H2SO4-H2O中硝酸铜对脱硫石膏晶须生长的影响

汪潇; 马晓晓; 金彪; 张小婷; 张建武; 杨留栓; 王宇斌

人工晶体学报, 2021, 50 (12): 2316, 网络出版: 2022-02-15

H₂SO₄-H₂O中硝酸铜对脱硫石膏晶须生长的影响

Influence of Cu(NO₃)₂ in H₂SO₄-H₂O on the Growth of Desulfurized Gypsum Whiskers

论文大纲

汪潇 ^1,*马晓晓 ²金彪 ¹张小婷 ¹张建武 ¹杨留栓 ¹王宇斌 ²

作者单位

¹ 河南城建学院材料与化工学院, 平顶山 467036

² 西安建筑科技大学资源工程学院, 西安 710055

脱硫石膏硝酸铜晶须 H2SO4-H2O体系结晶影响机制 desulfurized gypsum Cu(NO3)2 whisker H2SO4-H2O system crystallization influence mechanism

摘要

以处理后的脱硫石膏为原料, 在H2SO4-H2O体系中以Cu(NO3)2为晶形控制剂采用水热法制备脱硫石膏晶须, 探讨了Cu(NO3)2对脱硫石膏晶须生长的影响机理。结果表明: Cu(NO3)2对脱硫石膏有明显促溶作用, 其中Cu2+可减小溶液中各离子的活度系数, 使溶液中的Ca2+浓度增大。NO-3通过静电作用在Ca2+周围聚集并对SO2-4产生屏蔽作用, 导致脱硫石膏继续溶解并使Ca2+和SO2-4的浓度处于相对稳定状态, 有利于半水脱硫石膏晶体的形核与生长。此外, Cu2+还可在晶须的生长过程中选择性吸附在晶须表面, 生成CuSO4, 促进了脱硫石膏的结晶生长, 最终在Cu(NO3)2用量为2.0%(质量分数)时制备的脱硫石膏晶须长径比约为73。

Abstract

Desulfurized gypsum whiskers were prepared by hydrothermal method using treated desulfurized gypsum as raw materials, and Cu(NO3)2 was used as the crystal form control agent in the H2SO4-H2O system. The influence mechanism of Cu(NO3)2 on the growth of desulfurized gypsum whiskers was discussed. The results show that Cu(NO3)2 has obvious dissolution-promoting effect on desulfurized gypsum, and Cu2+ could reduce the activity coefficient of each ion in the solution and increase the concentration of Ca2+ in the solution. Moreover, NO-3 accumulate around Ca2+ and shield SO2-4 through electrostatic action, which cause the desulfurized gypsum dissolve continuously and keep the concentration of Ca2+ and SO2-4 in a relatively stable state, and facilitate the nucleation and growth of hemihydrate desulfurized gypsum crystals. In addition, Cu2+ selectively adsorb on the surface of the whiskers to generate CuSO4 during the growth of the whiskers, thereby improve the crystal growth of desulfurized gypsum whiskers. When the amount of Cu(NO3)2 is 2.0% (mass fraction), desulfurized gypsum whiskers with an aspect ratio of about 73 are prepared.

参考文献

[1] 李强,刘福立,尚超,等.微波外场强化电石渣制备硫酸钙晶须及其机理分析［J］.人工晶体学报,2020,49(1): 125-130.

[2] LIU C J, ZHAO Q, WANG Y G, et al. Surface modification of calcium sulfate whisker prepared from flue gas desulfurization gypsum［J］. Applied Surface Science, 2016, 360: 263-269.

[3] FENG X, ZHANG Y, WANG G L, et al. Dual-surface modification of calcium sulfate whisker with sodium hexametaphosphate/silica and use as new water-resistant reinforcing fillers in papermaking［J］. Powder Technology, 2015, 271: 1-6.

[4] 李强,刘福立,尚超,等.脱硫石膏制备硫酸钙晶须结晶动力学研究［J］.人工晶体学报,2018,47(11): 2305-2310.

[5] WANG X, JIN B, YANG L S, et al. Effect of CuCl2on hydrothermal crystallization of calcium sulfate whiskers prepared from FGD gypsum［J］. Crystal Research and Technology, 2015, 50(8): 633-640.

[6] 马文静,陈学青,郜丽丽,等.脱硫石膏制备γ-CaSO4晶须及Ⅱ-CaSO4晶须［J］.高校化学工程学报,2021,35(3): 520-528.

