胺接枝螯合絮凝剂的制备及其除铅性能研究

研究了以聚丙烯酰胺(PAM)、甲醛、二乙烯三胺(DETA)为原料,按照Mannich反应机理制备部分胺化接枝型螯合作用絮凝剂(CFA)及其从水中除铅性能。基于在聚丙烯酰胺的分子长链上引入具有螯合作用的基团,使得该螯合絮凝剂既具有捕捉Pb2+离子螯合作用又具有絮凝作用,因此可用于从低浓度含铅废水中絮凝沉降除铅。实验考察了螯合絮凝剂合成及从含铅废水中除铅的的最佳条件。结果表明,该螯合絮凝剂合成条件易于掌握、工艺简单易行、除铅快速、操作简便,对含铅50 mg/L的模拟含铅废水,以絮凝剂比废水为1∶125(体积比)加量,经絮凝沉淀后,可去除90%以上的铅,除铅效果明显。获得了一种新的、低成本的从含铅废水中去除铅的材料和方法。     

改良絮凝剂在高浊度及含油废水处理中的应用

依托Mannich反应在聚丙烯酰胺(PAM)上接枝二乙胺,合成叔胺型有机高分子阳离子絮凝剂(D-PAM),并用于高浊度水处理。通过比较不同的原料投料比、pH值、反应时间和反应温度,确定了制备D-PAM絮凝剂的最佳条件以及处理高浊度废水的最佳絮凝条件。结果表明,在摩尔比为PAM∶甲醛∶二乙胺=1∶0.7∶0.85、pH=9～11、反应温度45～50℃、甲醛反应时间t₁=1 h,二乙胺反应时间t₂=2 h,此时接枝效果最好。同时,该絮凝剂对高浊度废水有良好的处理效果,最佳絮凝条件为：在强酸或强碱条件下使用0.7 mL 1%D-PAM溶液、在300 r/min下快速搅拌4 min、然后180 r/min,搅拌7 min,静置沉降20 min,最高去浊率为99.81%。合成的絮凝剂在高浊度废水及含油废水的处理中具有一定优势,是一种可双功能处理废水的新型阳离子絮凝剂。     

淀粉-聚丙烯酰胺接枝共聚物的工艺优化与性能研究

通过玉米淀粉接枝聚丙烯酰胺(PAM)制成了新型复合絮凝剂S-g-PAM,进行了影响接枝共聚物合成的单因素实验和正交实验,以对高岭土悬浊液的絮凝性能为评价指标。结果表明,最佳合成条件为,m(玉米淀粉)∶m(PAM)=3∶0.001(质量比),NaOH∶NaOCl=2∶3(体积比),反应时间40 min,反应温度30℃,对高岭土溶液(110NTU)最佳去浊度效果为97%,投加量为30 mg/L。S-g-PAM使用的pH值范围为8~10,最佳温度范围20~40℃,与其它絮凝剂相比,其絮凝效果较好。     

2-巯基乙胺螯合凝胶的制备及其除汞性能的研究

以PAM凝胶、甲醛、2-巯基乙胺为原料,按照Mannich反应机理制备部分接枝螯合凝胶,考察了螯合凝胶合成及从含汞废水中除汞的最佳条件。结果表明,对含汞8.0 mg/L的模拟废水,按30 g/L的投加量(固液比1∶33),在pH为6,温度40℃,反应1.5 h的条件下进行处理后,接枝凝胶可去除99.6%的汞,除汞效果明显,一次处理后的水含汞0.032 mg/L,可达到国家排放标准。因此,螯合凝胶可用于低浓度含汞废水的处理。     

改性纤维素絮凝剂的制备与应用

以纤维素为主要原料,丙烯酰胺、乙酸乙烯酯为单体,硝酸铈铵为引发剂,甲醛和二甲胺为阳离子化试剂,通过接枝聚合反应合成改性的纤维素絮凝剂,并探讨了该絮凝剂对高岭土悬浊液的絮凝作用,着重考察了单体与处理后纤维素的配比、反应温度、反应时间、引发剂量对改性纤维素絮凝剂接枝率和接枝效率的影响。实验结果表明,改性纤维素絮凝剂最佳的合成条件为∶单体质量比为2∶1,引发剂用量为0.03g,反应温度为55℃,反应时间为4 h。絮凝试验表明:絮凝剂对高岭土悬浊液具有良好的絮凝效果。     

