pattern of HPG; (b) microstructure of HPG
圖 4 不同堆存溫度HPG結晶水質量分數變化過程
Figure 4. Variation process of the HPG crystal water mass fraction at different storage temperatures
圖 5 不同堆存溫度HCM試樣強度發展過程
Figure 5. Strength development process of HCM specimens at different storage temperatures
圖 6 不同堆存溫度下HPG膠凝性能標準化。（a）HPG結晶水質量分數標準化；（b）HCM強度標準化
Figure 6. Standardization of HPG properties at different storage temperatures: (a) standardization of HPG crystal water mass fraction; (b) standardization of HCM strength
圖 7 試樣標準化強度發展曲線斜率與截距誤差。（a）斜率誤差（3~90 d）；（b）截距誤差（3~90 d）
Figure 7. Slope and intercept error of the standardized strength development curve of the specimen: (a) slope error (3–90 d); (b) intercept error (3–90 d)
圖 9 不同堆存溫度下HCM微觀結構圖。（a）20 ℃；（b）40 ℃；（c）60 ℃；（d）80 ℃
Figure 9. HCM microstructure of different storage temperatures: (a) 20 ℃; (b) 40 ℃; (c) 60 ℃; (d) 80 ℃
中文字幕在线观看表 1 HPG化學成份及含水率測定結果表（質量分數）
Table 1. Hemihydrate phosphogypsum’s chemical composition and moisture content
% CaO Al2O3 SiO2 P2O5 MgO Fe2O3 SO3 SrO loss Free water Crystal water 37.86 2.46 4.20 1.37 0.28 0.45 44.82 0.36 0.20 22.10 5.40 
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參考文獻
[1] Cai M F, Xue D L, Ren F H. Current status and development strategy of metal mines. Chin J Eng, 2019, 41(4): 417蔡美峰, 薛鼎龍, 任奮華. 金屬礦深部開采現狀與發展戰略. 工程科學學報, 2019, 41(4):417 [2] Wu A X, Li H, Cheng H Y, et al. Status and prospects of researches on rheology of paste backfill using unclassified-tailings (Part 1): concepts, characteristics and models. Chin J Eng, 2020, 42(7): 803吳愛祥, 李紅, 程海勇, 等. 全尾砂膏體流變學研究現狀與展望(上): 概念、特性與模型. 工程科學學報, 2020, 42(7):803 [3] Sun X W, Wu T J. Experimental research of alkali-activated slag cementitious material. Bull Chin Ceram Soc, 2014, 33(11): 3036孫小巍, 吳陶俊. 堿激發礦渣膠凝材料的試驗研究. 硅酸鹽通報, 2014, 33(11):3036 [4] Liang Z Q. Review on development and application of new type backfilling cementing materials in mining industry. Met Mine, 2015(6): 164 doi: 10.3969/j.issn.1001-1250.2015.06.035梁志強. 新型礦山充填膠凝材料的研究與應用綜述. 金屬礦山, 2015(6):164 doi: 10.3969/j.issn.1001-1250.2015.06.035 [5] Zhang G C, Yang Z Q, Gao Q, et al. Development of early strength filling cementing material with phosphogypsum as substitute of traditional cement. Met Mine, 2015(3): 194張光存, 楊志強, 高謙, 等. 利用磷石膏開發替代水泥的早強充填膠凝材料. 金屬礦山, 2015(3):194 [6] Li J Q, Li Z J, Wang J C, et al. Development status and prospect of phosphogypsum filling material and technique. Mod Min, 2018(10): 1 doi: 10.3969/j.issn.1674-6082.2018.10.001李劍秋, 李子軍, 王佳才, 等. 磷石膏充填材料與技術發展現狀及展望. 現代礦業, 2018(10):1 doi: 10.3969/j.issn.1674-6082.2018.10.001 [7] Wang Y M, Wang Z K, Wu A X, et al. Preparation of new cementitious backfilling material and its curing mechanism analysis. Met Mine, 2018(6): 20王貽明, 王志凱, 吳愛祥, 等. 新型膠凝充填材料制備及固化機理分析. 金屬礦山, 2018(6):20 [8] Lan W T, Wu A X, Wang Y M, et al. Optimization of filling ratio of hemihydrate phosphogypsum based on orthogonal test. Chin J Nonferrous Met, 2019, 29(5): 1083蘭文濤, 吳愛祥, 王貽明, 等. 基于正交試驗的半水磷石膏充填配比優化. 中國有色金屬學報, 2019, 29(5):1083 [9] Lan W T, Wu A X, Wang Y M. Formulation optimization and formation mechanism of condensate expansion and filling composites. Acta Mater Compos Sin, 2019, 36(6): 1536蘭文濤, 吳愛祥, 王貽明. 凝水膨脹充填復合材料的配比優化與形成機制. 復合材料學報, 2019, 36(6):1536 [10] Jiang G Z, Wu A X, Wang Y M, et al. Effect of lime on properties of filling cementitious material prepared by hemihydrate phosphogypsum. J Chin Ceram Soc, 2020, 48(1): 86姜關照, 吳愛祥, 王貽明, 等. 生石灰對半水磷石膏充填膠凝材料性能影響. 