高岭土负载HPCS-MA对亚甲基蓝废水的絮凝性能

doi:10.16085/j.issn.1000-6613.2018-1435

摘要/Abstract

摘要：

以羟丙基壳聚糖（HPCS）、马来酸酐（MA）为原料合成N-马来酰化羟丙基壳聚糖（HPCS-MA）。采用红外光谱（FTIR）、核磁共振氢谱（¹H NMR）对其结构进行表征。考察了缚酸剂三乙胺用量、反应温度、反应时间及马来酸酐用量对产物羧基含量及特性黏数的影响。结果表明：在缚酸剂用量为5g，反应温度65℃，反应时间6h，马来酸酐用量为4.5g的条件下，产物的羧基含量和特性黏数均达到较佳值，为83.50%和211.96mL/g。利用高岭土负载HPCS-MA处理亚甲基蓝印染废水，研究了pH、投加量、絮凝温度、初始浊度对亚甲基蓝染料脱色性能的影响。结果表明，在亚甲基蓝浓度为3×10^-5mol/L的印染废水中，HPCS-MA絮凝脱色的适宜条件为：pH为1～5，投加量为4～8mg/L，温度为20～25℃，浊度为200～400NTU，在此条件下色度去除率均在96.5%以上。

关键词: 羟丙基壳聚糖, 马来酸酐, 亚甲基蓝, 脱色

Abstract:

Hydroxypropyl chitosan (HPCS) and maleic anhydride (MA) were used as raw materials to synthesize N-maleated hydroxypropyl chitosan (HPCS-MA). FTIR, ¹H NMR were used to characterize the structure of the sample. The effect of the amount of acid-binding agent triethylamine, reaction temperature, reaction time and the amount of maleic anhydride on the carboxyl content and intrinsic viscosity of the product was investigated. The results showed that under the conditions of acid binding agent dosage 5g, reaction temperature 65℃, reaction time 6h and MA dosage 4.5g, both carboxyl content and intrinsic viscosity of the product reached a good value of 83.50% and 211.96mL/g. The methylene blue printing and dyeing wastewater were treated with kaolin-loaded HPCS-MA. The effect of pH, dosage, flocculation temperature and initial turbidity on the decolorization performance of methylene blue dye was studied. The results showed that in the printing and dyeing wastewater with methylene blue concentration of 3×10^-5 mol/L, the suitable conditions for flocculation and decolorization of HPCS-MA was pH=1—5, dosage was 4—8mg/L, temperature was 20—25℃, initial turbidity was 200—400 NTU. Under these conditions, the chroma removal rate was above 96.5% .

Key words: hydroxypropyl chitosan, maleic anhydride, methylene blue, decolorization

中图分类号:

TQ317

郭睿, 张瑶, 高弯弯, 韩双, 王宁. 高岭土负载HPCS-MA对亚甲基蓝废水的絮凝性能[J]. 化工进展, 2019, 38(04): 1953-1960.

Rui GUO, Yao ZHANG, Wanwan GAO, Shuang HAN, Ning WANG. Flocculation performance of kaolin loading HPCS-MA on methylene blue wastewater[J]. Chemical Industry and Engineering Progress, 2019, 38(04): 1953-1960.

