基于煤基腐殖酸的高效减水剂合成与性能表征

doi:10.16085/j.issn.1000-6613.2022-1552

摘要/Abstract

摘要：

为了探索褐煤高值化利用途径，利用2-丙烯酰胺-2-甲基丙烷磺酸钠（AMPS）和丙烯酸（AA）分别对褐煤氧化解聚腐殖酸（OHA）和商品化腐殖酸（NHA）进行接枝共聚改性，制备了两种煤基腐殖酸（CHA）高效减水剂，考察了接枝共聚物结构及其单体配比对水泥砂浆和净浆流动度的影响，结合接枝共聚物结构表征对两种CHA高效减水剂的吸附性能及砂浆流动性、减水率、坍落度和机械强度等应用性能进行了评价，并与商品减水剂FDN-C进行了对比。结果显示，AMPS与AA接枝共聚改性可以显著提高CHA的水泥浆体流动性和减水率。其中，AA/AMPS=0.15时，接枝共聚物的改性效果最好；OHA接枝共聚改性效果优于NHA。OHA和NHA接枝共聚物的混凝土减水率分别达到24%和22%，28d抗压强度分别提升31.7%和40.0%，并且保坍能力明显高于FDN-C。CHA的芳香度高及含有丰富的酚羟基和羧基，有利于AMPS和AA接枝共聚反应，可以作为石油替代品用于制备水泥等材料的高效分散剂。

关键词: 褐煤, 氧化, 腐殖酸, 高效减水剂, 合成, 分散, 吸附

Abstract:

In order to develop the pathway of high value utilization of lignite, two coal-based humic acid (CHA) superplasticizers were prepared by grafting copolymerization of oxidative depolymerized humic acid of lignite (OHA) and commercial humic acid (NHA) with 2-acrylamide-2-methylpropane sulfonate (AMPS) and acrylic acid (AA), respectively. The effects of the structure and monomer ratio of graft copolymers on the fluidity of cement mortar and slurry were investigated. Combined with the structure characterization, the adsorption performance and the application properties of two synthesized CHA superplasticizers such as mortar fluidity, water-reducing rate, slump and mechanical strength were evaluated, and were further compared with commercial superplasticizer FDN-C. The results showed that the graft copolymerization by AMPS and AA on CHA can significantly improve the fluidity and water-reducing rate of cement paste. With 0.15 of AA/AMPS monomer mole ratio, the best modification effect of graft copolymer was obtained. The modification of OHA graft copolymer was better than that of NHA. The concrete water-reducing rates of OHA and NHA graft copolymers reached 24% and 22%, and their 28-day compressive strength were increased by 31.7% and 40.0%, respectively. Besides, the slump retention ability of OHA and NHA copolymers were significantly higher than that of commercial water-reducer FDN-C. CHA with high aromaticity and abundant oxygen-containing functional groups such as phenolic hydroxyl group and carboxyl group was beneficial to the graft copolymerization of AMPS and AA, and can be used as a substitute for petroleum to prepare the efficient dispersant.

Key words: lignite, oxidation, humic acid, superplasticizer, synthesis, dispersion, adsorption

中图分类号:

TQ536

王知彩, 刘伟伟, 周璁, 潘春秀, 闫洪雷, 李占库, 颜井冲, 任世彪, 雷智平, 水恒福. 基于煤基腐殖酸的高效减水剂合成与性能表征[J]. 化工进展, 2023, 42(7): 3634-3642.

WANG Zhicai, LIU Weiwei, ZHOU Cong, PAN Chunxiu, YAN Honglei, LI Zhanku, YAN Jingchong, REN Shibiao, LEI Zhiping, SHUI Hengfu. Synthesis and performance of a superplasticizer based on coal-based humic acid[J]. Chemical Industry and Engineering Progress, 2023, 42(7): 3634-3642.

图/表 13

表1 OHA与NHA的元素分析（质量分数） (%)

原料	C	H	O^①	N	S	H/C	O/C
OHA	58.46	2.49	36.13	2.37	0.55	0.51	0.46
NHA	52.61	2.54	41.82	1.46	1.57	0.58	0.60

表2 水泥化学组成（质量分数） (%)

SiO₂	Al₂O₃	CaO	Fe₂O₃	MgO	SO₃	K₂O	Na₂O	TiO₂	P₂O₅	LOSS
26.01	10.81	49.81	3.70	3.64	2.87	1.07	0.69	0.68	0.25	0.47

图1 OHA结构及其接枝共聚反应

图2 NHA和OHA及其合成产物的水泥浆体流动度与胶砂减水率

图3 单体AA/ATBS摩尔比对水泥浆体流动度和胶砂减水率的影响

图4 OHA、NHA及其不同接枝共聚减水剂红外光谱

表3 OHA、AcA′及OgAcA′的平均分子量及分布（GPC法）

样品	数均分子量（M_n） /g·mol^-1	重均分子量（M_w） /g·mol^-1	分散系数（PDI）
OHA	725	985	1.35
OgA	720	1430	1.99
AcA′	32507（1143）	105938（1518）	3.26（1.33）
OgAcA′	43350（1228）	95335（1528）	2.20（1.24）

