焦化废水中有机污染物经厌氧酸化后对好氧生物降解性能的影响

 采用厌氧酸化处理间歇装置和瓦勃氏微量呼吸测压仪，对萘等10种焦化废水中有机污染物进行厌氧酸化后好氧生物降解性能的研究。研究表明，受试的有机物经过厌氧酸化处理后均发生了不同程度的转化。萘、吡咯、咪唑、喹啉、吲哚生物氧化率有明显提高；联苯、三联苯、吡啶、咔唑从对好氧微生物的抑制状态转化为易于生物降解的物质；吩噻嗪抑制作用解除，但仍是难以生物降解物质。     

Analysis of organic compounds in coal gasification wastewater

A procedure for analysis of organic pollutants in coal gasification wastewater was developed, including a series extraction steps at different pH, followed by LC separation or resin adsorption, then analyzed by GC or GC/MS. More than 200 organic pollutants in 22 categories were determined. CH2CL2 extraction at NaHCO3 presence was used to separate carboxylic acids with phenolic compounds in aqueous. Derivatization with acetic anhydride was used for analyses of mono-, di-, poly-hydroxyl phenolic compounds. 21 mono-hydroxyl phenols and 13 di-hydroxyl phenols were determined from the coai gasification wastewater samples. Derivatization with BF3-CH3OH was used for analysis of carboxylic acid. 17 mono-carboxyl, 4 di-carboxyl acids and 6 aromatic acids were determined from coal gasification wastewater samples.     

Inhibition and recovery of nitrification in treating real coal gasification wastewater with moving bed biofilm reactor

Moving bed biofilm reactor (MBBR) was used to treat real coal gasification wastewater. Nitrification of the MBBR was inhibited almost completely during start-up period. Sudden increase of influent total NH3 concentration was the main factor inducing nitrification inhibition. Increasing DO concentration in the bulk liquid (from 2 to 3 mg/L) had little e ect on nitrification recovery. Nitrification of the MBBR recovered partially by the addition of nitrifying sludge into the reactor and almost ceased within 5 days. Nitrification ratio of the MBBR achieved 65% within 12 days by increasing dilute ratio of the influent wastewater with tap water. The ratio of nitrification decreased to 25% when influent COD concentration increased from 650 to 1000 mg/L after nitrification recovery and recovered 70% for another 4 days.     

Anaerobic treatment of wastewater containing methanol in upflow anaerobic sludge bed (UASB) reactor

The direct conversion of methanol into methane is the main process in anaerobic treatment of methanol containing wastewater. However, acetic acid can also be produced from methanol theoretically, which may probably result in an abrupt pH drop and deteriorate the anaerobic process. Therefore, it is interesting to know what would really happen in an anaerobic reactor treating methanol wastewater. In this study, an up-flow anaerobic sludge bed (UASB) reactor treating methanol wastewater was operated. The chemical oxygen demand (COD), acetic acid and pH of the effluent were monitored at different loadings and influent alkalinity. The results showed that the anaerobic reactor could be operated steadily at as low as 119 mg/L of influent alkalinity and high organic loading rate with no obvious pH drops. Volatile fatty acids accumulation was not observed even at strong shock loadings. The microorganisms in the sludge at the end of the test became homogeneous in morphology, which were mainly spherical or spheroidal in shape. __________ Translated from China Water & Wastewater, 2006, 22(13): 42–44,48 [译自: 中国给水排水]     

Inhibitory effect of high phenol concentration in treating coal gasification wastewater in anaerobic biofilter

In this paper, the inhibition of methanogens by phenol in coal gasification wastewater(CGW)was investigated by both anaerobic toxicity tests and a lab-scale anaerobic biofilter reactor(AF). The anaerobic toxicity tests indicated that keeping the phenol concentration in the influent under 280 mg/L could maintain the methanogenic activity. In the AF treating CGW,the result showed that adding glucose solution as co-substrate could be beneficial for the quick start-up of the reactor. The effluent chemical oxygen demand(COD) and total phenol reached1200 and 100 mg/L, respectively, and the methane production rate was 175 m L CH4/g COD/day.However, if the concentration of phenol was increased, the inhibition of anaerobic micro-organisms was irreversible. The threshold of total phenol for AF operation was 200–250 mg/L. The extracellular polymeric substances(EPS) and particle size distribution of anaerobic granular sludge in the different stages were also examined, and the results indicated that the influence of toxicity in the system was more serious than its effect on flocculation of EPS. Moreover, the proportion of small size anaerobic granular sludge gradually increased from10.2% to 34.6%. The results of high through-put sequencing indicated that the abundance of the Chloroflexi and Planctomycetes was inhibited by the toxicity of the CGW, and some shifts in the microbial community were observed at different stages.     

