Comparison between UV and VUV photolysis for the pre- and post-treatment of coking wastewater

In this study, ultraviolet (UV) and vacuum ultraviolet (VUV) photolysis were investigated for the pre-treatment and post-treatment of coking wastewater. First, 6-fold diluted raw coking wastewater was irradiated by UV and VUV. It was found that 15.9%–35.4% total organic carbon (TOC) was removed after 24 hr irradiation. The irradiated effluent could be degraded by the acclimated activated sludge. Even though the VUV photolysis removed more chemical oxygen demand (COD) than UV, the UV-irradiated effluent demonstrated better biodegradability. After 4 hr UV irradiation, the biological oxygen demand BOD₅/COD ratio of irradiated coking wastewater increased from 0.163 to 0.224, and its toxicity decreased to the greatest extent. Second, the biologically treated coking wastewater was irradiated by UV and VUV. Both of them were able to remove 37%–47% TOC within 8 hr irradiation. Compared to UV, VUV photolysis could significantly improve the transparency of the bio-treated effluent. VUV also reduced 7% more ammonia nitrogen (NH₄⁺–N), 17% more nitrite nitrogen (NO₂⁻–N), and 18% more total nitrogen (TN) than UV, producing 35% less nitrite nitrogen (NO₃⁻–N) as a result. In conclusion, UV irradiation was better in improving the biodegradability of coking wastewater, while VUV was more effective at photolyzing the residual organic compounds and inorganic N-species in the bio-treated effluent.     

Comparison between UV and VUV photolysis for the pre-and post-treatment of coking wastewater

In this study, ultraviolet(UV) and vacuum ultraviolet(VUV) photolysis were investigated for the pre-treatment and post-treatment of coking wastewater. First, 6-fold diluted raw coking wastewater was irradiated by UV and VUV. It was found that 15.9%–35.4% total organic carbon(TOC) was removed after 24 hr irradiation. The irradiated effluent could be degraded by the acclimated activated sludge. Even though the VUV photolysis removed more chemical oxygen demand(COD) than UV, the UV-irradiated effluent demonstrated better biodegradability. After 4 hr UV irradiation, the biological oxygen demand BOD5/COD ratio of irradiated coking wastewater increased from 0.163 to 0.224, and its toxicity decreased to the greatest extent. Second, the biologically treated coking wastewater was irradiated by UV and VUV. Both of them were able to remove 37%–47% TOC within 8 hr irradiation.Compared to UV, VUV photolysis could significantly improve the transparency of the bio-treated effluent. VUV also reduced 7% more ammonia nitrogen(NH+4–N), 17%more nitrite nitrogen(NO-2–N), and 18% more total nitrogen(TN) than UV, producing 35%less nitrite nitrogen(NO-3–N) as a result. In conclusion, UV irradiation was better in improving the biodegradability of coking wastewater, while VUV was more effective at photolyzing the residual organic compounds and inorganic N-species in the bio-treated effluent.     

Pulsed corona discharge for improving treatability of coking wastewater

Coking wastewater(CW) contains toxic and macromolecular substances that inhibit biological treatment. The refractory compounds remaining in biologically treated coking wastewater(BTCW) provide chemical oxygen demand(COD) and color levels that make it unacceptable for reuse or disposal. Gas-phase pulsed corona discharge(PCD) utilizing mostly hydroxyl radicals and ozone as oxidants was applied to both raw coking wastewater(RCW) and BTCW wastewater as a supplemental treatment. The energy efficiency of COD,phenol, thiocyanate and cyanide degradation by PCD was the subject of the research. The cost-effective removal of intermediate oxidation products with addition of lime was also studied. The energy efficiency of oxidation was inversely proportional to the pulse repetition frequency: lower frequency allows more effective utilization of ozone at longer treatment times. Oxidative treatment of RCW showed the removal of phenol and thiocyanate at 800 pulses per second from 611 to 227 mg/L and from 348 to 86 mg/L, respectively, at 42 k Wh/m~3 delivered energy, with substantial improvement in the BOD5/COD ratio(from 0.14 to 0.43).The COD and color of BTCW were removed by 30% and 93%, respectively, at 20 k Wh/m~3,showing energy efficiency for the PCD treatment exceeding that of conventional ozonation by a factor of 3–4. Application of lime appeared to be an effective supplement to the PCD treatment of RCW, degrading COD by about 28% at an energy input of 28 k Wh/m3 and the lime dose of 3.0 kg/m~3. The improvement of RCW treatability is attributed to the degradation of toxic substances and fragmentation of macromolecular compounds.     

