聚合氯化铁—聚环氧氯丙烷胺复合混凝剂的性能及机理研究
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摘要
本论文制备出一系列具有不同聚合氯化铁(PFC)的碱化度(B)、不同聚环氧氯丙烷-二甲胺(EPI-DMA)质量分数(w(E))和特性粘度(η)的无机-有机复合混凝剂PFC-EPI-DMA,并将其用于处理不同性质的模拟水样。通过烧杯试验、zeta电位的测定、Ferron逐时络合比色法、光散射法等多种化学分析方法及现代分析仪器测试技术对比研究了该复合混凝剂与传统混凝剂在模拟染料废水处理中的性能和混凝机理的差异,考察了w(E)值、η值、B值和熟化时间等对PFC-EPI-DMA复合混凝剂铁的水解形态分布和混凝性能的影响。主要结论归纳如下：
(1)采用Ferron逐时络合比色法研究PFC-EPI-DMA复合混凝剂体系中铁的形态分布,发现该复合混凝剂中EPI-DMA的加入会影响铁的水解形态分布。单就Feb含量而言,w(E)=3.5%、η=850 mPa·s、B=0.5的PFC-EPI-DMA复合混凝剂熟化1天时其含量最高。
(2)处理模拟活性艳红染料废水时PFC-EPI-DMA的性能明显优于PFC单独使用。与将PFC和EPI-DMA以不同的顺序投加相比,PFC-EPI-DMA在实验投加量范围内虽然电中和能力较弱,但是其脱色性能较高。而在处理模拟活性翠兰染料废水时PFC-EPI-DMA与PFC和EPI-DN(?)A以不同的顺序投加以及PFC单独使用相比,虽然其在较高投加量下电中和能力最强,但是其脱色性能最差。PFC-EPI-DMA处理模拟染料废水时一般在高w(E)值和高η值、低B值、低熟化时间、pH值接近中性条件下具有较好的脱色效果。
(3)与PFC相比,PFC-EPI-DMA复合混凝剂在处理活性艳红时可以大幅提高絮体生成速度,缩短混凝剂与污染物反应时间,并提高最终絮体粒度,同时会增大絮体差异性；但PFC-EPI-DMA在处理活性翠兰时,较低投加量下降低絮体生成速度,并减小最终絮体粒度和絮体差异性。处理活性艳红时,w(E)值越大,PFC-EPI-DMA形成的絮体增长速度越快,形成的最终絮体粒度越大,同时絮体差异性增大。处理活性翠兰时,在较低投加量下,w(E)值越小,PFC-EPI-DMA形成的絮体增长速度越快,形成的最终絮体粒度越大,同时絮体差异性增大；在较高投加量下,w(E)值越大,PFC-EPI-DMA形成的絮体增长速度越快,形成的最终絮体粒度越大,同时絮体差异性减小。在η值较高、B值较低和pH值接近中性(6.0-7.5)条件下,PFC-EPI-DMA与染料反应时间较短,絮体增长速度较快,絮体最终粒度较大,絮体差异性较小。絮体增长速度、絮体最终粒度和絮体差异性随着熟化时间的变化规律较为复杂,而且大多与两种混凝剂处理模拟染料废水时脱色率随着熟化时间的变化规律不符合。
(4)处理模拟天然地表水时,PFC-EPI-DMA与PFC相比其混凝效果有一定程度的降低。一般在低w(E)值和低B值、高η值条件下,PFC-EPI-DMA对模拟天然地表水具有较好的混凝效果。
上述研究初步明确了PFC-EPI-DMA处理不同模拟水样的混凝效果、混凝行为和机理等,为高效、经济的PFC-EPI-DMA复合混凝剂的研发和应用提供理论指导。
In this paper, a series of composite inorganic-organic coagulant was prepared by polyferric chloride (PFC) and epichlorohydrin-dimethylamine (EPI-DMA) with different basicity (B) of PFC, different mass fraction (w(E)) and intrinsic viscosity (η) of EPI-DMA. The advantage of PFC-EPI-DMA over PFC and successive addition of PFC and EPI-DMA in coagulation efficiency and the difference of them in coagulation mechanism were revealed. The effect of B value, w(E),ηvalue and aging period on coagulation efficiency, Fe(Ⅲ) species distribution and floc aggregation process were studied by a variety of methods and technology, such as jar test, zeta potential measurement, Fe-Ferron method and photometric dispersion analyzer. The main conclusions are as follows:
(1) Fe-Ferron method was used to examine Fe (Ⅲ) species distribution of PFC-EPI-DMA. The addition of EPI-DMA significantly affects the Fe (Ⅲ) species distribution of the composite coagulant. When w(E)=3.5%、η=850 mPa·s、B=0.5, the content of Feb was the highest in PFC-EPI-DMA with 1d aging.