图5 OHA及聚合物凝胶色谱

图6 掺入AcA′、NgAcA′及OgAcA′后水泥表面zeta电位和吸附量

图7 添加聚合物的胶砂经时流动度

图8 不同减水剂对混凝土性能的影响

图9 添加聚合物对胶砂强度的影响

图10 硬化3d胶砂SEM图

参考文献 32

1	张传祥, 张效铭, 程敢. 褐煤腐植酸提取技术及应用研究进展[J]. 洁净煤技术, 2018, 24(1): 6-12.
	ZHANG Chuanxiang, ZHANG Xiaoming, CHENG Gan. Research progress on extraction technology and application of lignite humic acid[J]. Clean Coal Technology, 2018, 24(1): 6-12.
2	程亮, 侯翠红, 徐丽, 等. 纳米腐殖酸动态吸附废水中镉离子及其洗脱特性[J]. 化工学报, 2016, 67(4): 1348-1356.
	CHENG Liang, HOU Cuihong, XU Li, et al. Dynamic adsorption and de-sorption characteristics of wastewater containing cadmium ion on nanoscale humic acid[J]. CIESC Journal, 2016, 67(4): 1348-1356.
3	隋明炜, 沈一丁, 赖小娟, 等. 腐植酸系水煤浆分散剂的合成表征及应用[J]. 煤炭科学技术, 2017, 45(10): 209-212.
	SUI Mingwei, SHEN Yiding, LAI Xiaojuan, et al. Synthesis characters and application of humic acid base dispersant applied to coal water mixture[J]. Coal Science and Technology, 2017, 45(10): 209-212.
4	司东永, 黄光许, 张传祥, 等. 腐殖酸基石墨化材料的制备及其电化学性能[J]. 材料导报, 2018, 32(3): 368-372.
	SI Dongyong, HUANG Guangxu, ZHANG Chuanxiang, et al. Preparation and electrochemical performance of humic acid-based graphitized materials[J]. Materials Review, 2018, 32(3): 368-372.
5	郭雅妮, 李金成, 惠璠, 等. 超声辅助法制备风化煤腐植酸-丙烯酸吸水树脂[J]. 功能材料, 2020, 51(4): 4164-4169.
	GUO Yani, LI Jincheng, HUI Fan, et al. Preparation of humic acid-acrylic acid absorbent resin from weathered coal by ultrasonic-assisted method[J]. Journal of Functional Materials, 2020, 51(4): 4164-4169.
6	FRANKE N W, KIEBLER M W, RUOF C H, et al. Water-soluble polycarboxylic acids by oxidation of coal[J]. Industrial & Engineering Chemistry, 1952, 44(11): 2784-2792.
7	WANG Wenhua, HOU Yucui, WU Weize, et al. Simultaneous production of small-molecule fatty acids and benzene polycarboxylic acids from lignite by alkali-oxygen oxidation[J]. Fuel Processing Technology, 2013, 112: 7-11.
8	LIU Fangjing, WEI Xianyong, ZHU Ying, et al. Oxidation of Shengli lignite with aqueous sodium hypochlorite promoted by pretreatment with aqueous hydrogen peroxide[J]. Fuel, 2013, 111: 211-215.
9	DOSKOČIL L, GRASSET L, VÁLKOVÁ D, et al. Hydrogen peroxide oxidation of humic acids and lignite[J]. Fuel, 2014, 134: 406-413.
10	GONG Lijiao, HOU Yucui, WU Weize, et al. Catalytic O₂ oxidation of lignite to carboxylic acids with iron-based catalysts in acidic aqueous solutions[J]. Fuel Processing Technology, 2019, 191: 54-59.
11	MIURA K, MAE K, OKUTSU H, et al. New oxidative degradation method for producing fatty acids in high yields and high selectivity from low-rank coals[J]. Energy & Fuels, 1996, 10(6): 1196-1201.
12	WANG Zhicai, WU Tao, WU Zequan, et al. A low carbon footprint method for converting low-rank coals to oxygen-containing chemicals[J]. Fuel, 2022, 315: 123277.
13	WANG Z C, WU Z Q, WANG Q, et al. Efficient oxidative depolymerization of Xilinguole lignite to produce humic acids with little CO₂ production[J]. Solid Fuel Chemistry, 2021, 55(5): 348-356.
14	WU Zequan, WANG Zhicai, WU Tao, et al. Boosting conversion efficiency of lignite to oxygen-containing chemicals by thermal extraction and subsequent oxidative depolymerization[J]. Fuel, 2022, 308: 122043.
15	莫祥银, 景颖杰, 邓敏, 等. 聚羧酸盐系高性能减水剂研究进展及评述[J]. 混凝土, 2009(3): 60-63.
	MO Xiangyin, JING Yingjie, DENG Min, et al. New research progress and summarization of polycarboxylate-type high performance superplasticizer[J]. Concrete, 2009(3): 60-63.
16	马正先, 宋沛霖, 周在波, 等. 新型高保坍降黏型聚羧酸减水剂制备及性能评价[J]. 硅酸盐通报, 2018, 37(11): 3386-3391.
	MA Zhengxian, SONG Peilin, ZHOU Zaibo, et al. Preparation and performance evaluation of new high slump reducing viscosity polycarboxylate superplasticizer[J]. Bulletin of the Chinese Ceramic Society, 2018, 37(11): 3386-3391.