Biological removal of antiandrogenic activity in gray wastewater and coking wastewater by membrane reactor process

A recombinant human androgen receptor yeast assay was applied to investigate the occurrence of antiandrogens as well as the mechanism for their removal during gray wastewater and coking wastewater treatment. The membrane reactor (MBR) system for gray wastewater treatment could remove 88.0% of antiandrogenic activity exerted by weakly polar extracts and 97.3% of that by moderately strong polar extracts, but only 32.5% of that contributed by strong polar extracts. Biodegradation by microorganisms in the MBR contributed to 95.9% of the total removal. After the treatment, the concentration of antiandrogenic activity in the effluent was still 1.05 μg flutamide equivalence (FEQ)/L, 36.2% of which was due to strong polar extracts. In the anaerobic reactor, anoxic reactor, and membrane reactor system for coking wastewater treatment, the antiandrogenic activity of raw coking wastewater was 78.6 mg FEQ/L, and the effluent of the treatment system had only 0.34 mg FEQ/L. The antiandrogenic activity mainly existed in the medium strong polar and strong polar extracts. Biodegradation by microorganisms contributed to at least 89.2% of the total antiandrogenic activity removal in the system. Biodegradation was the main removal mechanism of antiandrogenic activity in both the wastewater treatment systems.     

Treatment of coking wastewater by a novel electric assisted micro-electrolysis filter

A newly designed electric assisted micro-electrolysis filter(E-ME) was developed to investigate its degradation efficiency for coking wastewater and correlated characteristics. The performance of the E-ME system was compared with separate electrolysis(SE) and micro-electrolysis(ME) systems. The results showed a prominent synergistic effect on COD removal in E-ME systems. Gas chromatography/mass spectrometry(GC–MS) analysis confirmed that the applied electric field enhanced the degradation of phenolic compounds.Meanwhile, more biodegradable oxygen-bearing compounds were detected. SEM images of granular activated carbon(GAC) showed that inactivation and blocking were inhibited during the E-ME process. The effects of applied voltage and initial p H in E-ME systems were also studied. The best voltage value was 1 V, but synergistic effects existed even with lower applied voltage. E-ME systems exhibited some p H buffering capacity and attained the best efficiency in neutral media, which means that there is no need to adjust p H prior to or during the treatment process. Therefore, E-ME systems were confirmed as a promising technology for treatment of coking wastewater and other refractory wastewater.     

Characteristics of microbial community functional structure of a biological coking wastewater treatment system

Nitrogenous heterocyclic compounds are key pollutants in coking wastewater; however, the functional potential of microbial communities for biodegradation of such contaminants during biological treatment is still elusive. Herein, a high throughput functional gene array (GeoChip 5.0) in combination with Illumina HiSeq2500 sequencing was used to compare and characterize the microbial community functional structure in a long run (500 days) bench scale bioreactor treating coking wastewater, with a control system treating synthetic wastewater. Despite the inhibitory toxic pollutants, GeoChip 5.0 detected almost all key functional gene (average 61,940 genes) categories in the coking wastewater sludge. With higher abundance, aromatic ring cleavage dioxygenase genes including multi ring1,2diox; one ring2,3diox; catechol represented significant functional potential for degradation of aromatic pollutants which was further confirmed by Illumina HiSeq2500 analysis results. Response ratio analysis revealed that three nitrogenous compound degrading genes- nbzA (nitro-aromatics), tdnB (aniline), and scnABC (thiocyanate) were unique for coking wastewater treatment, which might be strong cause to increase ammonia level during the aerobic process. Additionally, HiSeq2500 elucidated carbozole and isoquinoline degradation genes in the system. These findings expanded our understanding on functional potential of microbial communities to remove organic nitrogenous pollutants; hence it will be useful in optimization strategies for biological treatment of coking wastewater.     

