摘要
印染废水和化工废水是典型的两类工业废水。其中,蒽醌染料是合成染料中重要的一类,是继偶氮染料之后使用量最大的一类染料,被广泛地应用于纺织、印染等行业。由于其具有很强的水溶性,工业生产中约50 %的蒽醌染料残留在生产废水中,导致废水色度极高且难生物降解,这给水环境带来了严重的危害。2,4-二氯苯酚(2,4-DCP)是芳香类化合物中用途较广、毒性较大、环境污染较严重的一类化合物,被广泛地用作木材防腐剂、防锈剂、杀真菌剂和一般杀虫剂等。中国、美国EPA等国家都将2,4-DCP列入了“优先控制污染物黑名单”。
本文以活性艳蓝KN-R和2,4-DCP为目标污染物,研究生物膜和活性污泥体系下,间歇水解-好氧循环工艺降解两种有机污染物的可行性,为间歇水解-好氧循环工艺处理高浓度难降解有机废水的工程应用奠定理论基础。
研究发现,循环流量、水解/好氧反应器有效液体体积比(水解/好氧反应器体积比)、好氧曝气流量是生物膜法和活性污泥法水解-好氧循环工艺降解活性艳蓝KN-R和2,4-DCP的关键工艺参数,对废水处理效果、反应器运行稳定性、菌体活性、微生物代谢产物累积情况及污泥特性等均有显著的影响。
生物膜法水解-好氧循环工艺降解活性艳蓝KN-R过程中,活性艳蓝KN-R初始浓度为600 mg/L,葡萄糖浓度2000 mg/L,在循环流量为10 mL/min,曝气流量3 L/min,水解/好氧反应器体积比2:2时,降解24 h,化学需氧量(COD)和色度的总去除率分别达到94.2 %和94.4 %。适当地增加循环流量,可以减轻水解反应器的酸化程度,避免挥发性脂肪酸(VFA)的积累对水解微生物的活性产生抑制。同时,提高了废水COD、色度的总去除率以及平均去除速率。但循环流量过高,导致水解反应器中溶解氧(DO)浓度增大,对水解微生物的生物降解活性产生抑制,不利于废水中活性艳蓝KN-R的降解。
活性污泥法水解-好氧循环工艺降解活性艳蓝KN-R过程中,活性艳蓝KN-R初始浓度为200 mg/L,葡萄糖浓度2000 mg/L,在循环流量为10 mL/min,曝气流量3 L/min,水解/好氧反应器体积比2:2时,COD和色度的总去除率分别达到90 %和85 %。废水COD和色度总去除率随着循环流量的增大呈现先增加后减小的趋势。循环流量增加,VFA浓度的峰值有所降低,水解和好氧污泥胞外多聚物(EPS)中胞外多糖(PS)和蛋白(PN)含量增加,污泥表面Zeta电位值减小,细胞表面相对疏水性增大,促进了微生物细胞间的相互粘附,有效地改善了污泥的沉降性能。
生物膜法水解-好氧循环工艺降解2,4-DCP过程中, 2,4-DCP初始浓度为20 mg/L,葡萄糖2000 mg/L,在循环流量为10 mL/min、曝气流量3 L/min、水解/好氧反应器体积比2:2时,降解24 h,COD和2,4-DCP的总去除率分别达到95 %和99 %。2,4-DCP和COD的总去除率随着循环流量增加而增大。但是,循环流量过高时,VFA浓度较高,水体的缓冲能力下降,水解微生物活性被抑制,不利于循环系统的稳定运行。在一定范围内提高曝气流量,可以提高废水2,4-DCP、COD的总去除率和去除速率。
活性污泥法水解-好氧循环工艺降解2,4-DCP过程中, 2,4-DCP初始浓度为20 mg/L,葡萄糖2000 mg/L,在循环流量为15 mL/min、曝气流量3 L/min、水解/好氧反应器体积比1:3时,降解24 h,COD和2,4-DCP的总去除率分别达到95 %和96 %。增大循环流量,加快了2,4-DCP、COD的总去除率和去除速率,VFA浓度的峰值逐渐降低且VFA达到最大值的时间加快,水解和好氧污泥EPS中胞外多糖和胞外蛋白质含量逐渐增加,污泥表面Zeta电位值减小。PN/PS也随循环流量增加呈线性增加趋势。同时,水解和好氧反应器内活性微生物量逐渐增加,污泥沉降性能得到改善。水解/好氧反应器体积比对2,4-DCP的降解有显著的影响。在1:3的体积比下,反应器中VFA浓度较低,体系保持较强的缓冲能力,微生物具有较强的活性,水解和好氧污泥EPS中胞外多糖和蛋白质含量最高,污泥的表面Zeta电位分布均最小,污泥整体性能稳定。
水解和好氧反应器间溶液的循环类似于天然水环境中厌氧和好氧界面间液体的传质。它将水解和好氧两个独立的过程“同时”进行,发挥了水解和好氧微生物间的协同作用,强化了水解和好氧降解过程,有效地解决了水解反应器中酸化抑制的难题,提高了废水的处理速率和效率。
Dyeing wastewater and chemical industry wastewater are two kinds of typical industry wastewater. Anthraquinone dyes constitute the second largest class of textile dyes after azo dyes, which are extensively used in the textile and dyeing industry because of their wide variety of color shades, high wet fastness profiles, ease of application, brilliant colors, and minimal energy consumption. Under typical industrial conditions, about 50 % of the dyes remain in the spent dye in unfixed or hydrolyzed form resulting in colored effluent, which brings major aesthetic problems for the industry. Thus, environmental concerns and the need of meeting the stringent international standards for rejecting wastewater have made the development of efficient and low cost processes for dealing with textile aqueous effluents an issue of major technological importance. Chlorophenols, such as 2,4-dichlorophenol (2,4-DCP), are used extensively in the manufacture of pesticides, herbicides, glue, paint, leather and pulp and wood preservatives. Due to its manufacture in large quantities and toxicity, DCP is an Environmental Protection Agency (EPA) priority pollutant identified in hazardous waste sites identified on the National Priorities List.