曝气生物流化床(ABFB)处理煤气化废水的研究

介绍一种曝气生物流化床的基本原理及特点,制作了总有效容积为1.5m³的曝气生物流化床(ABFB)中试设备,流化介质为合成高分子多孔材料,其物理性能为:持水量25倍、比表面积≥200m²/g、含氮量6.72%,载体带有-NH₂、-COOH、-OH、环氧基等活性基团可与微生物结合而固定化微生物,载体中生物量平均为28g/L(H₂O),故具有很高的处理效率.对平均值为COD 3450mg/L、NH₄⁺-N 451mg/L、挥发酚为177 mg/L的煤气化废水,经过ABFB处理后,其处理水中COD 57.7mg/L、NH₄⁺-N 0.285mg/L、挥发酚0.434mg/L,其运行效果优于曝气生物滤池(BAF)、接触氧化、活性炭流化床.ABFB具有运行稳定、抗冲击负荷强的特点,是一种先进的水处理技术.     

An advanced anaerobic biofilter with effluent recirculation for phenol removal and methane production in treatment of coal gasification wastewater

An advanced anaerobic biofilter (AF) was introduced for the treatment of coal gasification wastewater (CGW), and effluent recirculation was adopted to enhance phenol removal and methane production. The results indicated that AF was reliable in treating diluted CGW, while its efficiency and stability were seriously reduced when directly treating raw CGW. However, its performance could be greatly enhanced by effluent recirculation. Under optimal effluent recirculation of 0.5 to the influent, concentrations of chemical oxygen demand (COD) and total phenol in the effluent could reach as low as 234.0 and 14.2 mg/L, respectively. Also, the rate of methane production reached 169.0 mL CH₄/L/day. Though CGW seemed to restrain the growth of anaerobic microorganisms, especially methanogens, the inhibition was temporary and reversible, and anaerobic bacteria presented strong tolerance. The activities of methanogens cultivated in CGW could quickly recover on feeding with glucose wastewater (GW). However, the adaptability of anaerobic bacteria to the CGW was very poor and the activity of methanogens could not be improved by long-term domestication. By analysis using the Haldane model, it was further confirmed that high effluent recirculation could result in high activity for hydrolytic bacteria and substrate affinity for toxic matters, but only suitable effluent recirculation could result in high methanogenic activity.     

稠油乳化段废水厌氧处理过程中COD与BOD5的协同变化及可生化性研究

稠油乳化段废水中的主要污染物为有机聚合物和石油类污染物，BOD5／COD值极低，可生化性差，通过厌氧处理可使污染物发生水解反应，BOD5／COD值由0．08升为0．15（288h)，与其它难降解有机废水的厌处理结果不同，在BOD5增加的同时，COD亦大幅度增加，而在全部厌氧反应过程中，TOC一直呈下降趋势，表明水样中的污染物在生物作用下不断得到消减；在COD达到最高时，石油类污染物中胶质的浓度大幅度降低，烷烃的浓度升高，说明以胶质为代表的大分子污染物因子解反应，由K2Cr2O7不能氧化状态变为可氧化状态，导致COD测量值显著升高。     

Advanced treatment of biologically pretreated coal gasification wastewater by a novel heterogeneous Fenton oxidation process

Sewage sludge from a biological wastewater treatment plant was converted into sewage sludge based activated carbon(SBAC) with Zn Cl2 as activation agent, which was used as a support for ferric oxides to form a catalyst(Fe Ox/SBAC) by a simple impregnation method.The new material was then used to improve the performance of Fenton oxidation of real biologically pretreated coal gasification wastewater(CGW). The results indicated that the prepared Fe Ox/SBAC significantly enhanced the pollutant removal performance in the Fenton process, so that the treated wastewater was more biodegradable and less toxic. The best performance was obtained over a wide p H range from 2 to 7, temperature 30°C, 15 mg/L of H2O2 and 1 g/L of catalyst, and the treated effluent concentrations of COD, total phenols,BOD5 and TOC all met the discharge limits in China. Meanwhile, on the basis of significant inhibition by a radical scavenger in the heterogeneous Fenton process as well as the evolution of FT-IR spectra of pollutant-saturated Fe Ox/BAC with and without H2O2, it was deduced that the catalytic activity was responsible for generating hydroxyl radicals, and a possible reaction pathway and interface mechanism were proposed. Moreover, Fe Ox/SBAC showed superior stability over five successive oxidation runs. Thus, heterogeneous Fenton oxidation of biologically pretreated CGW by Fe Ox/SBAC, with the advantages of being economical, efficient and sustainable, holds promise for engineering application.     