Revealing the anaerobic acclimation of microbial community in a membrane bioreactor for coking wastewater treatment by Illumina Miseq sequencing

The dynamic change of microbial community during sludge acclimation from aerobic to anaerobic in a MBR for coking wastewater treatment was revealed by Illumina Miseq sequencing in this study. The diversity of both Bacteria and Archaea showed an increase–decrease trajectory during acclimation, and exhibited the highest at the domestication interim. Ignavibacteria changed from a tiny minority(less than 1%) to the dominant bacterial group(54.0%) along with acclimation. The relative abundance of Betaproteobacteria kept relatively steady, as in this class some species increased coupled with some other species decreased during acclimation. The dominant Archaea shifted from Halobacteria in initial aerobic sludge to Methanobacteria in the acclimated anaerobic sludge. The dominant bacterial and archaeal groups in different acclimation stages were indigenous microorganisms in the initial sludge, though some of them were very rare. This study supported that the species in"rare biosphere" might eventually become dominant in response to environmental change.     

UV/H2O2法处理焦化废水的试验研究

焦化废水是一种典型的成分复杂的难降解有机废水。实验利用UV／H2O2法对焦化废水的处理进行研究,探讨了不同反应时间、H2O2投加量、pH值等因素对COD去除率及色度降解效果的影响。结果表明．废水起始COD质量浓度为1334mg几时,H2O2投加浓度为45mmol/L,pH值=11,紫外灯照射60min,COD去除率可达70％以上;随着H2O2投加量的增加以及pH值的升高,污水的色度明显降低。     

Naval derusting wastewater containing high concentration of iron, treated in UV photo-Fenton-like oxidation

The UV photooxidation with Fe(III) and H2O2 was employed to treat a naval derusting wastewater, which contains the high COD (chemical oxygen demand) and various metal concentrations exceptionally with high concentrations of citric acid and iron. Because of its iron containment, the Fenton-like reaction automatically took place with the added amount of H2O2. The decomposition rate was found in a sequence of: UV/H2O2/Fe(III) > UV/H2O2 > Fe(II)/H2O2. Two H2O2 injection methods, single and multiple points, were evaluated. The multiple-point H2O2 injection was more e cient to decompose the citric acid. The decomposition of the synthetic citric acid and the real derusting citric acid wastewater was also compared. The 93% COD reduction of the derusting wastewater was achieved using the UV/H2O2/Fe(III) treatment.     

焦化废水水质组成及其环境学与生物学特性分析

焦化废水水质的复杂性及对环境、生态影响的不确定性制约了处理水质的全面达标,且可能对后续水体造成危害.为了解焦化废水的基本物化性质、环境学特性及生物学特性,采用离子色谱、ICP/MS、GC/MS等分析手段研究了广东韶关焦化厂废水的COD、BOD、色度、氨氮、主要阴阳离子、金属成分及有机物组成等,评价了该焦化废水组分的可处理性及环境危害性,分析了焦化废水生物处理过程及可能存在的惰性有机污染物.结果表明,焦化废水构成环境危害的主要组分有COD、氨氮,挥发酚、氰化物、硫化物、氟化物及油份等,重点是有机污染物;第一类污染物在原水及外排水中的浓度是安全的;焦化废水中以酚为代表的有机物及多环、杂环化合物在水中广泛存在,经处理后仍有间甲酚、长链烷烃、苯系物、酯类、醇类、卤代烃及胺类等进入环境;造成焦化废水处理效率不高的原因是各组分之间的不协调而难以维持生物系统的正常ATP酶活,富氮缺磷,氨的生物毒害,毒性有机物对生物的抑制,Na /K 比例失衡等.因此,有毒/难降解焦化废水的处理技术须综合考虑污染物的组成、合理的工艺及排放水的生态安全性.     

