壳聚糖衍生物用于市政废水阻垢
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摘要
以壳聚糖(CTS)、丙烯酸(AA)为单体,以过硫酸铵(APS)为引发剂,在体积分数为2%的冰醋酸水溶液中共聚,制备了N-羧乙基化壳聚糖(CEC)。采用红外光谱、核磁共振光谱等对壳聚糖衍生物CEC进行了表征。以阻垢性能为评判标准,通过单因素实验筛选出CEC的最佳合成条件为:m(AA)∶m(CTS)=5.30∶3.00,反应温度为75℃,反应时间为4 h,引发剂APS用量为3%(以单体总质量为基准,下同)。考察了CEC用于二级市政废水中的阻垢性能,结果表明,在经过二级处理的市政废水中,CEC阻CaCO3垢性能优异,当CEC的加药量为30 mg/L时,对CaCO3的阻垢率可达92.93%,明显优于市售阻垢剂羟基乙叉二膦酸(HEDP)。通过SEM、XRD对CEC阻CaCO3机理进行了初步探究,结果表明,CEC对CaCO3的作用机理主要是晶格畸变作用。
A new N-carboxylated chitosan(CEC) was synthesized by copolymerization of chitosan(CTS) and acrylic acid(AA) using ammonium persulfate(APS) as initiator in the presence of 2%(volume fraction) glacial acetic acid solution.The product was characterized by FTIR and 1 HNMR.According to scale inhibition performance,the synthesis conditions for CEC were optimized by single factor experiment.The optimal conditions were obtained as followed:the mass ratio of AA to CTS was 5.30∶3.00,the reaction temperature was 75 ℃,the reaction time was 4 h and the dosage of APS was 3%(based on the total mass of monomer,as the below).Then,the scale inhibition performance of CEC for secondary municipal wastewater treatment was studied.The results presented that the synthetic CEC exhibited excellent inhibition performance to CaCO3 and the scale inhibition rate could reach 92.93% in the presence of 30 mg/L of CEC,which was significantly better than commercially available scale inhibitor 1-hydroxyethylidene-1,1-diphosphonic acid(HEDP).The mechanism of CEC inhibiting CaCO3 was investigated by SEM and XRD.The results revealed that the mechanism of CEC on CaCO3 was mainly caused by lattice distortion.
A new N-carboxylated chitosan(CEC) was synthesized by copolymerization of chitosan(CTS) and acrylic acid(AA) using ammonium persulfate(APS) as initiator in the presence of 2%(volume fraction) glacial acetic acid solution.The product was characterized by FTIR and 1 HNMR.According to scale inhibition performance,the synthesis conditions for CEC were optimized by single factor experiment.The optimal conditions were obtained as followed:the mass ratio of AA to CTS was 5.30∶3.00,the reaction temperature was 75 ℃,the reaction time was 4 h and the dosage of APS was 3%(based on the total mass of monomer,as the below).Then,the scale inhibition performance of CEC for secondary municipal wastewater treatment was studied.The results presented that the synthetic CEC exhibited excellent inhibition performance to CaCO3 and the scale inhibition rate could reach 92.93% in the presence of 30 mg/L of CEC,which was significantly better than commercially available scale inhibitor 1-hydroxyethylidene-1,1-diphosphonic acid(HEDP).The mechanism of CEC inhibiting CaCO3 was investigated by SEM and XRD.The results revealed that the mechanism of CEC on CaCO3 was mainly caused by lattice distortion.
引文
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[23]Li Jianbo(李建波),Fang Fang(方钫),Liu Jianyi(刘建仪),et al.Synthesis of polyaspartic acid/O-carboxymethyl chitosan graft copolymer and its scale inhibition performance for barium sulfate[J].Fine Chemicals(精细化工),2017,34(2):227-234.
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[2]Huang Ganghua(黄刚华),Wang Yue(王月),Zhang Qiang(张强),et al.Research progress in effect of reuse of reclaimed water on recirculated cooling water system[J].Technology of Water Treatment(水处理技术),2016,24(2):15-18.
[3]Chen W,Lu S,Jiao W,et al.Reclaimed water:A safe irrigation water source?[J].Environmental Development,2013,8(1):74-83.
[4]Miller W G.Integrated concepts in water reuse:Managing global water needs[J].Desalination,2006,187(1):65-75.
[5]National Development and Reform Commission(中华人民共和国国家发展和改革委员会).Reusing wastewater quality standard for industrial circulating cooling water(循环冷却水用再生水水质标准):HG/T3923-2007[S].Beijing:Beijing United Publishing Company(北京联合出版社),2007.
