【作者】 刘立华；

【导师】 龚竹青；

【作者基本信息】 中南大学 ， 冶金物理化学， 2004， 博士

【摘要】 水污染已严重威胁人们的生活和经济的可持续发展。新型高效絮凝剂的开发对控制水污染具有十分重要的意义。有机-无机复合絮凝剂可兼具有机和无机絮凝剂的优点，是一类新型高效絮凝剂，已成为絮凝剂研究的一个重要新方向和研究热点。本研究合成了系列新型聚季铵盐与聚合硫酸铁复合絮凝剂（PQAS—PFS），并对其相关基础问题与应用性能进行了系统研究。 开发了合成二甲基二烯丙基氯化铵（DMDAAC）新的二步法工艺：先在高压釜中合成中间产物二甲基烯丙基胺（DMAA），将它与水相分离后，与等摩尔烯丙基氯在丙酮中反应合成DMDAAC；水相经浓缩、中和，使成盐的二甲胺再生，然后返回高压釜进入下一轮反应。DMAA的收率比采用交替滴加法合成DMAA的二步法工艺提高了27.1％，废液排放量下降了1.12mL／（mL DMAA）。获得高纯无色针状晶体DMDAAC，其熔点为144.5～146.1℃，总收率达89.07％。采用膨胀计法研究得到过硫酸铵水溶液引发体系中，DMDAAC均聚及其与丙烯酰胺（AM）和丙烯酸（AA）共聚动力学方程分别为：R_P=kc_I^0.76C_M^1.02（DMDAAC），R_P=kc_I^0.70C_M^2.23（DM-AM，4：1），R_P=kc_I^0.61C_M^2.83（DM-AA，4：1），相应的表观聚合活化能分别为71.958、58.221和64.312kJ／mol；测得DMDAAC与AM共聚的竞聚率为γ_DM=0.49、γ_AM=5.49，与AA的竞聚率为γ_DM=0.42、γ_AA=5.11。在此基础上，设计并合成了聚二甲基二烯丙基氯化铵（PDMDAAC）、二甲基二烯丙基氯化铵-丙烯酰胺共聚物（P（DM-AM））和二甲基二烯丙基氯化铵-丙烯酸共聚物（P（DM-AA））。 以二乙胺为溶剂和反应物，首次采用交替滴加烯丙基氯和NaOH合成中间产物二乙基烯丙基胺（DEAA），再使之与等摩尔烯丙基氯在丙酮中反应的二步法工艺，得到高纯柱状晶体二乙基二烯丙基氯化铵（DEDAAC），测定其熔点为199.5～201.0℃，总收率为58.41％。首次研究得到过硫酸铵水溶液引发体系中，DEDAAC均聚及与AM、AA共聚的动力学方程分别为：R_P=kc_I^0.76C_M^0.99（DEDAAC），R_P=kc_I^0.90C_M^2.53（DE-AM，4：1），R_P=kc_I^0.83C_M^2.94（DE-AA，4：1）；相应的聚合表观活化能分别为73.596、67.061和70.070kJ／mol；DEDAAC与AM共聚的竞聚率为γ_DE=0.32、γ_AM=5.27，与AA共聚的竞聚率为Y_DE=0.30、Y_AA=5.19。合成了新型聚季铵盐聚二乙基二烯丙基氯化铵（PDEDAAC）、二乙基二烯丙基氯化铵-丙烯酰胺共聚物（P（DE-AM））和二乙基二烯丙基氯化铵-丙烯酸共聚物（P（DE-AA））。 发现PDMDAAC和PDEDAAC、阳离子度大于30mol％的P（DM-AM）和P（DE-AM）、阳离子度大于65mol％的两性共聚物P（DM-AA）和P（DE-AA），以及中南大学博士学位论文摘要聚乙烯毗咯烷酮（P vP）和聚苯乙烯磺酸钠伽aPSS)能与PFS复配形成较稳定的均相溶液，合成了pnMnAAC一pFs、p(DM一AM卜PFs、p(DM.AA卜PFS、PDEnAAC-PFs、P(DE一AM卜PFs和p(DE^AA卜pFS等6类pQAS一pFS复合絮凝hIJ。 首次采用粘度法探讨了PQAs在PFS中的分子链运动形态，采用FT一IR、sEM、X一射线衍射和Fe一Ferron逐时络合比色法分别研究了PQAS与PFS的相互作用和PQAS一PFS中Fe（m）的分子形态分布的变化规律。结果表明，在一定的浓度范围内，PQAS在强酸性、高盐浓度的PFS体系中能够保持良好的分子链伸展构象，能在较宽的浓度和盐基度范围内与PFS复配形成稳定的均相复合溶液;PQAs一PFs中Fe（a）含量有所下降、Fe（b）明显减少、Fe（e）的含量明显增加;PQAs主要与铁的多核轻基络合物特别是高电荷的多核轻基络合物作用，如与pFS中Fe4石7（504）6（oH）2·20H2o物相发生作用，使其X一射线衍射峰消失。 探明了PQAs在PFS中稳定机制:①毗咯环周围的甲基或乙基构成对正电荷的天然屏障，使电场斥力区始终存在:②环状阳离子在主链上分布均匀，且环的体积大，保持较大的链刚性，使分子线团蜷缩的位阻大;③铁的高电荷阳离子基团能促使PQAS分子链伸展。 采用密度一密度相关函数法计算得到了PFS、PDMDAAC和上述6种PQAS一PFS处理硅藻土悬浊液产生的絮体分维。表明PQAS一PFS产生的絮体分维比PFS和PDMDAAC的大，不同类型的PQAS一PFS产生的絮体分维存在明显差异。从分形学的角度探讨了絮体沉降速度与分维的关系，发现分维大的絮体结构致密，沉降速度快。絮体内孔的可渗透性有利于降低沉降阻力，提高沉降速度。 对硅藻土模拟悬浊液和生活污水的处理表明，PQAS一PFS具有比PFS和PQAS更优的除污能力，有与PFS类似的较宽用量范围和适宜的pH范围，其使用效果比分开加入PQAS和PFS的效果好。处理浊度和COD分别为105.2和187.5mg/L的生活污水时，PQAS一PFS的较佳用量相当于4.27m叭PQAS和54.17mg/L pFS（以Fe计），单独使用pQAS和pFS的较佳用量分别为14.5和sl.27mg/L，其浊度去除率稍高于pFS，L匕pQAS高约10%;eOD的去除率比PFs高15%以上，比PQAS高10%左右;其药剂成本与PFS相当或稍低，但明显低于相应的PQAS。对活性污泥的脱水试验表明，PQAS一PFS在降低污泥比阻、滤液的浊度和COD等方面均比单独使用PFS、PQAS和实际应用的脱水剂CPF13O好，而其中PQAS和PFS两组分的用量分别比单独使用PQAS和PFS降低了一更多还原

