强化活性炭处理工艺去除焦化厂生化出水中的氰化物

以某焦化厂生化出水为研究对象,考寨了金属负载活性炭(简称负载炭)和Fenton氧化预处理等强化活性炭工艺对总氰化物(TCN)的去除效果.在TCN批式实验中,对负载炭的金属离子种类和固定方式进行了考察,同时研究了接触时间、DO对游离氰(KCN配水)、络合氰(K3Fe(CN)6配水)及焦化厂生化出水中TCN的去除效果.结果表明,负载金属离子可以有效提高活性炭对TCN的去除量,KI固定后的载铜活性炭对TCN的去除更有效.吸附作用在活性炭去除TCN过程中起着主要作用,同时TCN在活性炭表面也发生缓慢的催化氧化反应.在穿透实验中,采用了小型炭柱穿透和微型快速穿透实验方法,得到的TCN穿透曲线基本相同.含不同比例原煤炭和负载炭的小型炭柱处理经Fenton氧化预处理的焦化厂生化出水时,在18 d的启动阶段后形成生物活性炭柱,其出水能长期达到<城镇污水处理厂污染物排放标准>(GB 18918-2002)规定的要求.载铜话性炭可以提高活性炭工艺对TCN的去除能力,确保处理全程(57 d)出水的TCN达标.     

Biological treatment of a synthetic gold milling effluent

This paper reports on biological sludge acclimatisation and the results concerning the removal of free cyanide, thiocyanate and metallocyanides (copper, iron and zinc) from a synthetic gold milling effluent. The experiments were carried out in a continuous bench-scale bioreactor, and the experimental set-up consisted of two identical units, one of which served as control. The acclimatisation of the biomass was based on a stepwise procedure, in which the proportion of synthetic solution in the influent was gradually increased. The reactors were fed with a mixture of synthetic effluent and sewage, and the treatment efficiency was evaluated through the monitoring of the following parameters: chemical oxygen demand (COD), free cyanide, thiocyanate, copper, iron and zinc concentrations. A well adapted microbial consortium was obtained at the end of the acclimatisation period, which was able to remove more than 95% of free cyanide, thiocyanate, copper and zinc, originally found in the influent. These removal efficiencies were obtained when the reactor was operated with a hydraulic retention time (HRT) of about 8 h. The performance results of experiments carried out with lower HRT (5 h) and higher dissolved oxygen (DO) concentration (6.5 mg litre(-1)) are also presented and discussed in this study.     

焦化废水中COD、挥发酚和硫氰化物同步高效去除

采用两级膨胀颗粒污泥床(EGSB)反应器在微氧条件下处理焦化废水,考察了该工艺对焦化废水中挥发酚、硫氰化物、氰化物和COD的去除效果。研究结果表明,在进水流量为1 L/h,总水力停留时间(HRT)为24 h的条件下,两级EGSB反应器对COD的去除效果较好。稳定运行时,在进水挥发酚为56.8~185.1 mg/L、硫氰化物为287.1~539.9 mg/L、氰化物为0.17~0.72 mg/L的条件下,系统对其平均去除率分别为99.9%、96.8%和82.6%,出水挥发酚和氰化物均能达到《污水综合排放标准(GB8978-1996)》的一级标准。进水COD浓度在1 084~1 880 mg/L之间,平均去除率为76.9%,出水平均浓度为325 mg/L。     

废旧镍镉电池的生物沥滤处理——沥滤停留时间的影响研究

用污泥加硫酸化液沥滤镍镉电池中的重金属是一种全新的工艺,该工艺主要由生物酸化反应器和金属沥滤反应器两个反应器组成.生物酸化反应器中产生的酸液就是沥滤电池中重金属的反应液.研究表明,酸化液在沥滤反应池的停留时间对沥滤的效果有显著影响.在1、4、7、12 d 4个停留时间中,4 d的效果是最好的,对金属Cd和Ni都用40 d左右基本实现了全部滤除;1d略微慢一些,Cd用了40 d,Ni用了45 d;7 d和12 d的沥滤时间都长于50 d.4 d产生的金属废液量是1 d的1/4,考虑到后续处理金属沥滤废液的工作量,选择4d的停留时间要优于1d.     