[6]Standardization Administration of The People’s Republic of China(中国国家标准化管理委员会).The reuse of urban recycling water-Water quality standard for industrial uses(城市污水再生利用-工业用水水质):GB/T 7714-2006[S].Beijing:Standards Press of China(中国标准出版社),2006.
[7]Li Qian(李倩),Yu Ping(于萍),Luo Yunbai(罗运柏).Discussion on existing problems of reclaimed water reused in industrial circulating water system[J].Industrial Water&Wastewater(工业用水与废水),2012,43(2):6-8.
[8]Han Qiang(韩强),Zhang Jiuzhi(张久志),Li Ping(李萍).Development and application of reagent for circulating water system of municipal reclaimed water reuse power plant[J].Shandong Chemical Industry(山东化工),2018,47(4):75-78.
[9]Hou Yulin(侯玉琳).Research and application of water quality stabilization treatment of recycled cooling water system for reclaimed water[J].Tianjin Chemical Industry(天津化工),2013,27(3):42-43.
[10]Chi Jinbao(迟金宝),Zhang Xuefeng(张雪峰),Cang Daqiang(苍大强).Experimental research on static scale and corrosion inhibition using low frequency electromagnetic treatment of reclaimed Water[J].Iron and Steel(钢铁),2009,44(6):89-93.
[11]Yang R,Li H,Huang M,et al.A review on chitosan-based flocculants and their applications in water treatment[J].Water Research,2016,95:59-95.
[12]Guo X,Qiu F,Dong K,et al.Preparation,characterization and scale performance of scale inhibitor copolymer modification with chitosan[J].Journal of Industrial&Engineering Chemistry,2012,18(6):2177-2183.
[13]Editorial Board of Kurita Industrial Water Treatment Pharmacy Manual(栗田工业水处理药剂手册编委会).Water treatment agent manual[M].Beijing:China Petrochemical Press(中国石油化工出版社),1991:114-116.
[14]Jiang Linbin(蒋林斌),Zhang Yanyan(张艳艳),Liang Daxing(梁达星).Preparation and adsorption behavior of graft copolymer by chitosan with acrylic acid[J].Journal of Guangxi University(Nat Sci Ed)(广西大学学报:自然科学版),2013,38(3):515-520.
[15]Pestov A V,Zhuravlev N A,Yatluk Y G.Synthesis in a gel as a new procedure for preparing carboxyethyl chitosan[J].Russian Journal of Applied Chemistry,2007,80(7):1154-1159.
[16]Sinopec Group(中国石油化工集团公司).Cooling water analysis and test methods[M].Beijing:Petroleum Press(石油出版社),1989:71-374.
[17]Guo Rui(郭睿),Guo Yu(郭煜),Song Bo(宋博),et al.Synthesis and flocculation properties of succinyl-chitosan[J].Fine Chemicals(精细化工),2018,35(3):474-481.
[18]Mun G A,Nurkeeva Z S,Dergunov S A,et al.Studies on graft copolymerization of 2-hydroxyethyl acrylate onto chitosan[J].Reactive&Functional Polymers,2008,68(1):389-395.
[19]Jiang H,Wang Y,Huang Q,et al.Biodegradable hyaluronic acid/N-carboxyethyl chitosan/protein ternary complexes as implantable carriers for controlled protein release[J].Macromolecular Bioscience,2005,5(12):1226-1233.
[20]Zhong Xueming(钟学明),Shu Hongying(舒红英),Deng Anmin(邓安民),et al.Study on application and synthesis for high pure ammonium ceric nitrate[J].Jiangxi Chemical Industry(江西化工),2005,23(2):64-67.
[21]Wang W,Bo S Q,Li S Q,et al.Determination of the Mark-Houwink equation for chitosans with different degrees of deacetylation[J].International Journal of Biological Macromolecules,1991,13(5):281-285.
[22]Standardization Administration of The People's Republic of China(中国国家标准化管理委员会).Determination of the anti-fouling performance of water treatment agent calcium carbonate deposition method(水处理剂阻垢性能的测定碳酸钙沉积法):GB/T16632-2008[S].Beijing:Standards Press of China(中国标准出版社),2009.
[23]Li Jianbo(李建波),Fang Fang(方钫),Liu Jianyi(刘建仪),et al.Synthesis of polyaspartic acid/O-carboxymethyl chitosan graft copolymer and its scale inhibition performance for barium sulfate[J].Fine Chemicals(精细化工),2017,34(2):227-234.
[24]Gao Meiling(高美玲),Li Haihua(李海花),Zhang Lihui(张利辉),et al.Study on synthesis scale inhibition performance and mechanism of ESA/IA/AMPS copolymer[J].Speciality Petrochemicals(精细石油化工),2017,34(1):42-47.