图/表 11

图1 HPCS与 MA反应生成HPCS-MA的路线

图2 HPCS-MA的红外与核磁谱图

图3 三乙胺用量对HPCS-MA特性黏数及羧基含量的影响

图4 温度对HPCS-MA特性黏数及羧基含量的影响

图5 时间对HPCS-MA特性黏数及羧基含量的影响

图6 马来酸酐用量对HPCS-MA特性黏数及羧基含量的影响

图7 pH对色度去除率及浊度去除率的影响

图8 温度对色度去除率及浊度去除率的影响

图9 投加量对色度去除率及浊度去除率的影响

图10 pH 和HPCS-MA投加量对zeta电位的影响

图11 絮体的XPS谱图

参考文献 19

1	胡潇, 梁虎南, 于大禹 . 硅藻土处理染料废水的研究进展[J]. 硅酸盐通报, 2018, 37(1): 160-165.
	HU Xiao , LIANG Hunan , YU Dayu . Research progress on diatomite treatment of dye wastewater[J]. Bulletin of the Chinese Ceramic Society , 2018, 37(1): 160-165.
2	WANG X , LI X U , WANG P . Research progress of the wastewater treatment of dye industry[J]. Journal of Chemical Industry & Engineering, 2003, 24(4): 39-41.
3	FANG L , MENG G H , WEI W , et al . Application status and development of treatment for wastewater from benzene-dye intermediates[J]. Dyestuffs & Coloration, 2016, 53(4): 42-50.
4	刘向朝, 丛晓东, 闫红梅 . 高效脱色絮凝剂在印染废水处理中的应用[J]. 工业水处理, 2011, 31(4): 53-54.
	LIU Xiangchao , CONG Xiaodong , YAN Hongmei .Application of high-efficiency decolorization flocculant in printing and dyeing wastewater treatment[J]. Industrial Water Treatment, 2011, 31(4): 53-45.
5	FAN X D , ZHANG X K . Heavy metals leaching of active carbon from sewage sludge modified by chitosan for dye wastewater treatment[J]. Advanced Materials Research, 2013, 627: 399-403.
6	李世迁, 陈盛 . 壳聚糖/高岭土复合材料的制备及其对甲基橙吸附性能[C]//中国化学会2013年中西部地区无机化学化工学术研讨会，江西吉安, 2013.
	LING Shiqiang , CHEN Sheng . Preparation of chitosan/kaolin composite and its adsorption properties for methyl orange[C]//Seminar on Inorganic Chemistry and Chemical Engineering of the Central and Western Regions of the Chinese Chemical Society, Ji’an, Jiangxi, 2013.
7	陈彰旭, 辛梅华, 李明春, 等 . 壳聚糖/粉煤灰/高岭土的制备及其处理活性蓝模拟印染废水的研究[J]. 化工新型材料, 2013, 41(10): 165-168.
	CHEN Zhangxun , XIN Meihua , LI Mingchun , et al .Preparation of chitosan/fly ash/kaolin and its treatment of reactive blue simulated printing and dyeing wastewater[J]. New Chemical Materials, 2013, 41(10): 165-168.
8	郭睿, 郭煜, 宋博, 等 . 琥珀酰壳聚糖的合成及絮凝性能[J]. 精细化工, 2018, 35(3): 474-481.
	GUO Rui , GUO Yu , SONG Bo , et al . Synthesis and flocculation properties of succinyl-chitosan[J].Fine Chemicals, 2018, 35(3): 474-481.
9	WANG W , YUE Q , LI R , et al . Investigating coagulation behavior of chitosan with different Al species dual-coagulants in dye wastewater treatment[J]. Journal of the Taiwan Institute of Chemical Engineers, 2017, 78: 423-430.
10	JIANG X , CAI K , ZHANG J , et al ．Synthesis of a novel water-soluble chitosan derivative for flocculated decolorization [J]． Journal of Hazardous Materials, 2011, 185( 2 /3) : 1482-1488．
11	郭俊元, 陈诚, 张萍, 等 . 壳聚糖的改性及其去除废水中染料物质的性能研究[J]. 环境科学学报, 2018, 38(4): 1529-1536.
	GUO Junyuan , CHEN Cheng , ZHANG Ping , et al . Modification of chitosan and its performance in removing dyestuffs from wastewater[J]. Acta Scientiae Circumstantiae, 2018, 38(4): 1529-1536..
12	李盼盼, 周利, 张璐, 壳聚糖改性高岭土去除水中常见藻类的试验研究 [J]. 环境污染与防治， 2015, 37(1): 59-61, 67.
	LI Panpan , ZHOU Li , ZHANG Lu . Experimental study on removal of common algae by chitosan-modified kaolin[J]. Environmental Pollution & Control, 2015, 37(1): 29-61, 67.
13	刘荣香, 张焕祯, 刘峻平 . 高岭土负载壳聚糖处理铬渣污染地下水[J]. 工业水处理, 2012, 32(5): 44-47.
	LIU Rongxiang , ZHANG Huanzhen , LIU Junping . Treatment of groundwater polluted by chromium residue with kaoline-chitosan compound adsorbent[J].Industrial Water Treatment, 2012, 32(5): 44-47.
14	纪欢欢 . 离子液体条件下N-酰化壳聚糖的均相合成新工艺研究[D]. 青岛: 青岛科技大学, 2009.
	JI Huanhuan . Study on new process for homogeneous synthesis of N-acylated chitosan under ionic liquid conditions[D]. Qingdao: Qingdao University of Science and Technology, 2009.
15	应国清, 杨好, 李东华, 等 . N-马来酰化壳聚糖的合成和性能[J]. 化工进展, 2007, 26(3): 405-408.
	YING Huoqing , YANG Hao , LI Donghua , et al . Synthesis and properties of novel hyaluronic acid-like chitosan[J].Chemical Industry and Engineering Progerss, 2007, 26(3): 405-408.
16	卞林芝, 杨康, 纵朝阳 . 2-甲基-2-硝基-1-叠氮丙烷合成方法研究[J]. 精细化工, 2018, 35(1): 170-173.
	BIAN Linzhi , YANG Kang , ZONG Chaoyang . Study on the synthesis of 2-methyl-2-nitro-1-azidopropane[J]. Fine Chemicals, 2018, 35(1): 170-173.
17	郭俊元, 陈诚, 张萍, 等 . 壳聚糖的改性及其去除废水中染料物质的性能研究[J]. 环境科学学报, 2018, 38(4): 1529-1536.
	GUO Junyuan , CHEN Cheng , ZHANG Ping , et al . Modification of chitosan and its performance in removing dyestuffs from wastewater[J]. Acta Scientiae Circumstantiae, 2018,38 (4): 1529-1536.
18	郭睿, 郭煜, 王映月, 等 . 琥珀酰壳聚糖季铵盐的合成及絮凝性能[J]. 化工进展, 2018, 37(7): 2806-2813.
	GUO Rui , GUO Yu , WANG Yingyue , et al . Synthesis and flocculation properties of succinyl chitosan quaternary ammonium salt[J]. Chemical Industry and Engineering Progress, 2018, 37(7): 2806-2813.
19	李小芳, 冯小强, 杨声 . 硅藻土负载壳聚糖季铵盐处理甲基橙染料废水[J]. 非金属矿, 2012, 35(6): 74-76.
	LI Xiaofang , FENG Xiaoqiang , YANG Shen . Study on methyl orange waste water treatment through diatomite loading quaternary ammonium salt of chitosan[J]. Non-metallic Mines, 2012, 35(6): 74-76.

