水解酸化—颗粒填料复合式膜生物反应器处理涤纶碱减量废水研究
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摘要
涤纶碱减量废水中高浓度的对苯二甲酸和难降解的聚酯低聚物及各种助剂等使得碱减量废水成为纺织印染行业污染重、处理难度大的新型纺织印染废水。本文研究了水解酸化一颗粒填料复合式膜生物反应器(HMBR)组合工艺处理碱减量废水的技术,并对膜污染的控制和HMBR长期运行特性进行了探讨。得出了以下主要结果:
从废水处理工艺的角度,研究了对苯二甲酸(TA)在好氧和缺氧条件下的生物降解规律以及乙二醇(EG)对TA生物降解性的影响。TA的好氧降解不存在明显的抑制浓度,TA不会对微生物起毒害作用;微生物以TA、EG作为唯一的碳源均需要一定的驯化时间,EG的驯化时间比TA长,一旦微生物被驯化,EG、TA开始快速降解。在有氧条件下,EG不会抑制TA的初级生物降解,但会抑制TA的最终生物降解;在缺氧条件下,EG对TA的降解有抑制作用,一旦EG完全去除,TA又恢复降解。TA易好氧生物降解、几乎不能缺氧生物降解,EG既能好氧生物降解,又能缺氧生物降解。因此,这为碱减量废水分兼氧和好氧两段处理提供了理论依据。
活性污泥吸附、解吸等温线符合Freundlieh等温方程,好氧、兼氧污泥对TA的等温吸附方程分别为:q=8.6170C_e~(0.4207),q=4.0764C_e~(0.5405);好氧、兼氧污泥对TA的等温解吸方程分别为:q=9.4723C_e~(0.3271),q=4.2353C_e~(0.3688)。好氧、兼氧污泥的饱和吸附量分别为:39.06、31.45mgTA.gSS~(-1),TA的去除机制主要是生物降解作用,污泥吸附占TA总去除量的比例很小。
采用水解酸化一颗粒填料复合式膜生物反应器组合工艺处理实际碱减量废水是可行的。系统对有机污染物保持着很高的去除率,HRT为(9.0+7.2)h时,系统出水平均COD为55.9mg/L,COD平均去除率达到96%,TA去除率大于99%。水解酸化池的ηCOD<10%,ηTA<5%。HMBR的ηCOD>94%,ηTA>98%。水解酸化过程可以显著提高碱减量废水的可生化性。水解酸化系统受进水容积负荷Uv的影响很小;HMBR受进水容积负荷Uv的影响较大,进水容积负荷Uv小于6 gCOD.L~(-1).d~(-1)时,膜出水COD保持在80mpJL以下,ηCOD保持在95%左右。
HMBR在流体力学、微生物学、水处理工艺学、亚微观动力学等方面具有优越于普通MBR的特点。膜通量(J)、污泥浓度(X)、颗粒填料的体积含量(C)对膜过滤阻力上升速率(K)影响的次序为:CNow the polyester fabric alkali-peeling process wastewater (PAP-wastewater) is one kind of the popular textile industrial wastewater in China due to the high concentration of terephthalic acid (TA) and the poorly biodegradable polyester oligomer and chemical promoters. The treatment of PAP-wastewater by hydrolysis-acidification/ hybrid membrane bioreactor (HMBR), as well as the membrane fouling control and operational performance of HMBR, was investigated in this dissertation. The following results have been obtained:The biodegradation of TA on aerobic and anoxic condition, as well as the impact of ethylene glycol (EG) on the biodegradation of TA, was researched. It was found that TA was not toxic to the TA degrading cultures on the aerobic condition, whether the concentration of TA was high or low. There was a lag phase prior to degradation of TA and EG when TA and EG were fed as sole carbon source. Furthermore, the lag period of EG was longer than TA. However, once the cultures were acclimated, TA and EG started to be degraded rapidly. Although EG didn't inhibit the aerobic primary biodegradation of TA, it inhibited the aerobic ultimate biodegradation of TA. EG inhibited the anoxic biodegradation of TA, but TA was consumed at the same rate as in the experiments performed with TA as sole carbon source after complete consumption of EG It can be concluded that TA is easily degradable on aerobic condition and more difficult to be degraded on anaerobic condition and hardly degradable on anoxic condition, while EG is easily degraded on aerobic, anoxic and anaerobic condition.The result showed that the biosorption and desorption of TA by unadapted aerobic and facultative sludge could be characterized by Freundlich isotherm. Two Freundlich equations, q=8.6170C_e~(0.4207) and q=4.0764C_e~(0.5405), were established to describe the biosorption of TA by unadapted aerobic and facultative sludge, respectively. So q=
