Preparation of solid biopolymerized ferric sulfate and its flocculation performance

doi:10.16085/j.issn.1000-6613.2018-1503

Abstract

Abstract:

Industrial by-product ferrous sulfate heptahydrate (FeSO₄·7H₂O) was used to prepare bio-polymeric ferric sulfate (BPFS). Solid bio-polymeric ferric sulfate (SBPFS) was produced by decompression evaporation, which was applied to the removal of the water of Songhua River. The study included the curing temperature, the curing time and the determination of additives. The structures of the SBPFS were definitely characterized by scanning electron microscopy (SEM), infrared X-ray diffraction (XRD), spectroscopy (FTIR), and X-ray photoelectron spectroscopy (XPS). The results demonstrated that the flocculating agent had strong flocculation when the curing temperature was 55℃, the curing time was 4h, and the additive was KAl(SO₄)₂. The morphology of the SBPFS was observed with a scanning electron microscope, which showed that the material was bulky and the specific surface area was large; SBPFS was observed with X-ray diffraction which showed that the product was amorphous, and the solid powder particles had no specific shapes and structures; the structure and the main component of the SBPFS were demonstrated by spectroscopy and X-ray photoelectron spectroscopy. When the prepared BPFS and SBPFS were used to dispose Songhua River water, thee removal rate of turbidity and COD_Mn of SBPFS to Songhua River water was slightly better than that of BPFS. The removal efficiencies of turbidity and COD_Mn by SBPFS could reach 96% and 80%, respectively.

Key words: polymeric ferric sulfate, preparation, ceramic raschig ring, decompression evaporation, curing

摘要：

以工业FeSO₄·7H₂O为原料，制备生物聚合硫酸铁（bio-polymeric ferric sulfate，BPFS），采用减压蒸发技术制备固体生物聚合硫酸铁（solid bio-polymeric ferric sulfate，SBPFS），以松花江水为处理对象研究其絮凝性。研究内容包括固化温度、固化时间和添加剂的确定，通过扫描电子显微镜（SEM）、X射线衍射（XRD）、红外光谱分析（FTIR）和X射线光电子能谱分析（XPS）对其结构进行表征。研究结果表明：当固化温度55℃、固化时间4h、添加剂为KAl(SO₄)₂时，絮凝剂的絮凝性强。SEM表明产物质地膨松、比表面积大；XRD表明产物属于非晶态物质，固体粉末颗粒没有特定的形状和结构；FTIR表明了产物的结构；XPS表明产品的主要成分。将制备的BPFS和SBPFS用于处理松花江水时，SBPFS对松花江水浊度和COD_Mn的去除率略优于BPFS，除浊率和COD_Mn去除率分别可达96%和80%以上，絮凝效果佳。

关键词: 聚合硫酸铁, 制备, 陶瓷拉西环, 减压蒸发, 固化

CLC Number:

X703.1

Xiaohui XU, Min LU, Liu YANG, Yue WANG, Yaqi LIU, Xiaohui GUAN. Preparation of solid biopolymerized ferric sulfate and its flocculation performance[J]. Chemical Industry and Engineering Progress, 2019, 38(05): 2434-2440.

徐小惠, 鲁敏, 杨柳, 王悦, 刘雅琪, 关晓辉. 固体生物聚合硫酸铁的制备及其絮凝性能[J]. 化工进展, 2019, 38(05): 2434-2440.