Microbial kinetic analysis of three different types of EBNR process

The disadvantages of developed biological nutrient removal (BNR) processes (additional energy for liquid circulation and addition of external carbon substrate for denitrification in anoxic zones) were improved by reconfiguring the process into (1) an anaerobic zone followed by multiple stages of aerobic-anoxic zones (TNCU3 process) or (2) anaerobic, oxic, anoxic, oxic zones in sequence (TNCU2 process). These two pilot plants were operated at a recycling sludge ratio of 0.5 without internal recycle of nitrified supernatant. The sludge retention time was maintained at 10 d. The main objective of this study is to analyze the kinetics of different microorganisms in these two processes and A2O process by using the Activated Sludge Model No. 2d. The effective removal efficiency of carbon, total phosphorus and total nitrogen at 87-98%, 92-100% and 63-80%, respectively, were achieved in the testing runs. According to model simulations, the microbial kinetics in the TNCU3 and TNCU2 processes would be affected by different operations. When the step feeding strategy was adopted, the HRT was longer due to the less influent flowrate in the front stages and the microbes would grow in quantities by about 6% in the aerobic reactors. In the followed anoxic reactors, the microbes would decrease in quantities by about 12% due to the dilution effect. The dilution effects in TNCU3 and TNCU2 processes did not take place in A2O process because the recycling mixed liquid from the aerobic reactor to the anoxic reactor still contained particulate components. The XH, XPAO, and XAUT concentrations in the effluent of the last tank were lower when the step-feeding mode was adopted. The TNCU3 and TNCU2 processes could be operated efficiently without nitrified liquid circulation and addition of external carbon substrate for denitrification.     

Microbial degradation of metal complexed cyanides and thiocyanate from mining wastewaters

A microbiological examination of the soil from a cyanide wastewater storage basin was carried out. The storage basin contained water from the cyanidation process of gold extraction, and it was composed principally of simple cyanide, metal complexed cyanide, mainly cuprocyanide, ferro-ferricyanides and thiocyanate. Pseudomonas species were the principal bacteria identified in the soil. Using the storage basin soil as a seed sludge, its potential for the biodegradation of all the cyanide complexes in the mining wastewater was studied in the laboratory, using batch, fed-batch and continuous processes. The ammonia and sulphate produced were quantified. The presence of intermediate products was suspected. In the continuous process, total degradation of all cyanide was observed at a dilution rate of 0.066 day(-1).     

填料对厌氧移动床生物膜反应器运行效果的影响

通过对装有不同填料的2个厌氧移动床生物膜反应器(R1和R2)的有机负荷、COD去除率、沼气产量及其组成、出水挥发性有机酸(VFA)和出水pH值的对比,得出在填料充填率相同、进水COD和进水pH相似的情况下,填料比表面积是影响厌氧移动床生物膜反应器运行效果的主要因素.R1中填料的比表面积为528 m2/m3,R2中填料比表面积为211m2/m3.在整个运行阶段,填料比表面较大的R1反应器的运行结果较好.试验结束时,R1与R2的有机负荷比为1.61,而R1与R2填料上的污泥量之比为4.42.     

Assessment of the effluent quality from a gold mining industry in Ghana

The physical and chemical qualities of the process effluent and the tailings dam wastewater of AngloGold-Ashanti Limited, a gold mining company in Ghana, were studied from June to September, 2010. The process effluent from the gold extraction plant contains high amounts of suspended solids and is therefore highly turbid. Arsenic, copper and cyanide were identified as the major pollutants in the process effluent with average concentrations of 10.0, 3.1 and 21.6 mg?L^?1, respectively. Arsenic, copper, iron and free cyanide (CN^?) concentrations in the process effluent exceeded the Ghana EPA discharge limits; therefore, it is necessary to treat the process effluent before it can be discharged into the environment. Principal component analysis of the data indicated that the process effluent characteristics were influenced by the gold extraction process as well as the nature of the gold-bearing ore processed. No significant correlation was observed between the wastewater characteristics themselves, except for the dissolved oxygen and the biochemical oxygen demand. The process effluent is fed to the Sansu tailings dam, which removes 99.9 % of the total suspended solids and 99.7 % of the turbidity; but copper, arsenic and cyanide concentrations were still high. The effluent produced can be classified as inorganic with a high load of non-biodegradable compounds. It was noted that, though the Sansu tailings dam stores the polluted effluent from the gold extraction plant, there will still be serious environmental problems in the event of failure of the dam.     

