Effects of chemical admixtures on properties and hydration behaviors of solid waste based cementitious materials

doi:10.16085/j.issn.1000-6613.2024-0327

Abstract

Abstract:

In this study, solid waste based composite cementitious materials were prepared using coal gasification slag, circulating fluidized bed fly ash and cement. Sodium hydroxide (NaOH), sodium sulfate (Na₂SO₄) and sodium carbonate (Na₂CO₃) were selected as chemical admixtures. The effects of single admixture and the NaOH-Na₂SO₄ mixed admixture on the compressive strength, fluidity, setting time and shrinkage of composite cementitious materials were investigated. The hydration mechanism was analyzed using isothermal calorimetry, X-ray diffraction (XRD), simultaneous thermal analysis (TG-DTG) and scanning electron microscopy (SEM). Results showed that the incorporation of all three chemical admixtures could shorten the setting time of the composite cementitious system and reduce the fluidity of the system. The moderate addition of NaOH and the Na₂CO₃ could significantly improve the early strength of the composite cementitious system, the addition of Na₂SO₄ could significantly improve the 28d and 90d strength of the system, and the addition of NaOH-Na₂SO₄ composite admixture could improve the strength of different ages.

Key words: coal gasification slag, circulating fluidized bed fly ash, composite cementitious materials, chemical activator, comprehensive performance, hydration mechanism

摘要：

以煤气化渣、循环流化床粉煤灰和水泥为原料，制备了固废基复合胶凝材料。分别选取氢氧化钠（NaOH）、硫酸钠（Na₂SO₄）和碳酸钠（Na₂CO₃）作为化学外加剂，研究了单一外加剂和NaOH-Na₂SO₄复合外加剂在不同掺量下对复合胶凝材料抗压强度、流动度、凝结时间和收缩行为的影响；利用等温量热、X射线衍射（XRD）、同步热分析（TG）和扫描电子显微镜（SEM）分析了其水化机理。结果表明：3种化学外加剂的掺杂均可缩短复合胶凝体系的凝结时间，并使体系的流动度有所降低。NaOH和Na₂CO₃的适量掺杂可显著提高复合胶凝体系的早期强度，Na₂SO₄的掺杂可明显提高体系的28d和90d强度，NaOH-Na₂SO₄复合外加剂的加入可使不同龄期的强度均有所提高。化学外加剂的掺入可缩短体系的水化诱导期，提高水化反应速率，生成更多钙矾石和C-(A)-S-H凝胶等水化产物，使得基质更为致密，进而提升力学强度。本文研究结果可为固废基复合胶凝材料的性能调控提供理论支撑。

关键词: 煤气化渣, 循环流化床粉煤灰, 复合胶凝材料, 化学外加剂, 综合性能, 水化机理

CLC Number:

TU501

SUN Yajuan, DUAN Siyu, ZHANG Hong, ZHOU Dongdong, LU Guangjun, MA Zhibin. Effects of chemical admixtures on properties and hydration behaviors of solid waste based cementitious materials[J]. Chemical Industry and Engineering Progress, 2025, 44(3): 1739-1748.

孙雅娟, 段思宇, 张宏, 周冬冬, 路广军, 马志斌. 化学外加剂对固废基胶凝材料性能及水化行为的影响[J]. 化工进展, 2025, 44(3): 1739-1748.