Figures/Tables 13

References 35

1	刘维, 吴冰, 曹江林, 等. 钛对聚合硫酸铁制备与性能的影响[J]. 环境化学, 2012, 31(4): 437-442
	LIUWei, WUBing, CAOJianglin, et al． Effect of titanium on the preparation and coagulation efficiency of polyferric sulphate[J]. Environmental Chemistry, 2012, 31(4): 437-442.
2	万俐, 赵君凤, 付永胜, 等. 不同絮凝剂对活性污泥特性及除污效能的影响研究[J]. 环境工程, 2017, 35(2): 49-52.
	WANLi, ZHAOJunfeng, FUYongsheng, et al. Effect of flocculants on sludge characteristics and pollutant removal efficiency[J]. Environmental Engineering, 2017, 35(2): 49-52.
3	WANGH M, MINX B, CHAIL Y, et al. Biological preparation and application of poly-ferric sulfate flocculant[J]. Transactions of Nonferrous Metals Society of China, 2011, 21(11): 2542-2547.
4	关晓辉, 王立刚, 鲁敏, 等. 基于生物催化氧化技术的生物聚合硫酸铁制备及性能研究综述[J]. 东北电力大学学报, 2013, 33(4): 15-18.
	GUANXiaohui, WANGLigang, LUMin, et al. Progress in the preparation and properties of bio-polymeric ferric sulfate based on the bio-catalysis and oxidation technology[J]. Journal of Northeast Dianli University, 2013, 33(4): 15-18.
5	喻文超, 郭亚丹, 陈锦全, 等. 生物聚合硫酸铁絮凝剂去除废水中氟氯的实验研究[J]. 科学技术与工程, 2017,17(34): 166-173.
	YUWenchao, GUOYadan, CHENJinquan, et al. Experimental investigation for removal of fluoride and chloride from waste water with bio-polymeric ferric sulphate[J]. Science Technology and Engineering, 2017,17(34): 166-173.
6	周云, 刘英, 张志强, 等. 微生物絮凝剂制备的研究新进展[J]. 环境污染与防治, 2014, 36(4): 80-85.
	ZHOUYun,LIUYing, ZHANGZhiqiang,et al.Recent research progress on the preparation of microbial flocculcants[J].Environmental pollution & Control,2014,36(4):80-85.
7	皮姗姗, 李昂, 魏薇, 等. 微生物絮凝剂在水污染控制中的应用研究进展[J]. 中国给水排水, 2017, 33(16): 27-31.
	PIShanshan, LIAng, WEIWei, et al. Research progress on application of microbial flocculants in water pollution control[J]. China Water & Wastewater , 2017, 33(16): 27-31.
8	叶有权, 贺晶晶, 吕向红. 固体钙铁复合絮凝剂的制备及应用研究[J]. 水处理技术, 2012, 38(4): 58-61.
	YEYouquan, HEJingjing, XianghongLÜ. Experimental research on the preparation and application of Ca-Fe composite flocculant[J]. Technology of Water Treatment, 2012, 38(4): 58-61.
9	郑怀礼, 房慧丽, 蒋绍阶, 等. 负载硅藻土的固体聚合硫酸铁的制备及结构表征[J]. 光谱学与光谱分析, 2011, 31(7): 1917-1921.
	ZHENGHuaili, FANGHuili, JIANGShaojie, et al. Preparation and structural analysis of diatomite-supported SPF flocculant[J]. Spectroscopy and Spectral Analysis, 2011, 31(7): 1917-1921.
10	郑雅杰, 彭超. 膨化法制备固体聚合硫酸铁技术[J]. 环境科学学报, 2009, 29(9): 1939-1943.
	ZHENGYajie, PENGChao. A new technology for preparation of solid polyferric sulphate by gas expansion[J]. Acta Scientiae Circumstantiae, 2009, 29(9): 1939-1943.
11	关晓辉, 王维雪, 刘雅琪, 等. 固体生物聚合硫酸铁的制备及其结构和性能研究[J]. 东北电力大学学报, 2015, 35(4): 26-32.
	GUANXiaohui, WANGWeixue, LIUYaqi, et al. The preparation structure and performance study of solid bio-polymeric ferric sulphate[J]. Journal of Northeast Dianli University, 2015, 35(4): 26-32.
12	CHENGW．Hydrolysis characteris of polyferric sulfate coagulant and its optimal condition of preparation[J]. Colloids and Surfaces, A：Physicochemical and Engineering Aspects, 2001, 182(1/2/3): 57-63.
13	关晓辉, 王磊, 马啸飞, 等. 改性生物聚合硫酸铁的制备及其性能研究[J]. 中国电机工程学报, 2010, 30(32): 58-62.
	GUANXiaohui, WANGLei, XiaofeiMA, et al. Preparation and performance research of the modified bio-polymeric ferric sulphate[J]. Proceedings of the CSEE, 2010, 30(32): 58-62.
14	HONGH, CHANGJ H, HSU H S, et al. Metal removal by Acidithiobacillus ferrooxidans through cells and extra-cellular culture supernatant in biomachining[J]. CIRP Journal of Manufacturing Science and Technology, 2012, 5: 137-141.
15	CHANDRAPRABHAM N, NATARAJANK A. Role of outer membrane exopolymers of Acidithiobacillus ferrooxidans in adsorption of cells onto pyrite and chalcopyrite[J]. International Journal of Mineral Processing, 2013, 123： 152-157.
16	LIAOZ, ZHUB, XUEX, et al. Study on fermentation kinetics of yeast cells immobilized of Chinese ceramics[J]. Journal of Shaoguan University(Social Science Edition), 2001, 22(9): 131-138.
17	彭超. 膨化固化法制备固体聚合硫酸铁新工艺[D]. 长沙：中南大学, 2009.
	PENGChao. A new technology for preparation of solid polyferric sulphate by gas expansion[D]. Changsha：Central South University, 2009.
18	张良佺, 陈纪忠, 祝巨, 等. 固体聚合硫酸铁的制取及工艺优化研究[J]. 高校化学工程学报, 2004, 18(4): 494-500.
