活性污泥对染料废水吸附性能的研究
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摘要
吸附是印染废水处理的主要工艺之一。很久以前人们就注意到活性污泥对有机物的吸附作用,然而对于活性污泥吸附的主要影响因素、吸附模型、吸附机理以及活性污泥与其他吸附剂的比较研究罕有报道。
本研究以人工配制的结晶紫、酸性品红6B、活性黑5的模拟染料废水为处理对象,对活性污泥吸附染料的性能进行了系统的研究。采用正交实验,对比研究了活性污泥、活性炭、硅藻土对三种不同染料的吸附性能,分析了活性污泥的吸附机理。
研究表明,活性污泥对三种染料的吸附试验达到平衡的时间分别为30min,20min和70min左右,脱色率分别达81%、89%和10%左右。活性污泥投加量增加可以提高染料脱色率,但活性污泥的吸附容量降低。加大吸附过程的搅拌速度对活性污泥吸附染料的容量没有明显影响。pH值升高时,结晶紫吸附容量略有增大,而酸性品红6B的吸附容量略有减小,但脱色率均可达到90%以上。对于活性黑5,pH值由低升高时,活性污泥对它的吸附容量先快速降低,在pH值为6.6~9.9之间基本不变并维持在很低水平;之后,随着pH值的继续升高,吸附容量逐渐增加。
吸附模型研究表明,活性炭、硅藻土和活性污泥对三种染料的吸附符合Freundlich模型,对酸性品红和活性黑5的吸附还较好地符合Langmuir模型。活性污泥对三种染料吸附性能的优劣顺序为:酸性品红6B>结晶紫>活性黑5。二级动力学模型均能很好地描述三种染料在三种不同吸附剂上的吸附动力学行为。对于活性黑5,颗粒内扩散过程是其在三种吸附剂上吸附速率的控制步骤,颗粒内扩散也是活性污泥吸附三种染料的控制步骤,但不是唯一的控制步骤。对于活性炭和硅藻土吸附结晶紫与酸性品红,颗粒内扩散不是速率控制步骤。假一级吸附速率常数k1和假二级吸附速率常数k2的值随污泥量的增加而增大,而颗粒内扩散常数kp却随污泥量的增加而减小。
通过析因试验,证明了活性污泥对活性黑5的吸附主要是由于染料分子的磺酸基氧负电荷中心与-NH3+相结合而产生的化学吸附,同时也说明这种吸附机制主要发生在污泥中的微生物细胞外,吸附是细胞外物质的性质;pH值和离子浓度的交互作用达到极其显著的程度( F值达1128.67和1562.04),说明在中性或酸性条件下盐度对染料在污泥上的吸附有很大的影响。
Adsorption is one of the main approaches in dyeing wastewater treatment. The organic matter adsorption by activated sludge has been observed for a long time. However, systematic studies on this subject, including major factors affecting the adsorption process, the quantitative adsorption modeling, comparative studies of activated sludge with different adsorbents and its mechanism have not been reported yet.
Keeping the above points under consideration, a systematic study on the adsorption of activated sludge was carried out by using the simulated dye wastewater of acid fuchsine 6B (AF)、crystal violet (CV) and reactive black 5 (RB5) as the treatment object. Comparisions were made with activated carbon (AC) and diatomite and mechanism were discussed.
It was found that, the equilibrium time of CV、AF and RB5 onto live activated sludge is 30min,20min and 70min, color removal rate can reach 81%、89% and 10% respectly. When the dosing quatity of AS is increased, the color removal of dye wastewater increases, while the adsorption quantity decreases. High stirring rate has little effect on dyestuff adsorption. Increase of pH value can increase adsorption quantity of CV slightly, but decrease that of AF, while keeping their removal rate at above 90%. PH value had great effect on the adsorption of RB5. As pH value increased, its adsorption quantity decreases quckly. When pH value is around 6.6~9.9, it keeps stable but very low. And then it increases slightly with the increase of pH.