SMBBR处理焦化废水性能及菌群结构响应关系

采用特异性移动床生物膜反应器（SMBBR）处理焦化废水,连续监测生物反应器处理性能.通过HS-GC/MS和Illumina高通量测序探究污染物降解与生物膜菌群结构的响应关系;利用CCA分析废水变量对微生物菌群结构的影响关系.结果表明,系统稳定运行50d时总酚去除率达96.62%,100d时硫氰化物和氰化物完全降解,其中酚、硫氰化物和氰化物对NH₄⁺-N的降解具有毒性抑制作用.HS-GC/MS结果显示,经过好氧处理后,80%以上的有机物被完全去除,其中包括全部酚、部分含N、O杂环化合物和长链烷烃等.测序结果表明,反应时间的不同,生物膜菌群丰度和多样性存在差异.反应期间Proteobacteria（变形菌门）相对丰度最高（20.57%~34.55%）,促进了苯酚的降解;优势菌属为norank_f_ODP1230B8.23、unclassified_o_Micrococcales、norank_f_Anaerolineaceae;此外,Thauera（陶厄氏菌属）、Ottowia、unclassified_o_Rhizobiales（根瘤菌属）和Thiobacillus（硫杆菌属）为系统中苯酚、SCN^-和CN^-的降解优势菌.CCA分析表明,pH值与Nitrospira（硝化菌属）正相关性最大,有效控制pH值可有助于硝化反应的稳定运行.本文研究结论可为生物膜法处理焦化废水提供理论依据.     

Modeling of secondary treated wastewater disinfection by UV irradiation: Effects of suspended solids content

This work aimed to study UV-resistant strains of Pseudomonas aeruginosa, to propose a formulation of the kinetics of secondary treated wastewater disinfection and to underline the influence of suspended solids on the inactivation kinetics of these strains. Some investigations were carried out for the validation of some simulation models, from the simplest, the kinetics model of Chick-Watson reduced to first order, to rather complex models such as multi-kinetic and Collins-Selleck models. Results revealed that the involved processes of UV irradiation were too complex to be approached by a simplified formulation, even in the case of specific strains of microorganisms and the use of nearly constant UV radiation intensity. In fact, the application of Chick-Watson model in its original form is not representative of the kinetics of UV disinfection. Modification, taking into account the speed change during the disinfection process, has not significantly improved results. On the other hand, the application of Collins-Selleck model demonstrates that it was necessary to exceed a least dose of critical radiation to start the process of inactivation. To better explain the process of inactivation, we have assumed that the action of disinfectant on the survival of lonely microorganisms is faster than its action on suspended solids protected or agglomerated to each others. We can assume in this case the existence of two inactivation kinetics during the processes (parallel and independent) of the first-order. For this reason, the application of a new kinetic model by introducing a third factor reflecting the influence of suspended solids in water on disinfection kinetics appeared to be determinant for modeling UV inactivation of P. aeruginosa in secondary treated wastewater.     

焦化废水厌氧生物降解影响因素的识别

基于一系列焦化废水处理实地工程考察而尚未发现高浓度焦化废水厌氧产甲烷成功案例的实际问题,以广东韶钢焦化废水工程中COD为(4100±200)mg·L~(-1)的原水为研究对象,通过检测COD、TOC和苯酚等关键水质指标浓度变化及气体产量,以浓度梯度稀释的方法考察影响焦化废水厌氧降解的因素及其浓度阈值,主要涉及硫氰化物、苯酚、硫化物和氰化物,同时分析碳源结构改变所带来的厌氧降解特性的变异.结果发现:在pH为(7.0±0.5)、温度为(35.0±0.5)℃的条件下,当焦化废水COD被稀释至1500~1800 mg·L~(-1),接种活性污泥,能够检测到厌氧产甲烷的现象;在COD稀释至1800 mg·L~(-1)左右的焦化废水中分别投加不同浓度的硫氰化物、苯酚、硫化物和氰化物时,发现其单抑制浓度分别处在500~1500、1100~1250、200~250和30~40 mg·L~(-1);向未解除抑制的焦化废水(COD为2100 mg·L~(-1))中投加等COD浓度的乙酸钠、葡萄糖和甲醇3种常用的工业碳源改变原有的碳源结构时,发现乙酸型产甲烷菌的活性被抑制,而氢营养型产甲烷菌的活性并没受到明显抑制.上述研究结果说明,高浓度焦化废水难以厌氧降解,抑制因素的解除可以使厌氧菌激活,其中,氢营养型产甲烷菌较乙酸型产甲烷菌能够耐受更高的毒性物质浓度阈值.     