	ZHANGLiangquan, CHENJizhong, ZHUJu, et al. Study on manufacture and technology optimization of solid polymerized ferric sulphate[J]. Journal of Chemical Engineering of Chinese Universities, 2004, 18(4): 494-500.
19	晏井春, 朱富坤, 闫永胜, 等. 纳米聚合硫酸铁的制备、表征及应用研究[J]. 无机盐工业, 2007, 39(11): 27-29.
	YANJingchun, ZHUFukun, YANYongsheng, et al. Study on preparation, characterization and application of nano-sized poly ferric sulphate coagulant[J]. Norganic Chemicals Industry, 2007, 39(11): 27-29.
20	ZHUAG, ZHENGH, ZHANGZ, et al. Characterization and coagulation-flocculation behaviour of polymeric aluminium ferric sulphate (PAFS)[J]. Chemical Engineering Journal, 2011(178): 50-59.
21	ＭOUSSASP A, ZOUBOULISA I. A study on the properties and coagulation behaviour of modified inorganic polymeric coagulant——polyferric silicate sulphate(PFSiS)[J]. Separation and Purification Technology, 2008(63）:475-483.
22	张鹏, 王雨露, 张文, 等. 聚合硫酸铝钛的制备与结构表征[J]. 化工进展, 2018, 37(7): 2740-2747
	ZHANGPeng, WANGYulu, ZHANGWen, et al. Synthesis and characterization of an inorganic composite polymer coagulant of poly aluminum titanium sulfate[J]. Chemical Industry and Engineering Progress, 2018, 37(7): 2740-2747.
23	唐海, 冯玲, 颜酉斌, 等. 粉煤灰制备聚硅酸铁铝的结构特征与混凝机理[J]. 高效化学工程学报, 2013, 27(6): 1045-1050.
24	TANGHai, FENGLing, YANYoubin, et al. Structural characteristics and coagulation mechanisms of PSFA prepared by fly ash[J]. Journal of Chemical Engineering of Chinese Universities, 2013, 27(6): 1045-1050.
25	陈伟, 郑怀礼, 翟俊, 等. 聚合硫酸铁钛混凝剂的制备及红外、紫外-可见光谱分析[J]. 光谱学与光谱分析, 2016, 36(4): 1038-1042.
	CHENWei, ZHENGHuaili, ZHAIJun, et al. Study on the preparation of a new composite coagulant: poly-ferric-titanium-sulfate and analysis of FTIR spectrum and UV-vis spectrum[J]. Spectroscopy and Spectral Analysis, 2016, 36(4): 1038-1042.
26	赵湘骥, 马荣骏, 杨镜全. 固体聚合硫酸铁的制备及其特性研究[J]. 矿冶工程, 1995, 15(2): 33-38.
	ZHAOXiangji, RongjunMA, YANGJingquan. Preparion and characteristics of solid polyferric sulfate[J]. Ming and Metallurgical Engineering, 1995, 15(2): 33-38.
27	SADRI MOGHADDAS, ALAVI MOGHADDAMM, ARAMIM. Response surface optimization of acid red 119 dye from simulated wastewater using Al based waterworks sludge and polyaluminium chloride as coagulant[J]. J. Environ. Manage, 2011, 92(4): 1284-1291.
28	李文朴, 卢静芳, 柳美乐, 等. 高岭土对氢氧化镁混凝去除活性橙染料效果的影响[J]. 化工进展, 2017, 36(11): 4286-4292.
	LIWenpu, LUJingfang, LIUMeile, et al. Effect of Kaolin on the removal of reactive orange by magnesium hydroxide coagulation process[J]. Chemical Industry and Engineering Progress, 2017, 36(11): 4286-4292.
29	高倩, 张大为, 徐慧, 等. 水体中Cr(VI）对不同混凝剂混凝过程的影响[J]. 环境科学, 2018, 39(8): 3704-3712.
	GAOQian, ZHANGDawei, XUHui, et al. Effect of Cr(Ⅵ) on coagulation process of different coagulants[J]. Environmental Science, 2018, 39(8): 3704-3712.
30	ZHENGH, ZHUG, JIANGS, et al. Investigations of coagulation-flocculation process by performance optimization, model prediction and fractal structure of flocs[J]. Desalination, 2011, 269(1/2/3)：148-156.
31	HAMIDN A A, ISMAILA A F, MATSUURAT, et al. Morphological and separation performance study of polysulfone/titanium dioxide (PSF/TiO₂) ultrafiltration membranes for humic acid removal[J]. Desalination, 2011, 273(1): 85-92.
32	郑怀礼, 余炳宏, 阳春, 等．聚磷氯化铝的制备新方法及其性能研究[J]．土木建筑与环境工程, 2011, 33(5): 125-131
	ZHENGHuaili, YUBinghong, YANGChun, et al. On novel synthetic method and performance of polymeric phosphate-aluminum chloride(PPAC)[J]. Journal of Civil , Architectural & Environmental Engineering, 2011, 33(5): 125-131.
33	郑怀礼, 冯力, 蒋贞贞, 等. 聚合硫酸铁铝处理印染废水[J]. 土木建筑与环境工程, 2013, 35(5): 1-6
	ZHENGHuaili, FENGLi, JIANGZhenzhen, et al. Analysis on polymeric aluminum ferric sulfate(PFAS) in printing and dyeing wastewater treatment[J]. Journal of Civil , Architectural & Environmental Engineering, 2013, 35(5): 1-6.
34	郑怀礼, 陈文源, 张智, 等. 无机高分子复合混凝剂聚合硫酸铝铁的制备与应用[J]. 重庆大学学报, 2013, 36(7): 114-120.
	ZHENGHuaili, CHENWenyuan, ZHANGZhi, et al. Preparation and applications of inorganic polymer composite flocculant poly aluminum ferric sulfate[J]. Journal of Chongqing University, 2013, 36(7): 114-120.
35	ZHUG, ZHENGH , CHENW, et al. Preparation of a composite coagulant: polymeric aluminum ferric sulfate (PAFS) for wastewater treatment[J]. Desanlination, 2012, 285: 315-323.