[1]	田芳, 郭光, 丁克强, 杨凤, 刘翀, 王慧雅. 降解偶氮染料嗜盐菌的分离、降解特性及机制[J]. 化工进展, 2023, 42(4): 2115-2121.
[2]	赖槐东, 程德书, 王坚, 罗菊香. α-甲基苯乙烯马来酸酐共聚物微球固载β-环糊精的制备及应用[J]. 化工进展, 2023, 42(4): 2038-2046.
[3]	范娇, 谢学辉, 秦艳, 陈小光, 方英荣, 杨珊珊, 赵江贵, 莫浩楠, 郑航蜜, 刘娜, 张庆云, 宋新山. 功能菌群DDMZ1共代谢脱色降解不同结构染料差异效应[J]. 化工进展, 2022, 41(8): 4449-4463.
[4]	陈彰旭, 陈冰冰, 王荣财, 叶晨光, 郑炳云. β-NaYF₄:Yb³⁺,Tm³⁺/g-C₃N₄复合水凝胶材料的制备及其应用[J]. 化工进展, 2022, 41(6): 3146-3154.
[5]	陈泳, 马妍楠, 徐成. 吸附电活性染料的活性炭电极电化学性能[J]. 化工进展, 2022, 41(5): 2537-2545.
[6]	樊相汝, 羊依金, 郭旭晶, 张全碧. 软锰矿-含油污泥基活性炭对亚甲基蓝的吸附特性[J]. 化工进展, 2022, 41(12): 6664-6671.
[7]	刘叶凤, 孙奎, 黄廷洪, 李延芬. 构型限制Co-P催化剂的设计合成及对亚甲基蓝的光催化降解[J]. 化工进展, 2021, 40(S1): 231-237.
[8]	宗莉, 唐洁, 牟斌, 王爱勤. 凹凸棒石/炭复合吸附材料研究进展[J]. 化工进展, 2021, 40(1): 282-296.
[9]	方文强,祝琳华,司甜,孙彦琳,何艳萍. SMA的合成及其对香精的分散和微胶囊制备的影响[J]. 化工进展, 2020, 39(2): 702-708.
[10]	王元芳, 尹孟华, 钱佳丽, 耿启金, 杨金美, 陈刚. 混凝与光催化联用处理水体中的复合染料[J]. 化工进展, 2020, 39(12): 5290-5298.
[11]	张华, 张子鹏, 张澜澜, 张晓飞, 刘译阳. H₂O₂强化光催化处理苯胺化工废水的应用试验[J]. 化工进展, 2020, 39(12): 5299-5308.
[12]	周自成,李煦,郭琳琳,范小振. 十二烷基硫酸钠修饰NiFe₂O₄对亚甲基蓝的类芬顿催化氧化性能[J]. 化工进展, 2019, 38(12): 5532-5538.
[13]	朱丹琛,肖伽励,杨丽丽,傅明连. 水热合成MnO₂及其染料吸附性能的构效关系[J]. 化工进展, 2019, 38(08): 3774-3781.
[14]	蔡炜, 魏砾宏, 梁法光, 李润东, 李彦龙. 铝锂合金化铣废液合成γ-AlOOH及表征[J]. 化工进展, 2019, 38(04): 1839-1845.
[15]	龚新怀, 辛梅华, 李明春, 李素琼, 赵晓杰. 磁性响应茶渣制备及其对水溶液中亚甲基蓝的吸附[J]. 化工进展, 2019, 38(02): 1113-1121.