Adsorption model study showed that the adsorption of these three dyestuffs onto AC, diatomite and AS fit well with Freundlich model and their adsorption of AF and RB5 also fit well with Langmuir model. The order of adsorption capacity of AS for the three dyestuffs was as follow: AF>CV>RB5. The adsorption of these three dyesuffs all followed the psudo-second kinetic model. For the adsorption of RB5 onto the three adsorbents and the three dyestuffs adsorbed onto AS, the intrapaticle disffusion is one of rate controlling step, whereas for the adsorption of AF and CV onto AC and diatomite, the intra-paticle disffusion is not the rate controlling step. It was also observed that the psudo-first rate constant k1 and psudo-second rate constant k2 all increased with the increasing of AS dosage, while the intra-paticle rate constant kp decreased.
The results of the cause-analyzing experiments upheld our hypothesis about the mechanism of the adsorption of RB5 onto AS. It also indicates that the mechanism of the adsorption occurs mainly outside the microbial cell, it is the nature of extracellular substances. The interaction of pH and ionic concentration achieved a very notable degree (the numbers of F are 1128.673 and 1562.044), which tells us that the ionic concentration may wield tremendous influence on the sludge’s adsorption to dyestuffs in neutral or acidic conditions.
本研究以人工配制的结晶紫、酸性品红6B、活性黑5的模拟染料废水为处理对象,对活性污泥吸附染料的性能进行了系统的研究。采用正交实验,对比研究了活性污泥、活性炭、硅藻土对三种不同染料的吸附性能,分析了活性污泥的吸附机理。
研究表明,活性污泥对三种染料的吸附试验达到平衡的时间分别为30min,20min和70min左右,脱色率分别达81%、89%和10%左右。活性污泥投加量增加可以提高染料脱色率,但活性污泥的吸附容量降低。加大吸附过程的搅拌速度对活性污泥吸附染料的容量没有明显影响。pH值升高时,结晶紫吸附容量略有增大,而酸性品红6B的吸附容量略有减小,但脱色率均可达到90%以上。对于活性黑5,pH值由低升高时,活性污泥对它的吸附容量先快速降低,在pH值为6.6~9.9之间基本不变并维持在很低水平;之后,随着pH值的继续升高,吸附容量逐渐增加。
吸附模型研究表明,活性炭、硅藻土和活性污泥对三种染料的吸附符合Freundlich模型,对酸性品红和活性黑5的吸附还较好地符合Langmuir模型。活性污泥对三种染料吸附性能的优劣顺序为:酸性品红6B>结晶紫>活性黑5。二级动力学模型均能很好地描述三种染料在三种不同吸附剂上的吸附动力学行为。对于活性黑5,颗粒内扩散过程是其在三种吸附剂上吸附速率的控制步骤,颗粒内扩散也是活性污泥吸附三种染料的控制步骤,但不是唯一的控制步骤。对于活性炭和硅藻土吸附结晶紫与酸性品红,颗粒内扩散不是速率控制步骤。假一级吸附速率常数k1和假二级吸附速率常数k2的值随污泥量的增加而增大,而颗粒内扩散常数kp却随污泥量的增加而减小。
通过析因试验,证明了活性污泥对活性黑5的吸附主要是由于染料分子的磺酸基氧负电荷中心与-NH3+相结合而产生的化学吸附,同时也说明这种吸附机制主要发生在污泥中的微生物细胞外,吸附是细胞外物质的性质;pH值和离子浓度的交互作用达到极其显著的程度( F值达1128.67和1562.04),说明在中性或酸性条件下盐度对染料在污泥上的吸附有很大的影响。
Adsorption is one of the main approaches in dyeing wastewater treatment. The organic matter adsorption by activated sludge has been observed for a long time. However, systematic studies on this subject, including major factors affecting the adsorption process, the quantitative adsorption modeling, comparative studies of activated sludge with different adsorbents and its mechanism have not been reported yet.
Keeping the above points under consideration, a systematic study on the adsorption of activated sludge was carried out by using the simulated dye wastewater of acid fuchsine 6B (AF)、crystal violet (CV) and reactive black 5 (RB5) as the treatment object. Comparisions were made with activated carbon (AC) and diatomite and mechanism were discussed.