(2) For the treatment of synthetic reactive red wastewater, PFC-EPI-DMA was more efficient than PFC. Compared with successive addition of PFC and EPI-DMA in two reactive dyes wastewater, PFC-EPI-DMA gave higher color removal efficiency but weaker charge neutralization ability in reactive red wastewater treatment, whereas it gave lower color removal efficiency but stronger charge neutralization ability in reactive blue wastewater treatment. In the middle pH range, PFC-EPI-DMA generally achieved better color removal efficiency at higher w(E) andηvalue, lower B value and aging period.
(3) For the treatment of synthetic reactive red wastewater, floc growth velocity (Growth rate), the average floc size (Ratio) and the time-weighted steady state variance (TWV) of PFC-EPI-DMA were larger than those of PFC. However, these three parameters of PFC-EPI-DMA were smaller than those of PFC at lower dosage range when treated synthetic reactive blue wastewater. With the increase of w(E) value, three parameters were all increased in reactive red wastewater treatment. For the treatment of synthetic reactive blue wastewater, PFC-EPI-DMA achieved larger Growth rate and Ratio but lower TWV at lower dosage with increasing w(E) value. However, the orders of three parameters at high dosage were contrary to those at low dosage. In the middle pH range, PFC-EPI-DMA with higherηvalue and lower B value achieved larger Growth rate and Ratio, smaller TWV. The effect of aging time on three parameters was complicated.
(4) Compared with PFC, PFC-EPI-DMA achieved worse turbidity and organic matter removal in synthetic natural surface water treatment. Generally speaking, PFC-EPI-DMA with higherηvalue, lower w(E) and B value achieved better coagulation performance.
The primary coagulation efficiency, coagulation behavior and coagulation mechanism of PFC-EPI-DMA were confirmed in different synthetic water treatment. These contents will provide the theory for impoldering and applying PFC-EPI-DMA.
(1)采用Ferron逐时络合比色法研究PFC-EPI-DMA复合混凝剂体系中铁的形态分布,发现该复合混凝剂中EPI-DMA的加入会影响铁的水解形态分布。单就Feb含量而言,w(E)=3.5%、η=850 mPa·s、B=0.5的PFC-EPI-DMA复合混凝剂熟化1天时其含量最高。
(2)处理模拟活性艳红染料废水时PFC-EPI-DMA的性能明显优于PFC单独使用。与将PFC和EPI-DMA以不同的顺序投加相比,PFC-EPI-DMA在实验投加量范围内虽然电中和能力较弱,但是其脱色性能较高。而在处理模拟活性翠兰染料废水时PFC-EPI-DMA与PFC和EPI-DN(?)A以不同的顺序投加以及PFC单独使用相比,虽然其在较高投加量下电中和能力最强,但是其脱色性能最差。PFC-EPI-DMA处理模拟染料废水时一般在高w(E)值和高η值、低B值、低熟化时间、pH值接近中性条件下具有较好的脱色效果。
(3)与PFC相比,PFC-EPI-DMA复合混凝剂在处理活性艳红时可以大幅提高絮体生成速度,缩短混凝剂与污染物反应时间,并提高最终絮体粒度,同时会增大絮体差异性；但PFC-EPI-DMA在处理活性翠兰时,较低投加量下降低絮体生成速度,并减小最终絮体粒度和絮体差异性。处理活性艳红时,w(E)值越大,PFC-EPI-DMA形成的絮体增长速度越快,形成的最终絮体粒度越大,同时絮体差异性增大。处理活性翠兰时,在较低投加量下,w(E)值越小,PFC-EPI-DMA形成的絮体增长速度越快,形成的最终絮体粒度越大,同时絮体差异性增大；在较高投加量下,w(E)值越大,PFC-EPI-DMA形成的絮体增长速度越快,形成的最终絮体粒度越大,同时絮体差异性减小。在η值较高、B值较低和pH值接近中性(6.0-7.5)条件下,PFC-EPI-DMA与染料反应时间较短,絮体增长速度较快,絮体最终粒度较大,絮体差异性较小。絮体增长速度、絮体最终粒度和絮体差异性随着熟化时间的变化规律较为复杂,而且大多与两种混凝剂处理模拟染料废水时脱色率随着熟化时间的变化规律不符合。
(4)处理模拟天然地表水时,PFC-EPI-DMA与PFC相比其混凝效果有一定程度的降低。一般在低w(E)值和低B值、高η值条件下,PFC-EPI-DMA对模拟天然地表水具有较好的混凝效果。
上述研究初步明确了PFC-EPI-DMA处理不同模拟水样的混凝效果、混凝行为和机理等,为高效、经济的PFC-EPI-DMA复合混凝剂的研发和应用提供理论指导。