焦化废水后物化处理的臭氧-混凝-吸附原理选择与协同机制

以焦化废水生物出水为研究对象,对比了活性炭吸附、混凝沉淀、臭氧氧化原理及其协同的工艺技术处理效果,考察处理前后废水的分子量分布、紫外可见光谱、三维荧光光谱（EEM）和GC/MS等表征的溶液性质变化.结果表明,废水生物工艺出水的后物化深度处理的最佳组合原理序列为臭氧-混凝-吸附,响应曲面模型预测的最优反应条件为：臭氧反应时间62.56 min,聚合硫酸铁（PFS）投加量为0.87 g·L^-1,以及活性炭投加量为1.10 g·L^-1.实验过程的总有机碳（TOC）去除率达到98.29%,与模拟值98.74%相对偏差为0.45%.活性炭吸附、混凝沉淀和臭氧氧化3种技术原理对焦化废水生物出水中污染物具有选择性分离与转化的作用,组合工艺能够实现废水中残余组分有机物、UV₂₅₄吸光物质、荧光物质等的有效去除,存在废水溶液性质与工艺技术原理有效性协同增强的操作空间.     

电-多相臭氧催化工艺深度处理焦化废水

本文采用新型电-多相臭氧催化（E-catazone）工艺深度处理焦化废水生化二级出水,开展工艺可行性研究.通过与O₃/TiO₂纳米花（TiO_2-NF）与O₃/TiO_2-NF/H₂O₂及单独电化学氧化工艺相比较,对E-catazone工艺技术优势及氧化机理进行探究.结果表明：在相同条件下（O₃浓度84mg/L）,电-多相臭氧催化获得的COD和TOC的去除率（分别为67.9%,50.0%）显著优于O₃/TiO_2-NF获得的去除率（25.8%,20.9%）,即便在O₃/TiO_2-NF体系中投加5g/L的H₂O₂以促进臭氧均相催化效果,但COD和TOC去除率也仅分别提高到63.6%,43.6%.     

电-多相臭氧催化工艺深度处理焦化废水

本文采用新型电-多相臭氧催化（E-catazone）工艺深度处理焦化废水生化二级出水,开展工艺可行性研究.通过与O₃/TiO₂纳米花（TiO_2-NF）与O₃/TiO_2-NF/H₂O₂及单独电化学氧化工艺相比较,对E-catazone工艺技术优势及氧化机理进行探究.结果表明：在相同条件下（O₃浓度84mg/L）,电-多相臭氧催化获得的COD和TOC的去除率（分别为67.9%,50.0%）显著优于O₃/TiO_2-NF获得的去除率（25.8%,20.9%）,即便在O₃/TiO_2-NF体系中投加5g/L的H₂O₂以促进臭氧均相催化效果,但COD和TOC去除率也仅分别提高到63.6%,43.6%.     

焦化废水中不同极性组分的光谱分析及可生物降解特性

焦化废水是典型难降解工业有机废水,构成其成分的复杂及种类的繁多使其难以实现高效的生物降解过程,制约了水处理的水质达标.为了探明其中生物降解强抑制组分,采用DAX-8大孔树脂将焦化废水分离出疏水酸性组分(HOA)、疏水碱性组分(HOB)、疏水中性组分(HON)和亲水性组分(HIS)等4种极性不同的组分,分析了各组分的有机物含量分布,紫外吸收光谱和三维荧光光谱,并用两种方法考察了各组分的可生物降解性能.结果表明,HOA是主要的有机组分,其COD和TOC分别占比55.9%和56.8%;HOA也是主要的芳香物质及荧光组分,而HON是芳香构造化程度最高和类腐殖质占比P(Ⅲ+Ⅴ)最高的组分;各组分的BOD5/COD值及脱氢酶活性的抑制结果显示其难降解程度依次为HONHOBHIS原水HOA,而HON是焦化废水中生物抑制最强组分,其BOD5/COD值仅为0.21±0.02,对脱氢酶活性的抑制达到38.5%;SUVA和P(Ⅲ+Ⅴ)与可生物降解性的关联分析发现,焦化废水中难降解组分并不都是芳香性化合物造成的,类腐殖质对其中难降解有机组分的指示作用相比SUVA更加灵敏.     