9.4723Ce03271 and q= 4.2353 Ce03688 for desorption of aerobic and facultative sludge, respectively. The maximum biosorptive uptakes of TA by aerobic and facultative sludge were 39.06, 31.45mgTA.gSS"1, respectively. The difference between biosortion and desortion Freudlich constants suggested that biosorption of TA was an partly irreversible process. In bioreactor the removal of TA by activated sludge was due to biodegradation rather than biosorption.The experiment demonstrated that the hydrolysis-acidification/ HMBR process was an economically attractive alternative for the treatment of PAP-wastewater. The effluent COD average 55.9mg/L and the following results were obtained at HRT =(9.0+7.2)h: t)Cod=96% and tita>99% for the total system, r|CoD<10% and TyrA<5% for hydrolysis-acidification bioreactor, t|cod>94% and t|Ta>98% for HMBR. The hydrolysis-acidification pretreatment improved the biodegradability of PAP-wastewater. The impact of volumetric loading rate (Uv) was slightly on the performance of hydrolysis-acidification bioreactor, but largely on HMBR. The effluent COD was below 80 mg/L and ticod averaged 95% for HMBR when Uv of HMBR was below egCOD.I/'.d"1.The observations revealed that suspended carriers played an important role in governing the filtration conditions and decreasing fouling resistance. The results indicated that the cake resistance of HMBR decreased by 86%, the critical flux increased by about 20% and the rate of membrane fouling decreased by 70% in comparison with MBR. The effects of the membrane flux (J), sludge concentration (X) and carriers volume (C) on the increasing rate of the transmembrane pressure were in decreasing order: C HMBR stabilized at about 14gMLSS/L. No obvious trend of MLVSS/MLSS was observed, but it was found that the particle size of sludge floes decreased with operation time. Filtration resistance of mixed liquor of MBR increased slower than HMBR with operation time. The results revealed that the colloids in the supernatant were the main contributors to the rapid increasing of filtration resistance of mixed liquor. The soluble microbial products (SMP) could accumulate in bioreactor, but also its components could change. The sludge dehydrogenase activity was measured in the long-term running and it was found that it decreased with operation time.On the condition of no sludge wasted, the theoretical yield factors (Y) and the biomass decay constants (Kj) for bioreactor in MBR and HMBR were below that in the traditional activated sludge process: Y(MBR)= 0.315, Y(HMBR)= 0.301mgVSS/mgCOD, Kd(MBR)= 0.03 Id"1, Kd(HMBR)= 0.035 d"1. On the condition of SRT=50d, Y and Kd for bioreactor in MBR and HMBR corresponded to that in the traditional activated sludge process: Y(MBR)= 0.375, Y(HMBR)= 0.353mgVSS/mgCOD, Kd(MBR)= 0.071 d"1, Kd(HMBR)= 0.067 d"1. The substrate degradation rate constant (K) of TA artificial wastewater, (TA+EG) artificial wastewater and PAP-wastewater were 0.001, 0.00078 and 0.00072d"\ respectively. Compared with K (0.004-0.03) in the traditional activated sludge process, the K value in HMBR (or MBR) was very low.The acid precipitation pretreatment was adopted before the biodegradation of PAP-wastewater in terms of the resource reclaim and reuse of wasted resource. The parameters of acid precipitation process were obtained as follows: pH3.5-4.0, normal temperature, stirring at reaction for 1-2 minutes with 300rpm and at flocculation for 10 minutes with 60-100rpm, sedimentation for 12h. The particle size of TA floes reclaimed by acid precipitation averaged 11.56um. The recovery rate of TA was 77% and the removal rate of COD arrived at 50.5%. The B/C value of PAP-wastewater before and after acid precipitation were 0.37 — 0.40 and 0.27-0.31 respectively, which indicated that TA improved the biodegradability of PAP-wastewater. There was 78% effluent COD below 50mg/L and the following results were obtained: ticod=97% and t|ta>99% for the total system. It should be noted that the relative contributions of hydrolysis-acidification
bioreactor and HMBR to the total removal rate were 29.8*^ 67%.