Formation of free cyanide and cyanogen chloride from chloramination of publicly owned treatment works secondary effluent: laboratory study with model compounds.

The potential generation of cyanide species in wastewater upon chlorination in the presence of residual ammonia (resulting in chloramine formation) was investigated in experiments with synthetic solutions and publicly owned treatment works (POTW) secondary effluent. This study demonstrated that low concentrations (approximately 5 to 25 microg/L as cyanide) of cyanogen chloride (CNCI), a highly toxic cyanide species not measured in total or free cyanide analyses, could be detected as a result of chloramination reactions in POTW secondary effluent. The potential for chloramination of nitrogen-bearing organic compounds to yield CNCl and/or free cyanide was demonstrated in experiments with synthetic solutions spiked with selected precursor organics: L-serine, benzene, catechin, and humic acid. The amino acid L-serine yielded the largest concentrations of CNCI upon chloramination. Additionally, detectable cyanide (approximately 10 microg/L) was observed in solutions of L-serine and in POTW secondary effluent that was chloraminated followed by dechlorination to prevent destruction of any free cyanide produced. Thus, chlorination of POTW secondary effluent containing residual ammonia can lead to chloramination of organic compounds and the resulting production of CNCl and free cyanide.     

Case study I: application of the divalent cation bridging theory to improve biofloc properties and industrial activated sludge system performance-direct addition of divalent cations.

The objectives of this study were to examine the application of the divalent cation bridging theory (DCBT) to improve settling, dewatering, and effluent quality in pilot-scale reactors and a full-scale system treating an industrial wastewater. This was accomplished by lowering the monovalent-to-divalent (M/D) cation ratio by direct divalent cation addition. Research has shown that the M/D ratio is a potential indicator for settling and dewatering problems at wastewater treatment plants, and M/D ratios above 2 have been associated with poor settling, dewatering, and effluent quality. The M/D ratio of the wastewater in this study ranged from 6 to 20. The cations studied were calcium and magnesium. Results showed that the addition of calcium improved floc properties compared to control reactors with no calcium addition. The reductions in sludge volume index, effluent chemical oxygen demand (COD), and effluent total suspended solids (TSS) were approximately 35, 34, and 55%, respectively, when the M/D ratio was decreased to approximately 2:1. In addition, the cake solids from a belt filter press simulator increased by 72% and the optimum polymer dose required for conditioning was reduced by 70% in the reactor fed the highest calcium concentration when compared to control reactors with no calcium addition. The addition of calcium also decreased the negative effect of high filamentous organism numbers. In general, the addition of magnesium (Mg2+) had similar effects on effluent quality and dewatering properties, although some differences were measured. A full-scale test using calcium addition was performed. Measurements of effluent quality and floc properties were performed before, during, and after the calcium (Ca2+) addition period. The average M/D ratio during these periods was 6.2, 4.6, and 14.0, respectively. The addition of Ca2+ decreased the effluent five-day biochemical oxygen demand, effluent TSS, and effluent COD. The increased Ca2+ concentration also improved dewatering measured by a decrease in specific resistance to filtration and capillary suction time. Overall, the addition of divalent cations to the pilot- and full-scale activated sludge systems improved floc properties and the data fit well with the DCBT.     

Cyanide generation during preservation of chlorinated wastewater effluent samples for total cyanide analysis.