乙二胺接枝型絮凝剂处理有机工业废水的研究

以聚丙烯酰胺、甲醛、乙二胺为原料,按照曼尼奇反应机理合成一种新型阳离子絮凝剂——乙二胺接枝型絮凝剂,实验表明,制备接枝型絮凝剂的最佳的条件为:聚丙烯酰胺∶甲醛∶乙二胺反应物质的量比=1∶1.40∶0.67,pH=10,温度=45℃,时间=4 h。实验证实接枝型絮凝剂处理模拟有机工业废水得到良好的效果:对于含苯废水COD为450.326 mg/L,经处理后剩余COD为66.502 mg/L,去除率达到了88.44%;对于含烃废水为695.060 mg/L,处理后剩余COD为65.990 mg/L,去除率达到了90.19%,均达到了国家规定的一级工业废水排放标准(COD≤100 mg/L)。     

壳聚糖-聚丙烯酰胺絮凝剂的制备及其絮凝性能研究

在氮气保护下,以硝酸铈铵为引发剂,壳聚糖(CS)和丙烯酰胺(AM)为原料,接枝制得壳聚糖-聚丙烯酰胺接枝共聚物P(CS-AM).以正交试验法得到CS接枝AM的最佳反应条件为:m(CS)∶m (AM)为1∶4,反应pH值为3,引发剂溶质占溶液质量分数为0.1％,水浴温度为55℃.分别采用红外光谱(FT-IR),扫描电镜(SEM),热重分析(TG)对产物进行表征.以处理高岭土模拟水样来评价其絮凝性能,考察了接枝率、絮凝剂投加量和体系pH对絮凝性能的影响,在此基础上,对比了CS、P(AM-CS)、聚丙烯酰胺(PAM)和聚合硫酸铝铁(PAFS)这4种絮凝剂的絮凝性能.结果 表明,P(CS-AM)处理高岭土模拟水样的上清液浊度为8NTU,絮凝性能明显优于CS、PAM和PAFS.     

新型双功能螯合絮凝剂的制备与性能研究

本文研究了以聚丙烯酰胺,甲醛,三乙烯四胺为原料,按照曼尼奇反应机理制备胺化接枝型双功能螯合絮凝剂及其性能研究.由于在聚丙烯酰胺的分子长链上引入了具有螯合作用的N原子,使得所得产物既具有捕捉金属离子的螯和作用又具有絮凝作用,因此处理含重金属离子的废水能力增强.以对重金属离子汞的去除率为考核指标选择最佳反应条件,考察了温度,聚合体系的pH值、反应时间、反应物料比对产物性能的影响.确定了适宜的反应条件为:反应温度35℃,聚合体系pH值为9,反应时间3.5 h,物料比(摩尔比)为聚丙烯酰胺∶甲醛∶三乙烯四胺=1∶0.54∶0.34.用所得絮凝剂分别处理含重金属离子汞、铜的高岭土悬浮液模拟废水,处理后的水能够达到国家允许的排放标准.     

疏水改性阳离子胶原蛋白絮凝剂制备条件优化

以皮革废弃物提取的明胶为原料,丙烯酰胺(AM)、丙烯酰氧乙基三甲基氯化铵(DAC)和丙烯酸丁酯(BA)为单体[n(AM)∶n(DAC)∶n(BA)=80∶18∶2],叔丁基过氧化氢和焦亚硫酸钠为引发剂,接枝共聚合成了疏水改性阳离子胶原蛋白絮凝剂P(C-AM-DAC-BA)。以絮凝剂对油田模拟废水浊度的去除率为指标,探讨了明胶与单体的质量比、引发剂浓度、接枝温度、接枝时间对絮凝效果的影响。通过响应面法优化得到了P(C-AM-DAC-BA)接枝共聚最佳条件为m(明胶)∶m(单体)=1∶2.04、引发剂浓度0.032 mol/L、接枝温度49℃、接枝时间2.8 h。在该条件下,P(C-AM-DAC-BA)对油田模拟废水浊度去除率为91.5%。     

海泡石/黄原胶复合絮凝剂的制备及应用研究

以过硫酸钾为引发剂,使丙烯酸/丙烯酰胺在黄原胶(XG)分子链上接枝聚合并复合海泡石纤维制备复合絮凝剂。研究了反应条件对含油废水COD去除率及浊度去除率的影响,利用红外光谱(FTIR)对接枝产物进行表征。实验结果表明,最佳合成条件为:m(丙烯酸/丙烯酰胺)∶m(黄原胶)=8∶1,引发剂、交联剂与黄原胶质量比分别为0.02,0.006,m(海泡石)∶m(黄原胶)=1∶2,反应温度60℃,用该絮凝剂处理含油废水,COD去除率和浊度去除率分别达到88.2%和95.6%。     

Stability constants of polymer‐bound iminodiacetate‐type chelating agents with some transition‐metal ions