In this paper, a series of composite inorganic-organic coagulant was prepared by polyferric chloride (PFC) and epichlorohydrin-dimethylamine (EPI-DMA) with different basicity (B) of PFC, different mass fraction (w(E)) and intrinsic viscosity (η) of EPI-DMA. The advantage of PFC-EPI-DMA over PFC and successive addition of PFC and EPI-DMA in coagulation efficiency and the difference of them in coagulation mechanism were revealed. The effect of B value, w(E),ηvalue and aging period on coagulation efficiency, Fe(Ⅲ) species distribution and floc aggregation process were studied by a variety of methods and technology, such as jar test, zeta potential measurement, Fe-Ferron method and photometric dispersion analyzer. The main conclusions are as follows:
(1) Fe-Ferron method was used to examine Fe (Ⅲ) species distribution of PFC-EPI-DMA. The addition of EPI-DMA significantly affects the Fe (Ⅲ) species distribution of the composite coagulant. When w(E)=3.5%、η=850 mPa·s、B=0.5, the content of Feb was the highest in PFC-EPI-DMA with 1d aging.
(2) For the treatment of synthetic reactive red wastewater, PFC-EPI-DMA was more efficient than PFC. Compared with successive addition of PFC and EPI-DMA in two reactive dyes wastewater, PFC-EPI-DMA gave higher color removal efficiency but weaker charge neutralization ability in reactive red wastewater treatment, whereas it gave lower color removal efficiency but stronger charge neutralization ability in reactive blue wastewater treatment. In the middle pH range, PFC-EPI-DMA generally achieved better color removal efficiency at higher w(E) andηvalue, lower B value and aging period.
(3) For the treatment of synthetic reactive red wastewater, floc growth velocity (Growth rate), the average floc size (Ratio) and the time-weighted steady state variance (TWV) of PFC-EPI-DMA were larger than those of PFC. However, these three parameters of PFC-EPI-DMA were smaller than those of PFC at lower dosage range when treated synthetic reactive blue wastewater. With the increase of w(E) value, three parameters were all increased in reactive red wastewater treatment. For the treatment of synthetic reactive blue wastewater, PFC-EPI-DMA achieved larger Growth rate and Ratio but lower TWV at lower dosage with increasing w(E) value. However, the orders of three parameters at high dosage were contrary to those at low dosage. In the middle pH range, PFC-EPI-DMA with higherηvalue and lower B value achieved larger Growth rate and Ratio, smaller TWV. The effect of aging time on three parameters was complicated.
(4) Compared with PFC, PFC-EPI-DMA achieved worse turbidity and organic matter removal in synthetic natural surface water treatment. Generally speaking, PFC-EPI-DMA with higherηvalue, lower w(E) and B value achieved better coagulation performance.
The primary coagulation efficiency, coagulation behavior and coagulation mechanism of PFC-EPI-DMA were confirmed in different synthetic water treatment. These contents will provide the theory for impoldering and applying PFC-EPI-DMA.
引文
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