17	高瑞军, 吕生华. 聚羧酸系减水剂的构性关系及其作用机理研究[J]. 材料导报, 2012, 26(3): 57-60.
	GAO Ruijun, Shenghua LYU. Study on the structure and performances and acting mechanisms of polycarboaylate-type superplasticizers[J]. Materials Review, 2012, 26(3): 57-60.
18	LEI Lei, PALACIOS M, PLANK J, et al. Interaction between polycarboxylate superplasticizers and non-calcined clays and calcined clays: A review[J]. Cement and Concrete Research, 2022, 154: 106717.
19	LIN Xiuju, PANG Hao, WEI Daidong, et al. Effect of superplasticizers with different anchor groups on the properties of cementitious systems[J]. Colloids and Surfaces A: Physicochemical and Engineering Aspects, 2021, 630: 127207.
20	ZHANG Tailong, GAO Jianming, DENG Xuan, et al. Graft copolymerization of black liquor and sulfonated acetone formaldehyde and research on concrete performance[J]. Construction and Building Materials, 2015, 83: 308-313.
21	CRÉPY L, PETIT J Y, WIRQUIN E, et al. Synthesis and evaluation of starch-based polymers as potential dispersants in cement pastes and self leveling compounds[J]. Cement and Concrete Composites, 2014, 45: 29-38.
22	陈宝璠. 水溶液中共聚合成MPEGAA-AA-AMPS聚羧酸高效减水剂及其性能[J]. 化工进展, 2013, 32(4): 898-904.
	CHEN Baofan. Synthesis and performance of superplasticizer of MPEGAA-AA-AMPS by free radical copolymerization in aqueous solution[J]. Chemical Industry and Engineering Progress, 2013, 32(4): 898-904.
23	李悦, 赵冰垠, 黄舟, 等. 抗泥型聚羧酸减水剂的研究进展[J]. 混凝土, 2020(11): 48-51.
	LI Yue, ZHAO Bingyin, HUANG Zhou, et al. Research status of anti-mud polycarboxylate superplasticizer[J]. Concrete, 2020(11): 48-51.
24	朱红姣, 张光华, 何志琴, 等. 抗泥型聚羧酸减水剂的制备及性能[J]. 化工进展, 2016, 35(9): 2920-2925.
	ZHU Hongjiao, ZHANG Guanghua, HE Zhiqin, et al. Preparation and properties of polycarboxylic superplasticizer with high tolerance to clay[J]. Chemical Industry and Engineering Progress, 2016, 35(9): 2920-2925.
25	李艳红, 庄锐, 张政, 等. 褐煤腐植酸的结构、组成及性质的研究进展[J]. 化工进展, 2015, 34(8): 3147-3157.
	LI Yanhong, ZHUANG Rui, ZHANG Zheng, et al. Research on the structure, chemical composition and characterization of humic acid from lignite[J]. Chemical Industry and Engineering Progress, 2015, 34(8): 3147-3157.
26	BEDDAA H, FRAJ A B, LAVERGNE F, et al. Effect of potassium humate as humic substances from river sediments on the rheology, the hydration and the strength development of a cement paste[J]. Cement and Concrete Composites, 2019, 104: 103400.
27	OZUZUN S, UZAL B. Performance of leonardite humic acid as a novel superplasticizer in Portland cement systems[J]. Journal of Building Engineering, 2021, 42: 103070.
28	ILG M, PLANK J. A novel kind of concrete superplasticizer based on lignite graft copolymers[J]. Cement and Concrete Research, 2016, 79: 123-130.
29	张光华, 刘龙, 李俊国, 等. 磺化腐植酸接枝改性共聚物合成及性能研究[J]. 煤炭转化, 2013, 36(2): 92-96.
	ZHANG Guanghua, LIU Long, LI Junguo, et al. Synthesis and properties research of sulfonated humic acid grafted copolymer[J]. Coal Conversion, 2013, 36(2): 92-96.
30	CHANG Xiaofeng, SUN Jinsheng, XU Zhe, et al. Synthesis of a novel environment-friendly filtration reducer and its application in water-based drilling fluids[J]. Colloids and Surfaces A: Physicochemical and Engineering Aspects, 2019, 568: 284-293.
31	WATANABE K, NISHIDA I, IMAI H. Dispersion of hydroxyapatite nanocrystals stabilized by polymeric molecules bearing carboxy and sulfo groups[J]. Colloid and Polymer Science, 2017, 295(9): 1491-1498.
32	王秀梅, 杨勇, 舒鑫, 等. 聚羧酸减水剂在水泥颗粒表面的吸附行为研究[J]. 新型建筑材料, 2017, 44(11): 13-16.
	WANG Xiumei, YANG Yong, SHU Xin, et al. Adsorption behavior of polycarboxylate superplascticizer on cement particle surfaces[J]. New Building Materials, 2017, 44(11): 13-16.

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