A chelating vinyl monomer, glycidyl methacrylate (GMA)–iminodiacetic acid (IDA), was formed by the reaction between GMA and IDA. Three polymeric chelating agents, PGMA–IDA, PGMA–IDA‐co‐methyl acrylate (MA), and PGMA–IDA‐co‐acrylamide (AAm), were also synthesized. Acid dissociation constants and stability constants of these chelating agents with Ni(II), Zn(II), and Co(II) were determined by means of potentiometric titration and ultraviolet–visible spectrophotometry, respectively. The values of K_a1 and K_a2 of all the polymeric chelating agents were smaller than those of GMA–IDA. The stability constants of all the polymeric chelating agents were larger than those of GMA–IDA. Increasing the MA content within PGMA–IDA‐co‐MA affected the stability constant only slightly. A proper molar ratio of AAm in PGMA–IDA‐co‐AAm, stability constants was 30–60 times greater than that of GMA–IDA. However, as the molar content of AAm increased, the stability constant of PGMA–IDA‐co‐AAm decreased. The results obtained in the polymer system are explained in terms of the polymer's stereo and entanglement structure, the neighboring effect, and the hydrophobic/hydrophilic nature of MA or AAm. © 2002 Wiley Periodicals, Inc. J Appl Polym Sci 86: 1986–1994, 2002     

螯合剂聚一烃基二硫代氨基甲酸钠的合成研究

以聚丙烯酰胺为初始原料,通过两步反应,合成了聚一烃基二硫代氨基甲酸钠(PADC)重金属离子螯合剂,用IR对中间产物PVAm.HC l及目标物PADC的结构进行了表征。用正交实验法考察了反应物料比、温度、反应时间、浓度等因素对中间产物PVAm.HC l及目标产物PADC转化率的影响,得到了PVAm.HC l最佳合成条件:反应温度-5℃,次氯酸钠、氢氧化钠与聚丙烯酰胺链节物质量之比为1∶1∶31,反应时间11 h,此时胺化度达到最大值81.6%。PADC最佳合成条件:反应温度30℃,聚乙烯胺盐酸盐浓度为40 g/L,CS2、NaOH与PVAm.HC l链节物质量之比为1.1∶1.9∶1,反应时间3 h,此时转化率达到最大值61.9%。     

亚胺基二乙酸树脂对金属镍的静态吸附及连续逆流U形解吸系统

研究了亚胺基二乙酸型螯合树脂R604对模拟含镍废水中镍离子静态交换吸附性能的主要影响因素,包括废水浓度、pH值、温度等,还研究了吸附平衡态、吸附过程的动力学,热力学,并给出了相应的模型,这些模型均与实验结果有很好的符合度,最后研究了独创的U形解吸柱系统对吸附饱和树脂的解吸性能,探讨了树脂停留时间、解吸液树脂流量比对解吸率和金属浓缩液浓度在柱体内分布的影响.研究表明,亚胺基二乙酸型树脂在废水金属离子镍的去除中有着高效、独特的性能,连续逆流U形解吸系统能提高重金属浓缩液浓度,并大幅度节省解吸液用量,减少解吸时间.     

Static adsorption properties of Ni（Ⅱ）by IDA resin and U-shaped continuous countercurrent desorption

研究了亚胺基二乙酸型螯合树脂R604对模拟含镍废水中镍离子静态交换吸附性能的主要影响因素,包括废水浓度、pH值、温度等,还研究了吸附平衡态、吸附过程的动力学、热力学,并给出了相应的模型,这些模型均与实验结果有很好的符合度。最后研究了独创的U形解吸柱系统对吸附饱和树脂的解吸性能,探讨了树脂停留时间、解吸液树脂流量比对解吸率和金属浓缩液浓度在柱体内分布的影响。研究表明,亚胺基二乙酸型树脂在废水金属离子镍的去除中有着高效、独特的性能,连续逆流U形解吸系统能提高重金属浓缩液浓度,并大幅度节省解吸液用量,减少解吸时间。     

Iron chelating polypropylene films: Manipulating photoinitiated graft polymerization to tailor chelating activity

Transition metals, especially iron, enhance the oxidative degradation of lipids. Nonmigratory metal chelating active packaging can inhibit lipid oxidation and meet consumer demand for ‘cleaner' labels. Recently, the development of iron chelating films prepared by photoinitiated graft polymerization of acrylic acid on polypropylene (PP‐g‐PAA) was reported. The objective of this study was to tailor the chelating activity of PP‐g‐PAA by manipulating graft conditions. Carboxylic acids graft density and PAA graft thickness increased with graft time and acrylic acid concentration, with carboxylic acids density of up to 143 ± 32 nmol cm^?2, PAA graft thickness of ～6–18 μm, and ligand (carboxylic acid) to metal (Fe²⁺) binding ratio of ～4–5. Reducing photoinitiator graft density decreased this ratio to ～2–2.5, suggesting that graft chain density influences chelating activity. This work demonstrates the ability to tailor chelating activity of PP‐g‐PAA with potential applications in active packaging, chelation therapy, and water purification. © 2013 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2014 , 131, 39948.     