Figures/Tables 12

References 29

1	QU Jiangshan, ZHANG Jianbo, LI Huiquan, et al. Occurrence, leaching behavior, and detoxification of heavy metal Cr in coal gasification slag[J]. Chinese Journal of Chemical Engineering, 2023, 58: 11-19.
2	芋艳梅, 刘永明. 固硫灰渣和粉煤灰的特性对比分析[J]. 水泥工程, 2021(4): 8-11.
	YU Yanmei, LIU Yongming. Properties analysis of sulfur-fixing ash and fly ash[J]. Cement Engineering, 2021(4): 8-11.
3	宁美, 王智, 钱觉时, 等. 固硫灰渣的特性及其与现行标准的适应性[J]. 硅酸盐通报, 2019, 38(3): 688-693, 701.
	NING Mei, WANG Zhi, QIAN Jueshi, et al. Characteristics of fluidized bed coal combustion fly ash and slag and its adaptability with current standards[J]. Bulletin of the Chinese Ceramic Society, 2019, 38(3): 688-693, 701.
4	朱菊芬, 李健, 闫龙, 等. 煤气化渣资源化利用研究进展及应用展望[J]. 洁净煤技术, 2021, 27(6): 11-21.
	ZHU Jufen, LI Jian, YAN Long, et al. Research progress and application prospect of coal gasification slag resource utilization[J]. Clean Coal Technology, 2021, 27(6): 11-21.
5	丁玉峰. 粉煤灰的形成过程及其火山灰活性来源分析[J]. 安徽建筑, 2023, 30(5): 103-104.
	DING Yufeng. Formation process of fly ash and analysis of its pozzolanic activity source[J]. Anhui Architecture, 2023, 30(5): 103-104.
6	MA Zhibin, SUN Yajuan, DUAN Siyu, et al. Properties and hydration mechanism of eco-friendly cementitious material prepared using coal gasification slag and circulating fluidized bed fly ash[J]. Construction and Building Materials, 2024, 420: 135581.
7	PROVIS John L, PALOMO Angel, SHI Caijun. Advances in understanding alkali-activated materials[J]. Cement and Concrete Research, 2015, 78: 110-125.
8	蔺喜强, 王栋民, 许晨阳, 等. 硫酸盐类及氯盐类激发剂对粉煤灰活性的影响[J]. 粉煤灰, 2012, 24(1): 4-7.
	LIN Xiqiang, WANG Dongmin, XU Chenyang, et al. The influence of sulfate/chlorine salt activators on activity of fly ash[J]. Coal Ash, 2012, 24(1): 4-7.
9	VELANDIA Diego F, LYNSDALE Cyril J, PROVIS John L, et al. Evaluation of activated high volume fly ash systems using Na₂SO₄, lime and quicklime in mortars with high loss on ignition fly ashes[J]. Construction and Building Materials, 2016, 128: 248-255.
10	杭美艳, 吕学涛, 郭艳梅, 等. 煤气化渣微粉活性激发效果的试验研究[J]. 硅酸盐通报, 2019, 38(3): 878-883, 888.
	HANG Meiyan, Xuetao LYU, GUO Yanmei, et al. Experimental study on activation effect of micropowder of coal gasification slag[J]. Bulletin of the Chinese Ceramic Society, 2019, 38(3): 878-883, 888.
11	刘娟红, 许鹏玉, 周昱程, 等. 改性煤气化渣用于矿山充填的试验研究[J]. 硅酸盐通报, 2020, 39(8): 2528-2535.
	LIU Juanhong, XU Pengyu, ZHOU Yucheng, et al. Experimental study on modified coal gasification slag used for mine filling[J]. Bulletin of the Chinese Ceramic Society, 2020, 39(8): 2528-2535.
12	宋维龙, 朱志铎, 浦少云, 等. 碱激发二元/三元复合工业废渣胶凝材料的力学性能与微观机制[J]. 材料导报, 2020, 34(22): 22070-22077.
	SONG Weilong, ZHU Zhiduo, PU Shaoyun, et al. Mechanical performance and micro-mechanism of alkali-activated binary/ternary composite industrial waste residues cementitious materials[J]. Materials Reports, 2020, 34(22): 22070-22077.
13	权娟娟, 张凯峰, 王可娜. 改性磷石膏对石膏矿渣水泥水化过程的影响研究[J]. 硅酸盐通报, 2017, 36(12): 4033-4037, 4043.
	QUAN Juanjuan, ZHANG Kaifeng, WANG Kena. Effect of modified phosphogypsum on the hydration process of gypsum slag cement[J]. Bulletin of the Chinese Ceramic Society, 2017, 36(12): 4033-4037, 4043.
14	ETCHEVERRY Juan Manuel, VILLAGRAN-ZACCARDI Yury Andres, VAN DEN HEEDE Philip, et al. Effect of sodium sulfate activation on the early age behaviour and microstructure development of hybrid cementitious systems containing Portland cement, and blast furnace slag[J]. Cement and Concrete Composites, 2023, 141: 105101.