一种高效提取焦化废水活性污泥总DNA的方法

对焦化废水活性污泥中微生物建立高质量的总DNA提取方法是开展分子生态学研究的重要前提.通过反复冻融-蛋白酶K-SDS、溶菌酶-反复冻融-SDS及溶菌酶-反复冻融-蛋白酶K-SDS这3种综合方法对焦化废水活性污泥总DNA进行提取,以OD260/OD280、OD260/OD230、产率、片段完整性、片段大小5个指标来评价样品总DNA的提取效果.结果表明,溶菌酶-反复冻融-蛋白酶K-SDS法所提取的总DNA的OD260/OD280值约为1.8,产率为1.90～16.30 μg·g-1,片断完整性好,主带清晰,大小约为23 kb,其PCR反应抑制物少,能够直接进行16S rRNA基因的PCR扩增.溶菌酶-反复冻融-蛋白酶K-SDS法能够为焦化废水活性污泥中微生物的分子生态学研究提供高质量的总DNA.     

焦化废水活性污泥法处理中微型动物群落及其与处理性能之间的关系

为了分析难降解焦化废水活性污泥法处理中的微型动物群落特征,本研究考察了活性污泥法焦化废水处理厂中的微型动物群落,分析了其与处理性能之间的相互关系.结果发现,本研究共采集的64个水样中,鉴别出28个种属微型动物,其中,原生动物27种(22种纤毛虫、4种鞭毛虫、1种有壳变形虫),1个类群微型后生动物.固着型和匍匐型纤毛虫为共优势群,固着型小口钟虫(Vorticella microstoma)为绝对优势种.除小口钟虫(V.microstoma)(出现频率100%)外,出现频率较高的种类还有轮虫(rotifers)(97%)、沟钟虫(Vorticella convallaria)(69%)等.与常规废水活性污泥法处理系统相比,焦化废水处理系统中的微型动物种类和数量相对偏低.相关性分析结果表明,生物学参数与出水水质、运行参数间存在着不同的相关性.其中,累枝虫属(Epistylis spp.)与出水氨氮(r=-0.740,p0.01)、氰化物(r=0.509,p0.05)和DO(r=0.514,p0.05)存在着显著的相关性;吸管虫属(Podophrya spp.)与硝化效率呈显著负相关(p0.05),它们可作为系统处理性能参数的指示微生物;其他种属与出水水质和运行参数间的相关性不显著(p0.05).因子分析揭示了与系统相关联的潜在的重要影响因素,以及某些微型动物种属间存在的相互关系.     

臭氧/活性炭/紫外光联用处理几种高浓度有机废水影响因素

以对硝基苯甲酸废水、鸟嘌呤废水、乙醛废水和乙醇胺废水为例,对臭氧/活性炭氧化去除废水中有机物的效果进行了初步研究,考察了臭氧投加量、pH值和紫外光等因素对臭氧/活性炭催化氧化高浓度有机废水的影响,并在最优条件下,验证了该工艺作为高浓度有机废水预处理手段,在去除废水中COD和提高可生化性(BOD5/COD)等方面的综合效果.结果表明,活性炭作为催化剂与臭氧共同作用,对对硝基苯甲酸废水COD的去除率明显高于单独臭氧氧化和活性炭吸附;臭氧/活性炭氧化对乙醛废水和乙醇胺废水这类短链类有机物降解作用不大,但对硝基苯甲酸废水、鸟嘌呤废水这些含有苯环类、长链类的有机物,去除效率较高;在中性偏碱时,pH的提高有利于COD的去除,但过高pH对COD的降解效果反而有所减弱,pH=9.0是比较合适的;在紫外光催化的条件下,采用臭氧/活性炭氧化工艺处理对硝基苯甲酸废水,COD去除率可达到52%,废水的生化性(BOD5/COD)由原来的0.10提高到0.32,大大提高了废水的可生化性.