Chelating polymer-based membranes. Preparation and use for metal ion scavenging and sorption of murine immunoglobulin G by immobilized Ni(II) ions

Copolymers of 2-(2-hydroxyethoxy)ethyl methacrylate and ethylene dimethacrylate in the form of homogeneous membrane sheets were modified by chelating groups of iminodiacetic acid (IDA) in a two step reaction. The obtained sorbents showed high chelating capacity for Ni(II), Cu(II) and Fe(III) ions (up to 1.3 mmol/g). The potential use of immobilized Ni(II)-IDA complexes for sorption of murine immunoglobulin G by the immobilized metal affinity (IMA) method was tested. The sorption behaviour was characterized by a Langmuir-Freundlich adsorption isotherm. It was shown that the chelating membranes could be used for the sorption of low amounts of protein.     

Synthesis of chelating resins with iminodiacetic acid and its wastewater treatment application

The chelating resins have high potential applications for the selective removal and recovery of metal ions from industrial waste solutions. The hydrophilic acrylate monomer with the iminodiacetic acid chelating group was prepared from glycidyl methacrylate and iminodiacetic acid at 60°C. The microbeads, prepared from acrylate monomer with the iminodiacetic acid chelating group, were employed by inversion suspension polymerization. In the pH range of 2–6, a reasonably good equilibrium sorption capacity is maintained for Cr³⁺ (ca. 2.7 mmol/g) and Cu²⁺ (ca. 1.8 mmol/g) in the chelating resins. The adsorption of Cd²⁺ and Pb²⁺ on microbeads is clearly affected by the pH of the solution, such that these ions' adsorption capacity increased with the pH of the aqueous solution. The adsorption of Cd²⁺ (ca. 1.25–1.87 mmol/g) and Pb²⁺ (ca. 0.99–1.89 mmol/g) showed a maximum at approximately pH = 5 and 6, respectively. The adsorption isotherms of Cr³⁺ and Cu²⁺ adsorbed on microbeads were following the Langmuir isotherm, but the adsorption behavior of Cd²⁺ and Pb²⁺ were not. The concentration of alkaline earth–metal cations on the range of 0–200 ppm had no influence on metal ions adsorbed capacity of chelating resins. Additionally, NTA (nitrilotriacetic acid) had no significant influence on metal ion adsorption by chelating resins. Furthermore, phenol pollutant can be adsorbed effectively by metal ions chelated microbeads; therefore, the microbeads were useful not only in recovering metal ions but also in the treating phenol pollutants in wastewater. © 2002 Wiley Periodicals, Inc. J Appl Polym Sci 84: 1353–1362, 2002; DOI 10.1002/app.10243     

废硫酸在双甘膦生产工艺中的应用

[目的]甘氨酸(Gly)法合成草甘膦产生大量的废硫酸,为了提高废硫酸的附加值,将其应用到亚氨基二乙酸(IDA)法草甘膦生产工艺中.[方法]采用废硫酸代替盐酸作为催化剂,以亚氨基二乙酸为主要原料与亚磷酸、甲醛发生反应生成双甘膦.[结果]实验结果表明:使用废硫酸对合成双甘膦反应收率及产品品质均无影响.[结论]对该工艺进行了经济效益分析,结果表明具有良好的经济效益.     

Biomimetic design of chelating interfaces

Siderophores are naturally occurring small molecules with metal binding constants greater than many synthetic chelators. Herein, we report a two‐step process to graft a siderophore‐mimetic metal chelating polymer from a polypropylene (PP) surface. Poly(methyl acrylate) was first grafted from the PP surface by photoinitiated graft polymerization, followed by the conversion into poly(hydroxamic acid) (PHA) to obtain PP‐g‐PHA films. ATR/FTIR, contact angle, SEM, and AFM were performed to characterize surface properties of films. Iron binding kinetics and the influence of pH (3.0–5.0) on the chelating ability of films were determined. PP‐g‐PHA exhibited significant iron chelating activity (～80 nmol/cm²) with an equilibration time of 24 h. The materials retained 50% chelating ability at pH 3.0 compared with pH 5.0, almost double the retention of previously reported polycarboxylate chelating interfaces. By using siderophore‐mimetic surface chemistry, such effective metal chelating interfaces can extend the applications of metal chelating polymers in environmental remediation, water purification, and active packaging areas. © 2014 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2015 , 132, 41231.