聚合氯化铝铁的制备、使用及混凝机制研究

doi:10.11962/1006-4990.2019-0441

摘要/Abstract

摘要：

以氯化铝和氯化铁为原料制备出一系列不同铝铁物质的量比及碱化度的无机高分子混凝剂——聚合氯化铝铁（PAFC）,并应用于地表水的混凝处理过程。考察PAFC的混凝效能及产生的絮体特性,进而对其使用条件进行优化并分析混凝机制。结果表明,PAFC为多羟基桥连的铝铁聚合物,水解后发生电中和作用使胶粒脱稳,而后通过羟桥和氧桥联接产生架桥和卷扫沉淀作用,混凝效果优异。PAFC的pH适用范围较宽,但铝铁物质的量比对其水解过程影响较大,在铝铁物质的量比为7:1、碱化度为0.5、投加量为10 mg/L时,絮体的粒度及生长速度最大,此时浊度和UV₂₅₄的去除率分别达84.93%和78.52%。此外,正交实验的结果表明水力条件对PAFC的混凝效能影响显著,其最佳使用条件为：快搅时间为20 s、快搅速度为200 r/min、慢搅时间为15 min、慢搅速度为40 r/min。

关键词: 聚合氯化铝铁, 混凝剂, 水力条件

Abstract:

With aluminium chloride and ferric chloride as raw materials,a series of inorganic polymer coagulants-polyalu-minium ferric chloride（PAFC） with different amount-of-substance ratio of Al/Fe and basicity were prepared,and then used in coagulation process of surface water.The coagulation efficiency and floc characteristics of PAFC were studied to optimize its application conditions,and meanwhile coagulation mechanisms were also analyzed.Results showed that synthesized PAFC possess a variety of hydroxy bridged aluminum-iron polymers.Colloidal particles became destabilization due to the charge neutralization mechanism of PAFC hydrolysate,and then the bridge between hydroxyl and oxygen could promote the bridging and sweeping precipitation action.The coagulation effect was excellent.The pH range of PAFC was wide,but the amount-of-substance ratio of aluminum to iron had a great influence on the hydrolysis process.The amount-of-substance ratio of Al/Fe was 7:1,the alkalinity was 0.5 and the dosage was 10 mg/L.Under the conditions,particle size and growth rate of flocs were the largest,and the removal rates of turbidity and UV₂₅₄ reached 84.93% and 78.52%,respectively.In addition,coagulation efficiency of PAFC was greatly influenced by hydraulic conditions.The optimum parameters were as follows：the fast stirring time was 20 s,the fast stirring speed was 200 r/min,the slow stirring time was 15 min and the slow stirring speed was 40 r/min.

Key words: polyaluminium ferric chloride, coagulant, hydraulic conditions

中图分类号:

TQ124.42

赵爽,徐梦辰,汪艳. 聚合氯化铝铁的制备、使用及混凝机制研究[J]. 无机盐工业, 2020, 52(7): 36-41.

Zhao Shuang,Xu Mengchen,Wang Yan. Preparation,application and coagulation mechanism of polyaluminium ferric chloride[J]. Inorganic Chemicals Industry, 2020, 52(7): 36-41.

