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焦化废水是炼焦工业中煤气净化及焦化产品制作回收等环节产生的混合工业废水[1]。焦化废水水质属性复杂多变,含有大量氨氮、苯酚、氰化物、硫氰化物等特征污染物,并且具有难降解、生物毒性强及生化性差等的特点[2-3]。工业水处理中常用的生物工艺有缺氧/好氧(A/O)工艺、厌氧/缺氧/好氧(A2/O)工艺[4-6]等,但这些工艺在处理焦化废水等高毒性的工业废水时,时常出现硝化失败的情况,其除碳脱氮效果不理想,出水水质不稳定[7-9]。针对上述问题,迫切需要开发更加先进高效的除碳脱氮工艺应用于毒性高的工业废水处理。
好氧-水解-好氧(OHO)作为一种新型脱氮工艺,其原理方面的研究以及工业应用已经证明,该工艺可以很好地解决传统生物工艺除碳脱氮效果不理想、出水水质不稳定的问题[10-12]。OHO工艺具有功能明确的组成单元,与传统工艺相比,采用流化床的三泥法运行模式可以选择性富集微生物群落,并可实现良好的工艺稳定性,突破了高毒性及高COD/TN比废水处理的负荷瓶颈,而且节能降耗。OHO工艺采用基于流化床的三污泥法运行模式,通过回流与超越操作手段,可以实现污泥生物量的富集与微生物功能/丰度调控,活性污泥与焦化废水中的污染物完全混合并充分接触,高效的混合与传质克服了毒性抑制问题。O1单元中好氧微生物氧化去除氰化物、硫氰酸盐、硫化物、苯酚等还原性物质,可大幅度削减废水毒性,为后续工艺单元提供良好的水质条件。毒性降低的焦化废水在H单元进行高效的反硝化脱氮。H单元采用长时间停留,具有容纳毒性负荷的能力,超越比例的控制以H单元中的微生物活性不受进水抑制为基础,与传统工艺相比,降低了厌氧单元的毒性负荷,表现出OHO-MBR工艺的先进性。潘建新[13]发现,异养菌在O1单元富集,自养硝化菌在O2单元富集,O1单元中相对丰度最高的菌属Comamonas贡献有机物的去除,O2单元中AOB菌也具有相当高的相对丰度,贡献了O2单元的硝化,体现了OHO工艺在稳定处理焦化废水时具有的差异化优势。
随着我国污/废水排放标准要求的不断提高,为实现废水零排放的目标,对焦化废水的有效处理、达标排放提出了更加严峻的挑战。膜生物反应器(membrane bioreactor, MBR)是生物处理与膜分离的有机结合,其优质的生物出水水质为后续的脱盐等深度处理营造了优越、稳定的水质条件,成为现有活性污泥处理工艺升级改造、实现废水零排放所优先考虑的生物处理工艺[14-15]。SUN等[16]采用厌氧-缺氧-好氧膜生物反应器(A2O-MBR)处理纺织助剂废水,在内循环比为1.5时,COD、
${\rm{NH}}_4^ + $ -N和TN的平均去除率分别约为87%、96%和55%。WANG等[17]开发了实验室规模的A2O-MBR系统处理煤气化废水,COD、${\rm{NH}}_4^ + $ -N和酚类物质的最大去除率分别为97.4%、92.8%和99.7%。ZHAO等[18]采用实验室规模的厌氧-缺氧-好氧膜生物反应器(A2O-MBR)系统处理高负荷、高毒性的焦化废水,其结果表明,A2O-MBR系统在污染物和急性毒性降低方面比传统的厌氧-缺氧-好氧系统更有效和更可靠。以上所实现的单污泥工艺结合膜生物反应器虽然对污染物去除效果较好,但因负荷高而产生严重的膜污染,对富集硝化菌也不利,需要的停留时间没有明显缩短。基于上述研究结果,本研究以OHO新型生物处理工艺为基础[11],在二级好氧池内加装膜组件,构建了OHO-MBR组合工艺,研究了其处理实际焦化废水的可行性;通过分析工艺对COD、
${\rm{NH}}_4^ + $ -N、${\rm{NO}}_2^ - $ -N、${\rm{NO}}_3^ - $ -N和TN等水质指标的转化关系及去除效果,考察了OHO-MBR工艺处理焦化废水的效能,分析了组合工艺的特点以及可能的技术应用方向。
OHO-MBR组合工艺处理实际焦化废水的可行性
Feasibility test of OHO-MBR combined process for actual coking wastewater treatment
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摘要: 焦化废水因其生物毒性强、高腐蚀性及高COD/TN比的特点,对传统生物处理工艺提出了更高的挑战,故新型生物工艺的探索对于特殊水质达标可行性及工艺经济性具有重要意义。为此,构建了新型好氧-水解-好氧(OHO)-膜生物反应器(MBR)组合工艺用于焦化废水处理,利用实际焦化废水开展了现场小试研究,考察了焦化废水中典型污染物的去除效果,结合工艺运行参数和水质指标测定结果,解析了典型污染物在OHO-MBR工艺中的转化规律。在稳定运行情况下,焦化废水经OHO-MBR工艺处理的实际运行结果表明:当总停留时间设定为56 h时,进水COD、TN、
${{\rm{NH}}_4^ +} $ -N、SCN−-N的平均值分别为3 063、146、27.3、85.1 mg·L−1的条件下,组合工艺即使在环境温度偏低(10~20 ℃)的情况下仍能实现对COD、TN、${{\rm{NH}}_4^ +} $ -N、SCN−-N平均85.9%、65.4%、95.1%、98.6%的去除;在膜通量为20 L·(m2·h)−1的条件下,工艺运行90 d,跨膜压差维持在10 kPa以内,表明组合工艺处理实际焦化废水的初步可行性;在OHO的O2反应器中添加膜组件可去除焦化废水中的悬浮物及胶体组分,有效截留和富集常规工艺中不易增殖的特种功能微生物,提高反应器处理负荷与抗冲击能力。以上结果表明,在无需对基建设施进行大规模改造的前提下,OHO-MBR可以作为现有工艺提升出水水质的改进技术选择。