15	黄科, 马玉玮, 郭奕群, 等. 碱激发粉煤灰/矿渣复合体系的性能研究[J]. 硅酸盐通报, 2015, 34(10): 2769-2774.
	HUANG Ke, MA Yuwei, GUO Yiqun, et al. Properties of alkali-activated fly ash/slag composite system[J]. Bulletin of the Chinese Ceramic Society, 2015, 34(10): 2769-2774.
16	LEE N K, JANG J G, LEE H K. Shrinkage characteristics of alkali-activated fly ash/slag paste and mortar at early ages[J]. Cement and Concrete Composites, 2014, 53: 239-248.
17	AVET François, SCRIVENER Karen. Investigation of the calcined kaolinite content on the hydration of limestone calcined clay cement (LC3)[J]. Cement and Concrete Research, 2018, 107: 124-135.
18	殷素红, 管海宇, 胡捷, 等. 碱激发粉煤灰-矿渣灌浆材料的流变性与流动性[J]. 华南理工大学学报(自然科学版), 2019, 47(8): 120-128, 135.
	YIN Suhong, GUAN Haiyu, HU Jie, et al. Rheological properties and fluidity of alkali-activated fly ash-slag grouting material[J]. Journal of South China University of Technology (Natural Science Edition), 2019, 47(8): 120-128, 135.
19	阎培渝, 张增起. 复合胶凝材料的水化硬化机理[J]. 硅酸盐学报, 2017, 45(8): 1066-1072.
	YAN Peiyu, ZHANG Zengqi. Review on hydration of composite cementitious materials[J]. Journal of the Chinese Ceramic Society, 2017, 45(8): 1066-1072.
20	刘卓, 赵志曼, 吴磊, 等. 磷石膏-脱硫石膏复合相石膏胶凝材料性能研究[J]. 非金属矿, 2020, 43(6): 46-48.
	LIU Zhuo, ZHAO Zhiman, WU Lei, et al. Study on properties of phosphogypsum-desulfurization gypsum composite gypsum cementitious material[J]. Non-Metallic Mines, 2020, 43(6): 46-48.
21	彭饶, 陈伟, 李秋, 等. 硫酸钠激发尾矿充填材料的性能与微观结构[J]. 建筑材料学报, 2020, 23(3): 685-691.
	PENG Rao, CHEN Wei, LI Qiu, et al. Properties and microstructure of cemented paste tailings activated by sodium sulfate[J]. Journal of Building Materials, 2020, 23(3): 685-691.
22	TAN Hongbo, DENG Xiufeng, HE Xingyang, et al. Compressive strength and hydration process of wet-grinded granulated blast-furnace slag activated by sodium sulfate and sodium carbonate[J]. Cement and Concrete Composites, 2019, 97: 387-398.
23	BALLEKERE KUMARAPPA Darshan, PEETHAMPARAN Sulapha, NGAMI Margueritte. Autogenous shrinkage of alkali activated slag mortars: Basic mechanisms and mitigation methods[J]. Cement and Concrete Research, 2018, 109: 1-9.
24	KISHAR Essam A. Hydration reaction of tricalciumaluminate in different systems[J]. Cement and Concrete Research, 2005, 35(8): 1638-1640.
25	WU Linmei, FARZADNIA Nima, SHI Caijun, et al. Autogenous shrinkage of high performance concrete: A review[J]. Construction and Building Materials, 2017, 149: 62-75.
26	席雅允, 沈玉, 刘娟红, 等. 化学激发对煤气化渣-水泥体系抗压强度影响机理研究[J]. 材料导报, 2021, 35(S2): 262-267, 274.
	XI Yayun, SHEN Yu, LIU Juanhong, et al. Study on the mechanism of chemical excitation on compressive strength of coal gasification slag-cement system[J]. Materials Reports, 2021, 35(S2): 262-267, 274.
27	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.
28	BILLONG Ndigui, Jonathan OTI, KINUTHIA John. Using silica fume based activator in sustainable geopolymer binder for building application[J]. Construction and Building Materials, 2021, 275: 122177.
29	刘守庆, 罗中秋, 和森, 等. 高炉矿渣-粉煤灰地聚合物胶凝材料固化砷钙渣[J]. 化工进展, 2017, 36(7): 2660-2666.
	LIU Shouqing, LUO Zhongqiu, HE Sen, et al. Solidification/stabilization of calcium arsenate waste with blast furnace slag and fly ash geopolymer materials[J]. Chemical Industry and Engineering Progress, 2017, 36(7): 2660-2666.