粉末活性焦强化A/A/O工艺处理煤气化废水的中试研究

煤气化废水水质复杂,是一种典型的难降解工业废水,而常规A/A/O工艺生化处理效率不高,严重制约了此类废水的处理和回用.因此,试验进行了粉末活性焦强化A/A/O工艺处理煤气化废水的中试研究,向好氧池投加粉末活性焦形成生物膜-悬浮污泥复合系统,并将剩余污泥回流至系统前段对原水进行预处理.研究结果表明,在活性焦投加量为250 mg·L-1,系统总HRT为105 h的优化条件下,CODCr、氨氮、总氮的去除率分别为97.4%、98.1%和80.5%,出水浓度分别为76 mg·L-1、0.3 mg·L-1和22.4 mg·L-1,达到《循环冷却水用再生水水质标准》(HG/T3923—2007)中CODCr≤80 mg·L-1、NH3-N≤15 mg·L-1、TN≤30 mg·L-1的要求.进一步机理研究表明,向好氧池中投加的粉末活性焦可作为微生物载体和菌胶团核心,投加活性焦后,好氧池的活性污泥浓度增加了57.9%.含焦剩余污泥对原水进行吸附预处理,石油类和SS的去除率分别为34.8%和61.5%,降低了废水对生化系统的毒害作用和冲击负荷,从而提高了系统的整体效率.     

金刚石膜电极电化学氧化提高废水可生化性的研究

采用掺硼金刚石膜电极(BDD)电化学氧化的方法提高2-氯苯酚废水的可生化性,与钛基钌铱氧化物电极(DSA)进行对比,研究了该方法的机理.结果表明,BDD电极电化学氧化2.0h后,BOD5/CODCr值达到0.42,有效提高了废水的可生化性,而DSA电极电化学氧化2.0h后,BOD5/CODCr值仅为0.24.机理研究表明,由于BDD电极具有高的析氧电位,可产生大量的羟基自由基(×OH),能够使2-氯苯酚的苯环充分开环,形成草酸、顺丁烯二酸等易生化处理的中间产物,从而使可生化性提高;而DSA电极的析氧电位较低,产生羟基自由基的能力较差,不能有效地提高废水的可生化性.     

Environmental benefits of underground coal gasification

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生物膜反应器降解生物质气化洗焦废水

陶瓷球作为固定介质 ,接种本实验室保藏的Pseudomonassp1和Pseudomonassp2混合菌种 ,应用生物膜反应器处理生物质气化过程中产生的洗焦废水 ,对反应器运转整个过程的进出水COD浓度、进出水苯、萘、菲、吡啶、喹啉、异喹啉的含量、反应器内和反应器出水含菌量进行测定 ,以了解生物膜反应器处理生物质气化洗焦废水的特性 .结果表明 ,反应器经挂膜、增菌后 ,可达到稳定运转状态 ,有效的控制了反应器内微生物细胞的流失 ,使生物质气化洗焦废水中的有机物得到较好去除 .     

Anaerobic biodegradability of terephthalic acid andits inhibitory effect on anaerobic digestion

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腈纶废水溶解性有机物的分级解析及可生化性

采用超滤膜法将腈纶废水中溶解性有机物分离为6个不同相对分子质量组分,分析不同组分的溶解性有机碳、UV₂₅₄、SUVA含量和分布情况,应用紫外吸收光谱、傅里叶变换红外光谱等光谱学分析方法对各组分物质结构进行定性分析,评价各组分的可生化性.结果表明废水中以相对分子质量< 3kDa的有机物为主,占比为（56.75±1.38）%;相对分子质量为3k~10kDa的有机物占比为（25.76±1.40）%;相对分子质量> 10kDa的有机物占比为（17.49±0.98）%,且该组分有机物的芳香度高.不同相对分子质量组分的紫外光谱和红外光谱均呈现相似吸收峰,均存在酰基、羧基、羰基及芳香族化合物和不饱和双键类有机物.各组分可生化性结果表明,废水中相对分子质量> 10kDa有机物是腈纶废水低可生化性的主要原因,可能是造成腈纶废水难以达标排放的根源.研究结果可为该废水处理工艺的开发与优化提供重要的指导.     

