Ⅱ型无水磷石膏凝结硬化过程调控技术

doi:10.16085/j.issn.1000-6613.2021-2506

摘要/Abstract

摘要：

为改善Ⅱ型无水磷石膏水化活性低、凝结硬化缓慢的问题，研制了一种复合助剂（β-半水石膏6%、改性钢渣3%、K₂SO₄ 2%、铝酸钙水泥0.5%）。研究表明，掺入复合助剂后Ⅱ型无水磷石膏初凝时间由744min（空白样）缩短至76min（改性样）。在此基础上添加25%的高炉矿渣微粉改善力学性能和耐水性，改性后的胶凝材料绝干抗压强度达到15.4MPa，软化系数达到0.83。研究了胶凝体系的水化率、液相离子浓度随时间的变化规律，结合X射线衍射（XRD）和扫描电子显微镜（SEM）对水化产物和水化硬化机理进行了分析。复合助剂加速了Ⅱ型无水磷石膏的溶解及二水石膏晶核的生成和长大，提高了Ⅱ型无水磷石膏的水化率，与矿渣协同作用促进生成3CaO·Al₂O₃·3CaSO₄·32H₂O、3CaO·Fe₂O₃·3CaSO₄·32H₂O等多种低溶度积复盐，改善了胶凝材料的凝结硬化性能和耐水性。

关键词: Ⅱ型无水磷石膏, 耐水性, 凝结性能, 复盐

Abstract:

In order to solve the problems of low hydration activity and long setting time of anhydrite-Ⅱ phosphogypsum, a composite additive was prepared which was composed of β hemihydrate gypsum 6%, sulfuric acid modified steel slag 3%, K₂SO₄ 2% and calcium aluminate cement 0.5%. It was indicated that the initial setting time was shortened from 744min (blank) to 76min (modified). Blast furnace slag powder was used to further improve water resistance and mechanical strength for the cementitious system. With the addition of slag 25%, the compressive strength of cementing material was 15.4MPa and the softening coefficient was up to 0.83. The changes of hydration rate and liquid ion concentration with time were investigated. The hydration products and hydration hardening mechanism of cementitious materials were analyzed by using XRD and SEM. The results showed that the composite additive promoted the dissolution of anhydrite-Ⅱ phosphogypsum as well as the formation and growth of dihydrate gypsum crystal nucleus, increasing the hydration rate. The combined use of the composite additive and blast furnace slag promoted the formation of a variety of low solubility double salts such as 3CaO·Al₂O₃·3CaSO₄·32H₂O and 3CaO·Fe₂O₃·3CaSO₄·32H₂O, which helped to improve the mechanical strength and water resistance of cementitious material.

Key words: anhydrite-Ⅱ phosphogypsum, water-resistance, setting time, double salt

中图分类号:

X705

张宇, 杨家豪, 刘瑜, 宋子玉, 何涵潇, 赵风清. Ⅱ型无水磷石膏凝结硬化过程调控技术[J]. 化工进展, 2022, 41(10): 5637-5644.

ZHANG Yu, YANG Jiahao, LIU Yu, SONG Ziyu, HE Hanxiao, ZHAO Fengqing. Regulating technology of setting and hardening process of anhydrite-Ⅱphosphogypsum[J]. Chemical Industry and Engineering Progress, 2022, 41(10): 5637-5644.