硅酸鹽學報, 2020, 48(1):86 [11] Lan W T, Wu A X, Wang Y M, et al. Ionic solidification and size effect of hemihydrate phosphogypsum backfill. China Environ Sci, 2019, 39(1): 210 doi: 10.3969/j.issn.1000-6923.2019.01.024蘭文濤, 吳愛祥, 王貽明, 等. 半水磷石膏充填體離子固化與尺寸效應. 中國環境科學, 2019, 39(1):210 doi: 10.3969/j.issn.1000-6923.2019.01.024 [12] Yang B. Study on the Process of Hydrothermal Treatment of Phosphogypsum [Dissertation]. Kunming: Kunming University of Science and Technology, 2006楊斌. 水熱法處理磷石膏過程研究[學位論文]. 昆明: 昆明理工大學, 2006 [13] Lan W T, Wu A X, Wang Y M, et al. Experimental study on influencing factors of the filling strength of hemihydrate phosphogypsum. J Harbin Inst Technol, 2019, 51(8): 128 doi: 10.11918/j.issn.0367-6234.201804082蘭文濤, 吳愛祥, 王貽明, 等. 半水磷石膏充填強度影響因素試驗. 哈爾濱工業大學學報, 2019, 51(8):128 doi: 10.11918/j.issn.0367-6234.201804082 [14] Yang L, Cao J X, Liu Y M. Mineralogical characteristics of hemi-hydrate phosphogypsum. Acta Petrol Mineral, 2015, 34(6): 827 doi: 10.3969/j.issn.1000-6524.2015.06.005楊林, 曹建新, 劉亞明. 半水磷石膏的礦物學特征. 巖石礦物學雜志, 2015, 34(6):827 doi: 10.3969/j.issn.1000-6524.2015.06.005 [15] Chitambira B. Accelerated Ageing of Cement Stabilised/Solidified Contaminated Soils with Elevated Temperatures [Dissertation]. Cambridge: Cambridge University, 2004 [16] Zhang R J, Zheng J J, Cheng Y S, et al. Experimental investigation on effect of curing temperature on strength development of cement stabilized clay. Rock Soil Mech, 2016, 37(12): 3463章榮軍, 鄭俊杰, 程鈺詩, 等. 養護溫度對水泥固化淤泥強度影響試驗研究. 巖土力學, 2016, 37(12):3463 [17] Morohoshi K, Yoshinaga K, Miyata M, et al. Design and long-term monitoring of Tokyo International Airport extension project constructed on super-soft ground. Geotech Geol Eng, 2010, 28(3): 223 doi: 10.1007/s10706-010-9312-x [18] Yao S, Han B, Wu A X, et al. The effect of temperature on strength of wet shotcrete in cold mining areas and its engineering application. J Min Saf Eng, 2017, 34(2): 384姚松, 韓斌, 吳愛祥, 等. 溫度對高寒礦山濕噴混凝土強度影響規律及工程應用研究. 采礦與安全工程學報, 2017, 34(2):384 [19] Wang D X, Gao X Y, Zou W L, et al. Study on strength predication of reactive MgO-slag/fly ash stabilized clay considering high temperature effect. J Huazhong Univ Sci Technol Nat Sci Ed, 2019, 47(6): 92王東星, 高向雲, 鄒維列, 等. 高溫效應下MgO-礦粉/粉煤灰固化土強度預測. 華中科技大學學報(自然科學版), 2019, 47(6):92 [20] Yang C J, Yang M, Cao J X. Study on hydration and hardening of duplex gypsum binder of hemihydrite phosphogypsum and anhydrite phosphogypsum. Non-Metallic Mines, 2014(6): 22 doi: 10.3969/j.issn.1000-8098.2014.06.008楊成軍, 楊敏, 曹建新. 半水/無水磷石膏復相膠凝材料水化硬化特性研究. 非金屬礦, 2014(6):22 doi: 10.3969/j.issn.1000-8098.2014.06.008 [21] Zhang J L. Research on the Effects of Water-reducing Agents on the Hydration and Setting of α-Calcium Sulfate Hemihydrates [Dissertation]. Hangzhou: Zhejiang University, 2008張佳莉. 減水劑對α半水石膏水化硬化過程的影響研究[學位論文]. 杭州: 浙江大學, 2008 [22] Lin Z S. Cementitious Materials Science. Wuhan: Wuhan University of Technology Press, 2014林宗壽. 膠凝材料學. 武漢: 武漢理工大學出版社, 2014 [23] Lan W T. Research on Hemihydrate Phosphogypsum Based Mineral Filling Composites and Its Pipe Flow Performance [Dissertation]. Beijing: University of Science and Technology Beijing, 2019蘭文濤. 半水磷石膏基礦用復合充填材料及其管輸特性研究[學位論文]. 北京: 北京科技大學, 2019 [24] Jiang G Z, Wu A X, Wang Y M, et al. Low cost and high efficiency utilization of hemihydrate phosphogypsum: Used as binder to prepare filling material. Constr Build Mater, 2018, 167: 263 doi: 10.1016/j.conbuildmat.2018.02.022 [25] Rong K W, Lan W T, Li H Y. Industrial experiment of goaf filling using the filling materials based on hemihydrate phosphogypsum. Minerals, 2020, 10(4): 324 doi: 10.3390/min10040324 -
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