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参考文献 24

[1]	Sillanpaa M, Ncibi M C, Matilainen A, et al. Removal of natural organic matter in drinking water treatment by coagulation:A comprehensive review[J]. Chemosphere, 2019,190:54-71. pmid: 28985537
[2]	Huang X, Zhao Y, Gao B Y, et al. Polyacrylamide as coagulant aid with polytitanium sulfate in humic acid-kaolin water treatment:Effect of dosage and dose method[J]. Journal of the Taiwan Institute of Chemical Engineers, 2016,64:173-179. doi: 10.1016/j.jtice.2016.04.011
[3]	Liu T, Lian Y L, Graham N, et al. Application of polyacrylamide flocculation with and without alum coagulation for mitigating ultrafiltration membrane fouling:Role of floc structure and bacterial activity[J]. Chemical Engineering Journal, 2019,307:41-48.
[4]	Yang Z L, Gao B Y, Wang Y, et al. The effect of additional poly-diallyl dimethyl ammonium-chloride on the speciation distribution of residual aluminum(Al) in a low DOC and high alkalinity reservoir water treatment[J]. Chemical Engineering Journal, 2012,197:56-66.
[5]	郑怀礼, 高亚丽, 蔡璐微, 等. 聚合氯化铝混凝剂研究与发展状况[J]. 无机盐工业, 2015,47(2):1-5.
[6]	Wu C D, Xu X J, Liang J L, et al. Enhanced coagulation for treating slightly polluted algae-containing surface water combining polyaluminum chloride(PAC) with diatomite[J]. Desalination, 2011,279:140-145. doi: 10.1016/j.desal.2011.06.007
[7]	Dong H Y, Gao B Y, Yue Q Y, et al. Effect of pH on floc properties and membrane fouling in coagulation-Ultrafiltration process with ferric chloride and polyferric chloride[J]. Chemosphere, 2015,130:90-97. pmid: 25867785
[8]	刘细祥, 吴启琳, 史兵方, 等. 利用铝型材厂废铝渣制备聚合氯化铝的研究[J]. 无机盐工业, 2014,46(4):53-55.
[9]	于海涛. 聚合氯化铁铝的制备及其对印染废水处理的应用研究[J]. 广州化工, 2014,42(5):56-58.
[10]	Zhao S, Gao B Y, Wang Y, et al. Influence of a new coagulant aidEnteromorpha extract on coagulation performance and floc characteristics of aluminum sulfate coagulant in kaolin-humic acid solution treatment[J]. Colloids and Surfaces A:Physicochemical and Engineering Aspects, 2013,417:161-169. doi: 10.1016/j.colsurfa.2012.10.062
[11]	Zhang W, Zhang T, Xi L, et al. Preparation of new type poly-silicat coagulant and its coagulation property[J]. Energy Procedia, 2012,17:1627-1634. doi: 10.1016/j.egypro.2012.02.290
[12]	Sun T, Liu L L, Wang L L, et al. Preparation of a novel inorganic polymer coagulant from oil shale ash[J]. Journal of Hazardous Materials, 2011,185:1264-1272. doi: 10.1016/j.jhazmat.2010.10.041 pmid: 21071139
[13]	Shi J, Zhang Y, Zou K, et al. Speciation characterization and coagulation of poly-silica-ferric-chloride:The role of hydrolyzed Fe(Ⅲ) and silica interaction[J]. Journal of Environmental Sciences, 2011,23(5):749-756. doi: 10.1016/S1001-0742(10)60471-8
[14]	Zhang P, Hahn H H, Hoffmann E, et al. Influence of some additives to aluminium species distribution in aluminium coagulants[J]. Chemosphere, 2004,57:1489-1494. doi: 10.1016/j.chemosphere.2004.08.066 pmid: 15519393
[15]	Zhu G, Zheng H, Zhang Z, et al. Characterization and coagulationflocculation behavior of polymeric aluminum ferric sulfate (PAFS)[J]. Chemical Engineering Journal, 2011,178:50-59. doi: 10.1016/j.cej.2011.10.008
[16]	章兴华, 周丽芸, 汤敏. 聚合氯化铝铁的红外光谱研究[J]. 光谱学与光谱分析, 2002(1):39-42.
[17]	王光辉, 孟红旗, 雷国元. 聚合氯化铝铁的形态分布研究[J]. 武汉科技大学学报:自然科学版, 2005,28(2):162-165.
[18]	康黛男. 聚合氯化铝铁絮凝剂的研制及其在废水处理中的应用[D]. 西安:长安大学, 2008.
[19]	任根宽. 复合型絮凝剂聚合氯化铝铁的合成[J]. 无机盐工业, 2011,43(6):55-58.
[20]	《正交试验法》编写组. 正交试验法[M]. 北京: 国防工业出版社, 1976: 57-73.
[21]	刘晓红, 荀开昺, 杨方麒, 等. 含铝废渣制备聚硅酸铝铁絮凝剂处理造纸废水[J]. 无机盐工业, 2016,48(3):63-65.
[22]	王迅, 李伟, 刘玉灿, 等. 新型混凝剂聚合氯化铝钛的制备及性能表征[J]. 水处理技术, 2019,45(2):27-31.
[23]	王景垒, 夏霆, 何涛, 等. 新型聚合硅酸氯化铝锌铁絮凝剂的制备及其除藻效果[J]. 净水技术, 2018,37(5):12-19.
[24]	孙翠珍. 新型聚合铝铁—有机复合絮凝剂的混凝性能及其絮体特性研究[D]. 济南:山东大学, 2012.