图/表 14

参考文献 30

1	白海丹. 2019年我国磷石膏利用现状、问题及建议[J]. 硫酸工业, 2020(12): 7-10.
	BAI Haidan. Current situation, problems and suggestions of phosphogypsum utilization of 2019 in China[J]. Sulphuric Acid Industry, 2020(12): 7-10.
2	李纯, 薛鹏丽, 张文静, 等. 我国磷石膏处置现状及绿色发展对策[J]. 化工环保, 2021, 41(1): 102-106.
	LI Chun, XUE Pengli, ZHANG Wenjing, et al. Disposal status of phosphogypsum in China and countermeasures for green development[J]. Environmental Protection of Chemical Industry, 2021, 41(1): 102-106.
3	田立楠. 磷石膏综合利用[J]. 化工进展, 2002, 21(1): 56-59.
	TIAN Linan. Comprehensive utilization of phosphogypsum[J]. Chemical Industry and Engineering Progress, 2002, 21(1): 56-59.
4	孟令佳, 吉忠海, 陈津. 工业副产石膏热分解脱硫的研究进展[J]. 化工进展, 2017, 36(2): 626-633.
	MENG Lingjia, JI Zhonghai, CHEN Jin. Advance of the thermal decomposition of industrial by-product gypsum[J]. Chemical Industry and Engineering Progress, 2017, 36(2): 626-633.
5	陈蜜蜜, 樊铁林, 赵风清. 复合胶凝剂和废玻璃钢纤维改性半水脱硫石膏[J]. 环境工程学报, 2017, 11(11): 6130-6136.
	CHEN Mimi, FAN Tielin, ZHAO Fengqing. Modification on desulfurization gypsum by compound gelling agent and waste glass-reinforced plastic fiber[J]. Chinese Journal of Environmental Engineering, 2017, 11(11): 6130-6136.
6	吴峰, 吴硕琮, 马家玉, 等. 金属离子对水热法制备半水硫酸钙晶须的形貌及粒径的影响[J]. 化工进展, 2018, 37(4): 1536-1543.
	WU Feng, WU Shuocong, MA Jiayu, et al. Effect of metal ions on crystal morphology and size of calcium sulfate hemihydratewhiskers preparated by hydrothermal method[J]. Chemical Industry and Engineering Progress, 2018, 37(4): 1536-1543.
7	WANG Qiang, CUI Yong, XUE Junfeng. Study on the improvement of the waterproof and mechanical properties of hemihydrate phosphogypsum-based foam insulation materials[J]. Construction and Building Materials, 2020, 230: 117014.
8	ZHAO Fengqing, LIU Hongjie, HAO Lixia, et al. Water resistant block from desulfurization gypsum[J]. Construction and Building Materials, 2012, 27(1): 531-533.
9	冯洋, 杨林, 曹建新, 等. 磷石膏煅烧改性制备自流平砂浆的研究[J]. 硅酸盐通报, 2020, 39(9): 2891-2897.
	FENG Yang, YANG Lin, CAO Jianxin, et al. Calcining modification of phosphogypsum to prepare self-leveling mortar[J]. Bulletin of the Chinese Ceramic Society, 2020, 39(9): 2891-2897.
10	陈家伟, 张仁亮. 工业副产石膏资源化利用生态环境技术发展报告[J]. 广州化工, 2020, 48(24): 1-3.
	CHEN Jiawei, ZHANG Renliang. Report on ecological environment technology development of industrial by-product gypsum resource utilization[J]. Guangzhou Chemical Industry, 2020, 48(24): 1-3.
11	杨奇玮, 杨新亚, 王义恒, 等. 复合型石膏在净浆和自流平砂浆中的性能研究[J]. 新型建筑材料, 2020, 47(8): 82-85.
	YANG Qiwei, YANG Xinya, WANG Yiheng, et al. Research on performance of composite gypsum on properties of paste and self-leveling mortar[J]. New Building Materials, 2020, 47(8): 82-85.
12	梁旭辉. 磷建筑石膏改性及自流平砂浆制备[D]. 重庆: 重庆大学, 2018.
	LIANG Xuhui. Study on modification of β-hemihydrate phosphogypsum and preparation of self-leveling screeds[D]. Chongqing: Chongqing University, 2018.
13	汪路, 谭宏斌, 李玉龙, 等. Ⅱ型无水石膏制备及水泥对其性能影响研究[J]. 非金属矿, 2020, 43(5): 52-54, 63.
	WANG Lu, TAN Hongbin, LI Yulong, et al. Preparation of Ⅱ-anhydrite gypsum and effect of cement on its properties[J]. Non-Metallic Mines, 2020, 43(5): 52-54, 63.
14	张建新. 天然硬石膏水化硬化及活性激发研究[D]. 重庆: 重庆大学, 2009.
	ZHANG Jianxin. Study on hydration and hardening of natural anhydrite and its activation[D]. Chongqing: Chongqing University, 2009.
15	邓鹏, 王培铭. 天然硬石膏的活性激发及改性[J]. 新型建筑材料, 2007, 34(1): 62-65.