Dechlorinating agents and pH adjustment are often used to preserve wastewater samples for cyanide analysis. The effects of four approved preservation protocols on the results of the total cyanide analysis of effluents from four water reclamation plants were examined. The results differed widely, and a clear pattern emerged. Immediate analysis without pH adjustment generally gave total cyanide concentrations below the reporting limit of 5 microg/L, irrespective of the dechlorinating agents used. When the pH was adjusted to > or =12, a slight increase in the measured total cyanide concentration was observed when thiosulfate was used to dechlorinate the samples, and a significant increase (>10 microg/L) was observed when arsenite was used as the dechlorinating agent. These results provide evidence that approved preservation protocols may give rise to cyanide formation in chlorinated wastewater effluent matrices.     

The occurrence of cyanide formation in six full-scale publicly owned treatment works.

This paper presents results from an intensive monitoring program implemented at six full-scale publicly owned treatment works (POTWs) to investigate the fate and formation of cyanide in wastewater treatment processes, with a focus on chlorination and dechlorination processes. A review of historical monitoring data for cyanide species in these POTWs was also conducted. This POTW monitoring program provided a database for the investigation of cyanide formation in wastewater secondary treatment. Data from participating POTWs showed evidence of cyanide formation in this 1-year monitoring effort, although the cyanide formation pattern varied significantly from one plant to another and among seasons. Generally, the chlorination of thiocyanate (SCN-) seems to be the most important mechanism for the formation of cyanide in wastewater treatment processes, especially in chlorination and dechlorination. This hypothesis is supported by the findings of a related laboratory study of mechanisms of cyanide formation in POTWs. It is recommended that POTWs monitor SCN in influent and secondary effluent to identify its presence and adjust chlorine dose appropriately.     

Cyanide detoxification by recombinant bacterial rhodanese

Cyanide is a major environmental pollutant of the chemical and metallurgical industries. Although extremely toxic, cyanide can enzymatically be converted to the less toxic thiocyanate by rhodaneses (thiosulfate:cyanide sulfurtransferases, EC 2.8.1.1). We engineered a genetic system to express high levels of recombinant Pseudomonas aeruginosa rhodanese (r-RhdA) in Escherichia coli, and used this organism to test the role of r-RhdA in cyanide detoxification. Inducible expression of the rhdA gene under the control of the hybrid T7-lacO promoter yielded active r-RhdA over a 4-h period, though r-RhdA-expressing E. coli showed decreased viability starting from 1 h post-induction. At this time, Western blot analysis and enzymatic assay showed r-RhdA partition between the cytoplasm (95%) and the periplasm (5%). The accessibility of thiosulfate to r-RhdA was a limiting step for the sulfur transfer reaction in the cellular system, but cyanide conversion to thiocyanate could be increased upon permeabilization of the bacterial membrane. Specific r-RhdA activity was higher in the whole-cell assay than in the in vitro assay with pure enzyme (2154 vs. 816 micromol min-1 mg-1 r-RhdA, respectively), likely reflecting enzyme stability. The r-RhdA-dependent cyanide detoxification resulted in increased resistance of r-RhdA overexpressing E. coli to 5 mM cyanide. Bacterial survival was paralleled by release of thiocyanate into the medium. Our results indicate that cyanide detoxification by engineered E. coli cells is feasible under laboratory conditions, and suggest that microbial rhodaneses may contribute to cyanide transformation in natural environments.     

Application of anaerobic and aerobic activated sludge to phosphorus-deficient wastewater treatment.

Anaerobic and aerobic (AnA) and completely aerobic (CA) sequencing-batch reactors (SBRs) were used to investigate the suitability of the AnA process for treating phosphorus (P)-deficient wastewaters with highly variable influent chemical oxygen demand (COD) loading. Both SBRs were subjected to influent COD loading patterns (LPs) that simulated (1) daily COD loading fluctuations, (2) weekend shutdowns, and (3) long weekend or holiday shutdowns. During LP 1, the AnA SBR produced lower average effluent soluble phosphorus concentrations than CA SBR (0.4 vs. 1.0 mgP/L). A similar result was observed during LP 2, but effluent acetate was detected after the first high COD loading cycle of the weekday loading period. During LP 3, the volatile suspended solids content of both reactors dropped sharply, and the effluent quality of both SBRs deteriorated. Model predictions suggest that the AnA process is stable when treating LP 1, but eventually fails when treating LP 2.     