参数	m（FeCl₃·6H₂O）/g	m（AlCl₃· 6H₂O）/g	m（Na₂CO₃）/ g	m（Na₂HPO₄· 12H₂O）/g
碱化度=0.5	2.758 1	17.245 3	2.163 2	0.292 2
碱化度=1.0	2.758 1	17.245 3	4.326 4	0.292 2
碱化度=1.5	2.758 1	17.245 3	6.489 6	0.292 2
n（Al）/n（Fe）=1:1	2.758 1	2.462 6	2.163 2	0.292 2
n（Al）/n（Fe）=3:1	2.758 1	7.387 8	2.163 2	0.292 2
n（Al）/n（Fe）=6:1	2.758 1	14.775 5	2.163 2	0.292 2
n（Al）/n（Fe）=7:1	2.758 1	17.245 3	2.163 2	0.292 2
n（Al）/n（Fe）=8:1	2.758 1	19.700 7	2.163 2	0.292 2
n（Al）/n（Fe）=9:1	2.758 1	22.163 3	2.163 2	0.292 2

因素	A 快搅时间/s	B 快搅速度/（r·min^-1）	C 慢搅时间/min	D 慢搅速度/（r·min^-1）	浊度去除率/%	UV₂₅₄去除率/%
实验1	20	100	5	30	78.73	74.46
实验2	20	200	15	40	83.79	80.94
实验3	20	300	25	50	67.71	72.30
实验4	30	100	5	30	79.02	74.82
实验5	30	200	15	40	81.53	79.14
实验6	30	300	25	50	66.60	69.78
实验7	40	100	5	30	79.25	75.18
实验8	40	200	15	40	80.39	75.90
实验9	40	300	25	50	73.10	73.02

参数		A	B	C	D
浊度	R	1.86	12.77	3.40	2.08
浊度	较优水平	A₃	B₂	C₂	D₂
UV₂₅₄	R	1.32	6.96	2.88	1.20
UV₂₅₄	较优水平	A₁	B₂	C₂	D₁、D₂

PAFC投加量/ （mg·L^-1）	达到稳定时的粒径/μm	达到平衡所需时间/min	絮体生长速度/ （μm·min^-1）
4	268	7	33.5
10	352	6	58.7
16	302	8	37.8

项目	铝铁物质的量比	碱化度	投加量/（mg·L^-1）	pH	水力条件	处理效能
文献[18]	9:1	未提及	75	4~10	250 r/min,2 min;50 r/min,5 min	针对含油废水,对COD及SS的去除率分别达75.7%及63.1%
文献[24]	5:2	1.0	9	4.5~9.5	200 r/min,1 min;40 r/min,15 min	针对腐殖酸-高岭土模拟地表水样,对浊度及DOC去除率可达96%及32%
本文结果	7:1	0.5	10	6~9	200 r/min,20 s;40 r/min,15 min	针对玉泉河水水样,对浊度及UV₂₅₄去除率最高可达90.31%及73.00%

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