	DENG Peng, WANG Peiming. Activation and modification of natural anhydrite[J]. New Building Materials, 2007, 34(1): 62-65.
16	乔秀臣, 马大伟, 薛玉兵. 煅烧硬石膏溶解特性对钙矾石形成的影响[J]. 硅酸盐通报, 2021, 40(1): 201-206.
	QIAO Xiuchen, MA Dawei, XUE Yubing. Influence of calcined anhydrite solubility on the formation of ettringite[J]. Bulletin of the Chinese Ceramic Society, 2021, 40(1): 201-206.
17	马保国, 李显良, 苏英, 等. 3种对硬石膏的改性试验研究[J]. 武汉理工大学学报, 2015, 37(8): 27-30.
	MA Baoguo, LI Xianliang, SU Ying, et al. Three kinds of experimental study on anhydrite’s modification[J]. Journal of Wuhan University of Technology, 2015, 37(8): 27-30.
18	PENG Fu, ZHONG Li guo. Fluorine gypsum modification and preparation of self-leveling material[J]. Applied Mechanics and Materials, 2014, 711: 133-136.
19	SIEVERT T, WOLTER A, SINGH N B. Hydration of anhydrite of gypsum (CaSO₄.Ⅱ) in a ball mill[J]. Cement and Concrete Research, 2005, 35(4): 623-630.
20	张立乾, 朱志鑫, 王能. 改性增强天然硬石膏的应用研究[J]. 建材发展导向, 2020, 18(4): 11-13.
	ZHANG Liqian, ZHU Zhixin, WANG Neng. Application research of modified and reinforced natural anhydrit[J]. Development Guide to Building Materials, 2020, 18(4): 11-13.
21	SINGH N B. The activation effect of K₂SO₄ on the hydration of gypsum anhydrite, CaSO₄(Ⅱ)[J]. Journal of the American Ceramic Society, 2004, 88(1): 196-201.
22	SCHIEFER Christopher, PLANK Johann. Mechanochemical syngenite as hydration accelerator for anhydrite-based self-levelling floor screeds[J]. Construction and Building Materials, 2021, 308: 124982.
23	漆寒梅, 周言凤, 陈利娟, 等. 硫酸钡重量法测定硫条件实验探讨[J]. 中国无机分析化学, 2021, 11(4): 31-34.
	QI Hanmei, ZHOU Yanfeng, CHEN Lijuan, et al. Discussion on the condition of measuring sulfur by barium sulfate gravimetric method[J]. Chinese Journal of Inorganic Analytical Chemistry, 2021, 11(4): 31-34.
24	陈华林, 冯忠琼, 张枝健, 等. EDTA滴定法测定钙离子浓度的影响因素与优化[J]. 西南民族大学学报(自然科学版), 2020, 46(6): 578-585.
	CHEN Hualin, FENG Zhongqiong, ZHANG Zhijian, et al. Influence factors and optimization on the EDTA titration of calcium[J]. Journal of Southwest Minzu University (Natural Science Edition), 2020, 46(6): 578-585.
25	陈雄木. 冶金废渣对β-半水石膏的改性及机理分析[D]. 石家庄: 河北科技大学, 2019.
	CHEN Xiongmu. Modification of β-semi-hydrated gypsum with waste metallurgical slags and the mechanism[D]. Shijiazhuang: Hebei University of Science and Technology, 2019.
26	庄楚强, 何春雄. 应用数理统计基础[M]. 3版. 广州: 华南理工大学出版社, 2006.
	ZHUANG Chuqiang, HE Chunxiong. Fundamentals of applied mathematical statistics[M]. 3rd ed. Guangzhou: South China University of Technology Press, 2006.
27	陈蜜蜜. 基于协同优化的石膏基胶凝材料改性研究[D]. 石家庄: 河北科技大学, 2017.
	CHEN Mimi. Gypsum cementing material modification based on synergistic optimization[D]. Shijiazhuang: Hebei University of Science and Technology, 2017.
28	罗立群, 舒伟, 程琪林, 等. 铁尾矿加气混凝土制备工艺及结构形成机理分析[J]. 化工进展, 2017, 36(4): 1482-1490.
	LUO Liqun, SHU Wei, CHENG Qilin, et al. Reaction mechanism on autoclaved aerated concrete made from low-grade vanadium titanium iron tailings[J]. Chemical Industry and Engineering Progress, 2017, 36(4): 1482-1490.
29	许林青, 周富涛, 石宗利. 利用磷石膏制备硬石膏水泥的研究[J]. 硅酸盐通报, 2010, 29(1): 102-106.
	XU Linqing, ZHOU Futao, SHI Zongli. Study on manufacture of anhydrite from phosphogypsum[J]. Bulletin of the Chinese Ceramic Society, 2010, 29(1): 102-106.
30	王智, 郑洪伟, 韦迎春. 钙矾石形成与稳定及对材料性能影响的综述[J]. 混凝土, 2001(6): 44-48, 56.
	WANG Zhi, ZHENG Hongwei, WEI Yingchun. Resume of ettringite formation and stabilization and its influences to materials[J]. Concrete, 2001(6): 44-48, 56.