Modeling external carbon addition in biological nutrient removal processes with an extension of the international water association activated sludge model

The aim of this study was to expand the International Water Association Activated Sludge Model No. 2d (ASM2d) to account for a newly defined readily biodegradable substrate that can be consumed by polyphosphate-accumulating organisms (PAOs) under anoxic and aerobic conditions, but not under anaerobic conditions. The model change was to add a new substrate component and process terms for its use by PAOs and other heterotrophic bacteria under anoxic and aerobic conditions. The Gdansk (Poland) wastewater treatment plant (WWTP), which has a modified University of Cape Town (MUCT) process for nutrient removal, provided field data and mixed liquor for batch tests for model evaluation. The original ASM2d was first calibrated under dynamic conditions with the results of batch tests with settled wastewater and mixed liquor, in which nitrate-uptake rates, phosphorus-release rates, and anoxic phosphorus uptake rates were followed. Model validation was conducted with data from a 96-hour measurement campaign in the full-scale WWTP. The results of similar batch tests with ethanol and fusel oil as the external carbon sources were used to adjust kinetic and stoichiometric coefficients in the expanded ASM2d. Both models were compared based on their predictions of the effect of adding supplemental carbon to the anoxic zone of an MUCT process. In comparison with the ASM2d, the new model better predicted the anoxic behaviors of carbonaceous oxygen demand, nitrate-nitrogen (NO3-N), and phosphorous (PO4-P) in batch experiments with ethanol and fusel oil. However, when simulating ethanol addition to the anoxic zone of a full-scale biological nutrient removal facility, both models predicted similar effluent NO3-N concentrations (6.6 to 6.9 g N/m3). For the particular application, effective enhanced biological phosphorus removal was predicted by both models with external carbon addition but, for the new model, the effluent PO4-P concentration was approximately one-half of that found from ASM2d. On a PO4-P removal percentage basis, the difference was small, that is, 94.1 vs. 97.1%, respectively, for the ASM2d and expanded ASM2d.     

Adaptation of the CAS test system and synthetic sewage for biological nutrient removal. Part II: design and validation of test units

A global increase in biological nutrient removal (BNR) applications in wastewater treatment and concern for potential effects of anthropogenic substances on BNR processes resulted in the adaptation of the Continuous Activated Sludge (CAS) laboratory test system (cf. guideline OECD 303A or ISO 11733). In this paper two novel systems are compared to the standard CAS unit: the Behrotest KLD4 and a University of Cape Town system (CAS-UCT). Both are 'single sludge' systems with an anoxic/aerobic and an anaerobic/anoxic/aerobic configuration, respectively. They both can simulate the essential processes of full-scale BNR installations. The units where fed with a specially designed synthetic sewage, Syntho (cf. Part I of this study), or its precursor BSR3 medium. The performance of the two new units was benchmarked against the standard CAS system in terms of carbon/nitrogen/phosphorus (C/N/P) removal, as well as primary biodegradation of the surfactants linear alkylbenzene sulfonate (LAS) and glucose amide (GA). Both systems allow to easily achieve stable excess N- and P-removal. Experimental C/N/P removal data compared closely with simulations obtained with the IAWQ Activated Sludge Model No. 2 (ASM2), and with full scale BNR plants with a similar configuration. In both units the effluent concentrations of the surfactants tested were significantly reduced in comparison to the standard CAS system (up to 50% less). No adverse effects on BNR were noted for the test surfactants dosed at 400 microg/l together with an overall surfactant background concentration in the feed of ca. 20 mg/l. The proposed systems hold potential to complement the standard CAS system for situations where advanced sewage treatment plants with BNR need to be simulated in the laboratory with minimum effort.     

Comparison of dissolved-organic-carbon residuals from air- and pure-oxygen-activated-sludge sequencing-batch reactors.