固化温度/℃	产品外观	溶解性
50	软，深黄	不易
55	脆，黄色	易溶
60	脆，黄色	易溶
65	脆，深黄	易溶
70	硬，发黑	不易

固化温度/℃	产品外观	溶解性
50	软，深黄	不易
55	脆，黄色	易溶
60	脆，黄色	易溶
65	脆，深黄	易溶
70	硬，发黑	不易

固化时间/h	产品外观	溶解性
2	软黏，深黄	不易
3	软黏，深黄	不易
4	脆，浅黄	易溶
5	脆，黄色	易溶

固化时间/h	产品外观	溶解性
2	软黏，深黄	不易
3	软黏，深黄	不易
4	脆，浅黄	易溶
5	脆，黄色	易溶

添加剂	投加比例(m_TFe:m_膨化剂)	固化时间/h	还原性物质质量分数 (以Fe²⁺含量计)/%	全铁质量分数/%	盐基度/%	产品外观	溶解性
—	—	5	0.062	22.46	17.86	脆，黄色	易溶
KAl(SO₄)₂	10∶1	3	0.016	20.33	19.23	脆，浅黄	易溶
SPFS	10∶1	4	0.034	21.70	16.78	脆，深黄	易溶
混合	10∶1	4	0.028	21.18	16.28	脆，深黄	易溶