Abstract: Coking wastewater poses a higher challenge to traditional biological treatment processes due to its strong biological toxicity, high corrosiveness, and high COD/TN ratio. The exploration of new biological processes is of great significance to the feasibility of meeting special water quality standards and the economy of the process. Based on these considerations, this study constructed a new type of Aerobic-Hydrolysis-Aerobic (OHO)-Membrane Bioreactor (MBR) combined process for coking wastewater treatment. The actual coking wastewater was used to carry out an on-site small test study and investigate the treatment effect of typical pollutants in the coking wastewater. Combining the measurement results of process operating parameters and water quality indicators, the conversion characteristics of typical pollutants in the OHO-MBR process were analyzed. Under stable operation conditions, the actual operation results of coking wastewater treated by OHO-MBR process showed that, under the conditions of HRT = 56 h and the average influent COD, TN,${\rm{NH}}_4^ + $ -N and SCN−-N of 3 063, 146, 27.3 and 85.1 mg·L−1, respectively, the average removal rates of COD, TN,${\rm{NH}}_4^ + $ -N and SCN−-N achieved by the combined process were 85.9%, 65.4%, 95.1% and 98.6% even at low ambient temperatures(10~20 ℃), respectively. After 3 months running of the process with the membrane flux of 20 L·(m2·h)−1 for the membrane module, the transmembrane pressure maintained below 10 kPa, which showed the preliminary feasibility of the combined process to treat actual coking wastewater. The potential direction of the process to further improve the effect of pollutant treatment was clarified. The existence of the membrane module in the O2 reactor of OHO could remove the suspended solids and colloidal components in the coking wastewater, effectively intercepted and enriched the special functional microorganisms that were not easy to proliferate in the conventional process. The loading rate and shock resistance capability increased for the process without the need for large-scale transformation of infrastructure facilities, and it can be used as an improvement technology option for the existing process to improve the quality of the effluent.-
Key words:
- coking wastewater /
- OHO /
- biological treatment /
- membrane bioreactor /
- bioaccumulate /
- nitrogen removal
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表 1 OHO-MBR各单元主要运行参数
Table 1. Main operating parameters of OHO-MBR.
工艺单元 HRT/h SRT/d MLSS/(mg·L−1) pH DO/(mg·L−1) O1 20 20 4 000~6 000 8.0~8.5 4~6 H 18 90 3 000~5 000 7.4~8.1 <0.2 O2-MBR 18 50 4 000~5 000 7.9~8.2 4~6 表 2 不同工艺对焦化废水的处理性能
Table 2. Treatment performance of coking wastewater by different processes
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