原材料	CaO	MgO	SiO₂	Fe₂O₃	Al₂O₃	SO₃	MnO	f-CaO	其他
钢渣	33.19	8.18	13.96	27.18	5.28	0.33	5.82	4.56	1.50
矿渣	34.15	8.47	41.20	13.66	0.84	1.11	—	—	0.57
β-半水石膏	38.16	0.19	7.45	0.42	1.13	48.41	—	—	4.24
Ⅱ型无水磷石膏	40.06	5.10	9.07	5.09	0.54	40.01	—	—	0.13

原材料	CaO	MgO	SiO₂	Fe₂O₃	Al₂O₃	SO₃	MnO	f-CaO	其他
钢渣	33.19	8.18	13.96	27.18	5.28	0.33	5.82	4.56	1.50
矿渣	34.15	8.47	41.20	13.66	0.84	1.11	—	—	0.57
β-半水石膏	38.16	0.19	7.45	0.42	1.13	48.41	—	—	4.24
Ⅱ型无水磷石膏	40.06	5.10	9.07	5.09	0.54	40.01	—	—	0.13

原材料	标准稠度需水量/%	凝结时间		3天绝干强度		软化系数
原材料	标准稠度需水量/%	初凝/min	终凝/min	抗折强度/MPa	抗压强度/MPa	软化系数
Ⅱ型无水磷石膏	45	744	2457	—	1.0	0.4
β-半水石膏	62	6	8	5.0	13.0	—

原材料	标准稠度需水量/%	凝结时间		3天绝干强度		软化系数
原材料	标准稠度需水量/%	初凝/min	终凝/min	抗折强度/MPa	抗压强度/MPa	软化系数
Ⅱ型无水磷石膏	45	744	2457	—	1.0	0.4
β-半水石膏	62	6	8	5.0	13.0	—

实验因素	因素水平与编码
实验因素	1	2	3	4
A/%	1.5	3	4.5	6
B/%	1	2	4	6
C/%	0.5	1	1.5	3
D/%	1	2	4	6