Literature shows that full-scale pure-oxygen activated sludge (O2-AS) wastewater treatment plants (WWTPs) generate effluents with higher dissolved-organic carbon (DOC) concentrations and larger high-molecular-weight fractions compared to air-activated-sludge (Air-AS) WWTP effluents. The purpose of this paper was to evaluate how gas supplied (air vs. pure oxygen) to sequencing-batch reactors affected DOC transformations. The main conclusions of this paper are (a) O2-AS effluent DOC is more refractory than air-AS effluent DOC; and (b) O2-AS systems may have higher five-day biochemical oxygen demand removals than air-AS systems; however, in terms of COD and DOC removal, air-AS systems are better than O2-AS systems. Analysis of a database from side-by-side O2- and air-AS pilot tests from literature supported these observations.     

新型活性炭固定化产品的制备及其处理焦化废水的特性

为解决优势菌种工程应用,研究不同固定化方法、载体和结构的固定化产品对焦化废水的降解特性。用活性炭粉末吸附菌种后,与聚乙烯醇和海藻酸钠混合制备了新型固定化球;用聚乙烯醇和海藻酸钠包埋吸附菌种的活性炭纤维毡,与立体弹性塑料填料连用,制备出3种不同形状的活性炭纤维膜片固定化产品复合填料。将游离菌和制备的4种活性炭固定化产品投入A/A/O工艺系统平行实验,考察处理焦化废水的效果。结果表明,活性炭纤维膜片固定化产品复合填料对焦化废水的降解能力优于其他固定化产品:缺氧池出水硝酸盐氮和亚硝酸盐氮浓度分别稳定在1.96 mg/L和0.49 mg/L,未产生氮的累积现象,COD去除率可达到60.92%。好氧池COD和氨氮降解效率分别为78.83%和85.52%,苯酚、氰化物降解效率均为97%以上。     

Characteristics of biotic and abiotic removals of dissolved organic carbon in wastewater effluents using soil batch reactors.

Biodegradable dissolved organic carbon (BDOC) analyses and abiotic adsorption of dissolved organic carbon (DOC) from different wastewater effluent were conducted to evaluate biotic and abiotic removal mechanisms as a function of the initial DOC concentration and source of DOC using soil batch reactors. To obtain high DOC concentrations, a laboratory-scale reverse osmosis unit was used. It was found that BDOC fraction was independent of the initial DOC concentration and was dependent on the source of wastewater and/or the types of wastewater treatment. The BDOC fractions varied from 9 to 73%. Trickling filter effluent (Tucson, Arizona) showed the highest BDOC, ranging from 65 to 73% biodegradable, while wastewater treated by the soil aquifer treatment (SAT) (NW-4) was found to be most refractory, with DOC removals of 9 to 14%. For nitrified/denitrified tertiary effluent (Mesa, Arizona) and secondary effluent (Scottsdale, Arizona), 36 to 42% removal of DOC was observed during the BDOC test. The amount of BDOC in the wastewater depended not on the concentration of DOC, but on the effectiveness of pretreatment. Abiotic adsorption capacity of wastewater effluent varied from 6 to 18%. Molecular weight distribution analyses showed that more than 50% of DOC in the Scottsdale concentrate had a molecular weight of less than 1000 Da, and no significant change in distribution profiles occurred after approximately 12% abiotic adsorption with both soils with acclimated microorganisms (SAT soil) and soils without acclimated microorganisms (non-SAT soils). Hence, preferential adsorption was not observed and the presence of acclimated microbes did not influence adsorption.     

不同碳源下的间歇曝气反硝化实验研究

本实验研究在序批式模式下高浓度硝酸盐的反硝化,比较用甲醇、醋酸钠和消化污泥上清液作碳源。实验发现,间歇曝气有助于提高反硝化污泥的沉降性能,而厌氧条件下,污泥的沉降性能差。污泥浓度4~5gVSS/L下,3种碳源都能有效地进行反硝化。最大硝酸盐去除率为0486gNO3N/gVSS·d。开始阶段,亚硝酸盐浓度增加,但用醋酸盐和硝化污泥上清液作碳源,其浓度最终下降为零。