【Abstract】 Water pollution has seriously threatened to people’s life and sustainable development of economy. The exploitation of new high-effective flocculants is of great importance to control water pollution. The organic-inorganic composite flocculant, a new type of high-effective flocculants, has become a hot issue and a new important development direction in the study of flocculant because it has not only the merits of organic constituents but also the merits of inorganic ones. In this paper, a series of new type polymeric quarternary ammonium salt and polyferric sulfate composite flocculants (PQAS-PFS) were synthesized, and the related fundamental theory and application properties of PQAS-PFS were studied systematically.A new two-step method for synthesizing dimethyldiallylammonium chloride (DMDAAC) was exploited: the in-process product dimethylallylamine (DMAA) was synthesized in autoclave firstly, and then reacted with equimolar allyl chloride in acetone to synthesize DMDAAC after separated from water phase; the chlorinated dimethylamine was regenerated by concentrating and neutralizing the separated water phase, and was returned to the autoclave to react next time. Compared with the synthesis of DMAA by adding allyl chloride and sodium hydroxide alternately, the yield of DMAA increased 27.1% and the emission of waste liquid decreased 1.12mL/(mL DMAA). Colorless spiculite DMDAAC (m.p. 144.5~146.1C) with high purity is obtained, and its total yield is up to 89.07%. The polymerization kinetic equations of DMDAAC and the copolymerization kinetic equations of DMDAAC with acrylamide (AM) or acrylic acid (AA) initiated by ammonium persulfate (APS) in aqueous solution are obtained by dilatometric method as follows:Rp=kcI0.76cM1.02 (DMDAAC)Rp=kcI0.70CM2.23 (DM-AM, 4 11)RP=kcI0.61cM2.83 (DM-AA, 4 : 1)The corresponding apparent polymerization activation energies are 71.958, 58.221 and 64.312kJ/mol. The monomeric reactivity ratios of DMDAAC with AM are determined to be r DM= 0.49, r am = 5.49, and those of DMDAAC with AA are r Dm = 0.42, raa= 5.11. On the base of polymerization kinetics and monomeric reactivity ratios, poly(DMDAAC) (PDMDAAC) with different intrinsic viscosity, poly (DMDAAC-AM)(P(DM-AM)) and poly (DMDAAC-AA) (P(DM-AA)) with different intrinsic viscosity and different cationic degrees are designed and synthesized.The columnar crystals diethyldiallylammonium chloride (DEDAAC) with higher purity were obtained firstly by two-step method in which the in-process product diethylallylamine (DEAA) was synthesized using diethylamine as reactant and solvent by adding allyl chloride and sodium hydroxide alternately, and DEDAAC was synthesized by adding equimolar DEAA and allyl chloride in acetone. Its melting point is determined to be 199.5-201.0 C, and its total yield is 58.41%. The polymerization kinetic equation of new type DEDAAC and the copolymerization kinetic equations of DEDAAC with AM or AA initiated by APS in aqueous solution are obtained as follows:Rp=kcI0.76CM0.99 (DEDAAC)Rp=kcI0.90cM2.53 (DE-AM, 4:1)RP=kcI0.83cM2.94 (DE-AA, 4 : 1)The corresponding apparent polymerization activation energies are 73.596, 67.061 and 70.070 kJ/mol, and the monomeric reactivity ratios of DEDAAC with AM are r DE = 0.32, r am = 5.27, and those of DEDAAC with AA are r De = 0.30, Y aa = 5.19. The new type of polymeric quarternary ammonium salts PDEDAAC, P(DE-AM) and P(DE-AA) are synthesized initially.It was firstly found that polymers PDMDAAC and PDEDAAC, copolymers P(DM-AM) and P(DE-AM) with cationic degree above 30mol%, amphoteric copolymers P(DM-AA) and P(DE-AA) with cationic degree above 65mol%, poly vinyl pyrrolidone (PVP) and poly(sodium styrenesulfonate) (NaPSS) could compound with PFS well and formed homogeneous phase composite solutions. Six kinds of PQAS-PFS as PDMDAAC-PFS, P(DM-AM)-PFS, P(DM-AA)-PFS, PDEDAAC-PFS, P(DE-AM)-PFS and P(DE-AA)-PFS were synthesized.The viscometer was firstly employed to study motion mode of PQAS molecular chain in PFS, FT-IR, SEM and X-ray diffraction and Fe更多还原