[7] 唐明亮,沈晓冬,黄金龙.晶习改变剂对α-CaSO4·0.5H2O晶体形貌的作用机理［J］.建筑材料学报,2014,17(2): 280-283+308.

[8] 张巨松,郑万荣,陈华,等.影响α半水石膏粒度、形貌及强度的因素［J］.沈阳建筑大学学报(自然科学版),2006,22(6): 930-934.

[9] 方羊.水热法制备半水硫酸钙晶须及其长径比的可控研究［D］.合肥: 合肥工业大学,2017.

[10] 陈平,田宇,胡成.盐溶液种类和浓度对α-半水脱硫石膏合成的影响［J］.无机盐工业,2020,52(10): 130-134.

[11] GUAN Q J, SUN W, HU Y H, et al. A facile method of transforming FGD gypsum to α-CaSO4·0.5H2O whiskers with cetyltrimethylammonium bromide (CTAB) and KCl in glycerol-water solution［J］. Scientific Reports, 2017, 7: 7085.

[12] 汪潇,杨留栓,朱新峰,等.K2SO4/KCl添加剂对脱硫石膏晶须结晶的影响［J］.人工晶体学报,2013,42(12): 2661-2668.

[13] 李强,尚超,石棕文,等.金属离子对硫酸钙晶须形貌影响的试验研究［J］.非金属矿,2019,42(1): 94-96.

[14] RABIZADEH T, STAWSKI T M, MORGAN D J, et al. The effects of inorganic additives on the nucleation and growth kinetics of calcium sulfate dihydrate crystals［J］. Crystal Growth & Design, 2017, 17(2): 582-589.

[15] ZHANG X T, WANG X, JIN B, et al. Crystal structure formation of hemihydrate calcium sulfate whiskers (HH-CSWs) prepared using FGD gypsum［J］. Polyhedron, 2019, 173: 114140.

[16] 汪潇,金彪,张小婷,等.MgSO4/MgCl2对脱硫石膏溶解度及其晶须结晶的影响［J］.河南科技大学学报(自然科学版),2018,39(2): 6-10+24+4.

[17] ZHENG X X, JING H J, FENG J Q, et al. Study on the solubility and morphology of calcium sulfate dihydrate in nitric acid and phosphoric acid aqueous medium［C］//2010 International Conference on Mechanic Automation and Control Engineering. June 26-28, 2010, Wuhan, China. IEEE, 2010: 3931-3934.

[18] 徐春华,李英峰,胡松青.硝酸钾电解质溶液的结构和热力学性质的计算机分子模拟［J］.中国石油大学学报(自然科学版),2006,30(2): 101-105+132.

[19] 汪潇,金彪,王宇斌,等.阴离子在脱硫石膏晶须水热结晶中的作用机理［J］.高等学校化学学报,2020,41(3): 473-480.

[20] YANG L S, WANG X, ZHU X F, et al. Preparation of calcium sulfate whisker by hydrothermal method from flue gas desulfurization (FGD) gypsum［J］. Applied Mechanics and Materials, 2012, 268/269/270: 823-826.

[21] FELDMANN T, DEMOPOULOS G P. Influence of impurities on crystallization kinetics of calcium sulfate dihydrate and hemihydrate in strong HCl-CaCl2 solutions［J］. Industrial & Engineering Chemistry Research, 2013, 52(19): 6540-6549.

[22] DONG F Q, HUANG Z Y, TAN H B, et al. Effect of additives on calcium sulfate hemihydrate whiskers morphology from calcium sulfate dehydrate and phosphogypsum［J］. Materials and Manufacturing Processes, 2016, 31(15): 2037-2043.

汪潇, 马晓晓, 金彪, 张小婷, 张建武, 杨留栓, 王宇斌. H₂SO₄-H₂O中硝酸铜对脱硫石膏晶须生长的影响[J]. 人工晶体学报, 2021, 50(12): 2316. WANG Xiao, MA Xiaoxiao, JIN Biao, ZHANG Xiaoting, ZHANG Jianwu, YANG Liushuan, WANG Yubin. Influence of Cu(NO₃)₂ in H₂SO₄-H₂O on the Growth of Desulfurized Gypsum Whiskers[J]. Journal of Synthetic Crystals, 2021, 50(12): 2316.

H₂SO₄-H₂O中硝酸铜对脱硫石膏晶须生长的影响

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