It was found that, the equilibrium time of CV、AF and RB5 onto live activated sludge is 30min,20min and 70min, color removal rate can reach 81%、89% and 10% respectly. When the dosing quatity of AS is increased, the color removal of dye wastewater increases, while the adsorption quantity decreases. High stirring rate has little effect on dyestuff adsorption. Increase of pH value can increase adsorption quantity of CV slightly, but decrease that of AF, while keeping their removal rate at above 90%. PH value had great effect on the adsorption of RB5. As pH value increased, its adsorption quantity decreases quckly. When pH value is around 6.6~9.9, it keeps stable but very low. And then it increases slightly with the increase of pH.
Adsorption model study showed that the adsorption of these three dyestuffs onto AC, diatomite and AS fit well with Freundlich model and their adsorption of AF and RB5 also fit well with Langmuir model. The order of adsorption capacity of AS for the three dyestuffs was as follow: AF>CV>RB5. The adsorption of these three dyesuffs all followed the psudo-second kinetic model. For the adsorption of RB5 onto the three adsorbents and the three dyestuffs adsorbed onto AS, the intrapaticle disffusion is one of rate controlling step, whereas for the adsorption of AF and CV onto AC and diatomite, the intra-paticle disffusion is not the rate controlling step. It was also observed that the psudo-first rate constant k1 and psudo-second rate constant k2 all increased with the increasing of AS dosage, while the intra-paticle rate constant kp decreased.
The results of the cause-analyzing experiments upheld our hypothesis about the mechanism of the adsorption of RB5 onto AS. It also indicates that the mechanism of the adsorption occurs mainly outside the microbial cell, it is the nature of extracellular substances. The interaction of pH and ionic concentration achieved a very notable degree (the numbers of F are 1128.673 and 1562.044), which tells us that the ionic concentration may wield tremendous influence on the sludge’s adsorption to dyestuffs in neutral or acidic conditions.
引文
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2 P. CooPer. Removing colour from dye house wastewaters-a critieal review of Technology available. J. Sbc. Dyers Col. 1993(109): 97~100
3 S. B. Wang, H. T. Li. Kinetic modeling and mechanism of dye adsorption on Unburned carbon. Dyes and Pigments. 2007, 72: 308~314
4 A. Feryal. Adsorption of basic dyes from aqueous solution onto pumice powder. Journal of Colloid and Interface Science. 2005, 286: 455~458
5 S. B. Wang, Y.Boyjoo, A.Choueib A. Comparative study of dye removal using Fly Ash treated by different methods. Chemosphere. 2005, 60: 1401~1407
6 E. Eren, B. Afsin. Investigation of a basic dye adsorption from aqueous solution onto raw and pre-treated bentonite surfaces. Dyes and Pigments. 2007, 73:162~167
7 Z Aksu. Application of biosorption for the removal of organic pollutants: a Review. Proc.Biochem., 2005, 40: 997~1026
8 F Veglio, F Beolchini.Removal of metals by biosorption: a review Hydro-Metallurgy. 1997, 44: 301~3161
9汤岳琴等.生物吸附研究进展.四川环境. 2001, 20(2): 12~17
10 B. W. Atkinson, F. Bux, H. C. Kasan. Bioremediation of metal-contaminated Industrial effluents using water sludge. Water Science Technology. 1996, 34(9): 9~15
11马晓航等.硫酸盐还原生物法处理含锌废水.环境科学. 1995, 16(4):20~21
12 M. H Cheng, et al. The binding of heavy metal to algal surface. Jour. Water Poll. Control Fed. 1975. 47(2): 362~376
13 P. O. Nelson, et al. Jour. Some properties of a sequencing batch reactor system for removal of vat dyes. Water Poll.Control Fed. 1981, 53(8): 1323~1333
14吴涓等.白腐真菌吸附铅的研究.微生物学报. 1992, 39(l): 87~90
15黄民生等.微生物对水中铀的富集与还原.核技术. 2002, 25(2): 123~131
16汤岳琴等.产黄青霉废菌体对铅的吸附机理(Ⅱ).四川大学学报(工程科学报). 2001, 33(4): 45~49
17屠娟等.非活性黑根霉菌对废水中重金属离子的吸附.环境科学. 1995, 16(1): 12~15
18 J. G. Sillen. Stability Cinstants of metal Ion Complexes. London: In SPecial Publication. The Chemical Society. 1964, 17
19 A. Parsons, et al. D2-40 and CD31 analysis of retiform hemangioendotheliomas. Appl. Microbiol., 1971, 21: 657
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