Nitrogen removal from coal gasification wastewater by activated carbon technologies combined with short-cut nitrogen removal process

A system combining granular activated carbon and powdered activated carbon technologies along with shortcut biological nitrogen removal （GAC-PACT-SBNR） was developed to enhance total nitrogen （TN） removal for anaerobically treated coal gasification wastewater with less need for external carbon resources. The TN removal efficiency in SBNR was significantly improved by introducing the effluent from the GAC process into SBNR during the anoxic stage, with removal percentage increasing from 43.8%49.6% to 68.8%-75.8%. However, the TN removal rate decreased with the progressive deterioration of GAC adsorption. After adding activated sludge to the GAG compartment, the granular carbon had a longer service-life and the demand for external carbon resources became lower. Eventually, the TN removal rate in SBNR was almost constant at approx. 43.3%, as compared to approx. 20.0% before seeding with sludge. In addition, the production of some alkalinity during the denitrification resulted in a net savings in alkalinity requirements for the nitrification reaction and refractory chemical oxygen demand （COD） degradation by autotrophic bacteria in SBNR under oxic conditions. PACT showed excellent resilience to increasing organic loadings. The microbial community analysis revealed that the PACT had a greater variety of bacterial taxons and the dominant species associated with the three compartments were in good agreement with the removal of typical pollutants. The study demonstrated that pre-adsorption by the GAC-sludge process could be a technically and economically feasible method to enhance TN removal in coal gasification wastewater （CGW）.     

Supercritical gasification for the treatment of o-cresol wastewater

The supercritical water gasification of phenolic wastewater without oxidant was performed to degrade pollutants and produce hydrogen-enriched gases. The simulated o-cresol wastewater was gasified at 440-650℃ and 27.6 MPa in a continuous Inconel 625 reactor with the residence time of 0.42-1.25 min. The influence of the reaction temperature, residence time, pressure, catalyst, oxidant and the pollutant concentration on the gasification efficiency was investigated. Higher temperature and longer residence time enhanced the o-cresol gasification. The TOC removal rate and hydrogen gasification rate were 90.6% and 194.6%, respectively, at the temperature of 650℃ and the residence time of 0.83 min. The product gas was mainly composed of H2, CO2, CFL and CO, among which the total molar percentage of H2 and CFL was higher than 50%. The gasification efficiency decreased with the pollutant concentration increasing. Both the catalyst and oxidant could accelerate the hydrocarbon gasification at a lower reaction temperature, in which the catalyst promoted H2 production and the oxidant enhanced CO2 generation. The intermediates of liquid effluents were analyzed and phenol was found to be the main composition. The results indicate that the supercritical gasification is a promising way for the treatment of hazardous organic wastewater.     

高浓度甲醇废水厌氧处理中颗粒污泥和产甲烷细菌的耐酸性

采用两段UASB处理工艺和间歇培养试验,对高浓度甲醇废水厌氧处理的运行特性进行了研究,并较深入地研究了颗粒污泥和产甲烷菌的耐酸特性及代谢活性.试验结果表明,两段UASB反应器的pH值较低,分别为4.9～5.8和5.5～6 2,显然,这不是一般产甲烷细菌适宜的pH范围.系统中的产甲烷菌即巴氏产甲烷八叠球菌,具有一定耐酸性,在pH为5.0时仍然能够降解甲醇,如果进一步培养,其耐酸性将有所提高.系统中的颗粒污泥能够保护其内部的产甲烷菌,较少地受酸性环境的影响,并在pH为4.5时仍能降解甲醇.颗粒污泥的这种性能与其结构、细菌种类和颗粒体内细菌分布情况有很大关系.     

褐煤地下气化过程汞析出规律的研究

在褐煤地下气化模型试验的基础上 ,研究了褐煤中汞的赋存形态 ,褐煤地下气化煤气中汞含量的变化及存在形态 ,以及气化工艺的影响 ;分析了地下气化过程中汞的析出及反应机理 .实验结果表明 ,汞在试验褐煤中主要以硫化物结合态和残渣态形式存在 ;褐煤地下气化煤气中汞含量随气化时间的变化而变化 ,且主要以Hg0 (g)的形态存在 ;水蒸汽的存在会降低Hg0 (g)被其它气体氧化为Hg2 (g)的趋势 ;与地面气化及燃煤过程不同 ,煤地下气化产物中 ,气态汞占总汞比例低于 2 0 % ,明显低于地面气化及燃煤     

烟煤地下气化过程中硫的转化规律研究

在烟煤炭地下气化模型试验的基础上,研究了气化炉温度、气化工艺等对硫转化的影响;在纯氧气化工艺条件下,煤气中含硫气体的形态和含量主要受温度的影响,产生的H2S浓度在600～700℃达到最大值为7400mg·m-3,SO2在1000℃时达到最大值为270 mg·m-3.在纯氧-水蒸气工艺阶段,煤气中的含硫气体形态主要受煤气中氢气含量的影响,但在纯氧-水蒸气工艺后期,含硫气体量又转变为温度的函数.煤炭地下气化过程中,煤中的硫大部分以含硫气体的形式分布在煤气中;只有小部分硫分布在灰渣、焦油和冷凝水中.