从废水处理工艺的角度,研究了对苯二甲酸(TA)在好氧和缺氧条件下的生物降解规律以及乙二醇(EG)对TA生物降解性的影响。TA的好氧降解不存在明显的抑制浓度,TA不会对微生物起毒害作用;微生物以TA、EG作为唯一的碳源均需要一定的驯化时间,EG的驯化时间比TA长,一旦微生物被驯化,EG、TA开始快速降解。在有氧条件下,EG不会抑制TA的初级生物降解,但会抑制TA的最终生物降解;在缺氧条件下,EG对TA的降解有抑制作用,一旦EG完全去除,TA又恢复降解。TA易好氧生物降解、几乎不能缺氧生物降解,EG既能好氧生物降解,又能缺氧生物降解。因此,这为碱减量废水分兼氧和好氧两段处理提供了理论依据。
活性污泥吸附、解吸等温线符合Freundlieh等温方程,好氧、兼氧污泥对TA的等温吸附方程分别为:q=8.6170C_e~(0.4207),q=4.0764C_e~(0.5405);好氧、兼氧污泥对TA的等温解吸方程分别为:q=9.4723C_e~(0.3271),q=4.2353C_e~(0.3688)。好氧、兼氧污泥的饱和吸附量分别为:39.06、31.45mgTA.gSS~(-1),TA的去除机制主要是生物降解作用,污泥吸附占TA总去除量的比例很小。
采用水解酸化一颗粒填料复合式膜生物反应器组合工艺处理实际碱减量废水是可行的。系统对有机污染物保持着很高的去除率,HRT为(9.0+7.2)h时,系统出水平均COD为55.9mg/L,COD平均去除率达到96%,TA去除率大于99%。水解酸化池的ηCOD<10%,ηTA<5%。HMBR的ηCOD>94%,ηTA>98%。水解酸化过程可以显著提高碱减量废水的可生化性。水解酸化系统受进水容积负荷Uv的影响很小;HMBR受进水容积负荷Uv的影响较大,进水容积负荷Uv小于6 gCOD.L~(-1).d~(-1)时,膜出水COD保持在80mpJL以下,ηCOD保持在95%左右。
HMBR在流体力学、微生物学、水处理工艺学、亚微观动力学等方面具有优越于普通MBR的特点。膜通量(J)、污泥浓度(X)、颗粒填料的体积含量(C)对膜过滤阻力上升速率(K)影响的次序为:C
9.4723Ce03271 and q= 4.2353 Ce03688 for desorption of aerobic and facultative sludge, respectively. The maximum biosorptive uptakes of TA by aerobic and facultative sludge were 39.06, 31.45mgTA.gSS"1, respectively. The difference between biosortion and desortion Freudlich constants suggested that biosorption of TA was an partly irreversible process. In bioreactor the removal of TA by activated sludge was due to biodegradation rather than biosorption.The experiment demonstrated that the hydrolysis-acidification/ HMBR process was an economically attractive alternative for the treatment of PAP-wastewater. The effluent COD average 55.9mg/L and the following results were obtained at HRT =(9.0+7.2)h: t)Cod=96% and tita>99% for the total system, r|CoD<10% and TyrA<5% for hydrolysis-acidification bioreactor, t|cod>94% and t|Ta>98% for HMBR. The hydrolysis-acidification pretreatment improved the biodegradability of PAP-wastewater. The impact of volumetric loading rate (Uv) was slightly on the performance of hydrolysis-acidification bioreactor, but largely on HMBR. The effluent COD was below 80 mg/L and ticod averaged 95% for HMBR when Uv of HMBR was below egCOD.I/'.d"1.The observations revealed that suspended carriers played an important role in governing the filtration conditions and decreasing fouling resistance. The results indicated that the cake resistance of HMBR decreased by 86%, the critical flux increased by about 20% and the rate of membrane fouling decreased by 70% in comparison with MBR. The effects of the membrane flux (J), sludge concentration (X) and carriers volume (C) on the increasing rate of the transmembrane pressure were in decreasing order: C
bioreactor and HMBR to the total removal rate were 29.8*^ 67%.
引文
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