The objectives of the present work were to investigate the feasibility of a batch operated biofilm and activated sludge hydrolytic-aerobic recycling process (HARP) in degrading anthraquinone dye Reactive Blue KN-R (KN-R) and 2,4-DCP in wastewater. This study may be valuable for experimental design and engineering application of high concentration organic wastewater treatment by the batch hydrolytic-aerobic recycling process.
The results showed that recycling flux, hydrolytic/aerobic reactor volume ratio and aeration flux were the key process parameters for the batch operated biofilm and activated sludge hydrolytic-aerobic recycling process in treating KN-R and 2,4-DCP wastewater, which had great effects on removal efficiency and rate, stability of process, activity of microorganisms and characteristics of activated sludge and so on.
When the synthetic wastewater of KN-R 600 mg/L and glucose 2000 mg/L was treated by the batch operated biofilm hydrolytic-aerobic recycling process with recycling flux 10 mL/min, aeration flux 3 L/min, hydrolytic/aerobic reactor volume ratio 2:2, chemical oxygen demand (COD) and color removal efficiency could be up to 94.2 % and 94.4 %, respectively. Increase in recycling flux would alleviate acidification degree in the hydrolytic reactor and decrease volatile fatty acids (VFA) accumulation. Moreover, COD and color removal efficiency and average removal rate could be greatly enhanced. However, when recycling flux was much higher, the dissolved oxygen (DO) in the hydrolytic reactor was gradually increasing, which resulted in the fact that the activity of hydrolytic microorganisms was depressed and removal efficiency of COD and color was decreased.
When the synthetic wastewater of KN-R 200 mg/L and glucose 2000 mg/L was treated by the batch operated activated sludge hydrolytic-aerobic recycling process with recycling flux 10 mL/min, hydrolytic/aerobic reactor volume ratio 2:2, aeration flux 3 L/min, COD and color removal efficiencies reached 90 % and 85 %, respectively. With recycling flux increasing from 5 mL/min to 15 mL/min, COD and color removal efficiency increased and the maximum of VFA decreased. Meanwhile, the increase of the content of polysaccharide (PS) and protein (PN) in extracellular polymeric substances (EPS) of hydrolytic and aerobic activated sludge resulted in the increasing of Zeta potential and accelerated the conglutination and the settling of activated sludge.
When the synthetic wastewater of 2,4-DCP 20 mg/L and glucose 2000 mg/L was treated by the batch operated biofilm hydrolytic-aerobic recycling process with recycling flux 10 mL/min, hydrolytic/aerobic reactor volume ratio 2:2, aeration flux 3 L/min, COD and 2,4-DCP removal efficiencies could be up to 95 % and 99 %, respectively. COD and 2,4-DCP removal efficiency rose with recycling flux increasing from 5 mL/min to 10 mL/min. However, when recycling flux was above 10 mL/min, the trace amounts of oxygen transported to the hydrolytic reactor by recycling solution from the aerobic reactor could reduce the activity of hydrolytic microorganisms. COD and 2,4-DCP removal efficiency could be greatly enhanced by increasing aeration flux.
When the synthetic wastewater of 2,4-DCP 20 mg/L and glucose 2000 mg/L was treated by the batch operated activated sludge hydrolytic-aerobic recycling process with recycling flux 15 mL/min, hydrolytic/aerobic reactor volume ratio 1:3, aeration flux 3 L/min, COD and 2,4-DCP removal efficiencies reached 95 % and 96 %, respectively. With recycling flux increasing from 5 mL/min to 15 mL/min, COD and 2,4-DCP removal efficiency increased and the maximum of VFA decreased.
Meanwhile, the increase of the content of PS and PN in EPS of hydrolytic and aerobic activated sludge resulted in the decreasing of Zeta potential. As a result, the conglutination and the settling performance of activated sludge were enhanced. The linear increase in PN/PS values with increasing of recycling flux was observed. Hydrolytic/aerobic reactor volume ratio had great effects on 2,4-DCP and COD removal. When hydrolytic/aerobic reactor volume ratio was 1:3, VFA concentrations were much lower, which indicated that the activity of hydrolytic microorganisms had not been inhibited and the whole process maintained a stable condition. The content of PS and PN in EPS of hydrolytic and aerobic activated sludge were highest and the Zeta potential was lowest at volume ratio 1:3. This implied that the stability of hydrolytic and aerobic activated sludge during the recycling process was enhanced.
The above results suggested that the KN-R and 2,4-DCP in wastewater could be highly removed in the batch operated hydrolytic-aerobic recycling process. The exchange of metabolites between hydrolytic reactor and aerobic reactor could be compared to the metabolite exchange at interfaces between the anaerobic and aerobic zones of natural eco-process (sediments, bacterial colonies, stratified lakes and seas, microbial mats, biofilm, etc.). But the resistance to mass transfer across the hydrolytic-aerobic“interface”in reactors of the recycling process was much lower than it was in the natural process. The hydrolytic-aerobic recycling process benefited from the combination of“reductive and oxidative degradation mechanisms”and“cooperative metabolism”caused by the exchange of metabolites between hydrolytic and aerobic reactor. The metabolic and kinetic limitations to hydrolytic and aerobic microorganisms could be overcome in the recycling process. Meanwhile, the hydrolytic-aerobic recycling process could successfully solve the problem of over-acidification and effectively enhance the removal efficiency and rate of KN-R, 2,4-DCP and COD.
引文
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