原料	SiO₂/%	Al₂O₃/%	CaO/%	SO₃/%	Fe₂O₃/%	Na₂O/%	MgO/%	K₂O/%	烧失量/%
CGS	46.78	25.25	14.66	0.35	8.12	0.61	0.61	1.38	5.40
CFBFA	32.28	23.55	21.47	11.90	6.65	0.35	0.53	0.86	6.89
OPC	20.70	7.72	55.30	2.37	3.45	0.33	2.74	0.64	2.69

原料	SiO₂/%	Al₂O₃/%	CaO/%	SO₃/%	Fe₂O₃/%	Na₂O/%	MgO/%	K₂O/%	烧失量/%
CGS	46.78	25.25	14.66	0.35	8.12	0.61	0.61	1.38	5.40
CFBFA	32.28	23.55	21.47	11.90	6.65	0.35	0.53	0.86	6.89
OPC	20.70	7.72	55.30	2.37	3.45	0.33	2.74	0.64	2.69

样品简称	CGS/%	CFBFA/%	OPC/%	化学外加剂			W/B
样品简称	CGS/%	CFBFA/%	OPC/%	NaOH/%	Na₂SO₄/%	Na₂CO₃/%	W/B
对照组	—	—	—	—	—	—	—
CSF-1NH	—	—	—	1	—	—	—
CSF-3NH	—	—	—	3	—	—	—
CSF-5NH	—	—	—	5	—	—	—
CSF-1NS	—	—	—	—	1	—	—
CSF-3NS	—	—	—	—	3	—	—
CSF-5NS	40	20	40	—	5	—	0.5
CSF-1NC	—	—	—	—	—	1	—
CSF-3NC	—	—	—	—	—	3	—
CSF-5NC	—	—	—	—	—	5	—
CSF-2NH2NS	—	—	—	2	2	—	—
CSF-3NH1NS	—	—	—	3	1	—	—
CSF-3NH3NS	—	—	—	3	3	—	—

样品简称	CGS/%	CFBFA/%	OPC/%	化学外加剂			W/B
样品简称	CGS/%	CFBFA/%	OPC/%	NaOH/%	Na₂SO₄/%	Na₂CO₃/%	W/B
对照组	—	—	—	—	—	—	—
CSF-1NH	—	—	—	1	—	—	—
CSF-3NH	—	—	—	3	—	—	—
CSF-5NH	—	—	—	5	—	—	—
CSF-1NS	—	—	—	—	1	—	—
CSF-3NS	—	—	—	—	3	—	—
CSF-5NS	40	20	40	—	5	—	0.5
CSF-1NC	—	—	—	—	—	1	—
CSF-3NC	—	—	—	—	—	3	—
CSF-5NC	—	—	—	—	—	5	—
CSF-2NH2NS	—	—	—	2	2	—	—
CSF-3NH1NS	—	—	—	3	1	—	—
CSF-3NH3NS	—	—	—	3	3	—	—

养护龄期	温度范围	样品结合水失重率/%
养护龄期	温度范围	对照组	CSF-5NS	CSF-5NC	CSF-3NH	CSF-2NH2NS
28d	室温~414℃	8.16	10.41	9.66	9.74	10.87
	414~470℃	1.56	0.82	0.92	0.86	0.75
	470~700℃	5.08	5.08	5.72	5.41	5.21
	室温~700℃	14.80	16.31	16.30	16.01	16.83
90d	室温~414℃	9.55	12.53	10.15	9.78	11.50
	414~470℃	1.25	0.88	0.94	0.96	0.91
	470~700℃	4.11	4.66	4.69	4.69	4.75
	室温~700℃	14.91	18.07	15.78	15.43	17.16