催化湿式氧化高浓度SDBS废水的研究

以过渡金属氧化物CuO为主活性组分,通过复合第二活性组分Co3O4和掺入电子助剂CeO2的考察,研制出适用于催化湿式氧化处理高浓度十二烷基苯磺酸钠(SDBS)废水的复合催化剂。实验结果表明,新制备的复合催化剂有较好的催化活性。通过对反应温度、氧气分压和废水pH值等工艺条件的考察,得出催化湿式氧化处理高浓度SDBS废水适宜的工艺条件为:反应温度为280℃、氧气分压为3 MPa、pH值为8.2,在此条件下用自制的催化剂处理初始COD质量浓度为4 942.1 mg/L的SDBS废水,在120 min内,COD去除率达到88.1%,而在相同条件下未加催化剂的湿式氧化COD去除率只有30.7%。     

Leachate detoxification by combination of biological and TiO2-photocatalytic processes.

Landfill leachates are a problematic wastewater due to their variable concentration, volume changing in time and presence of refractory and hazardous components. In this paper, the results of a new approach to photocatalysis assisted by biological process for the detoxification of stabilised landfill leachate are presented. The biologically pre-treated leachate still contained a significant amount of non-biodegradable COD and TOC amounting to 500 and 200 mg/L, respectively. The 300 min of photocatalytic treatment (UVC/TiO2) brought about a significant decrease in more than 80% refractory organics remaining in leachate. The effect of pH and catalyst loading on mineralisation, colour removal rate and biodegradability (BOD/COD) improvement in the photoreactor were discussed. The bio-accessibility of formed photocatalytic oxidation intermediates was confirmed by oxygen uptake rate (OUR) measurements. Consequently, a part of COD was successfully removed in post-biological treatment.     

ABR反应器对垃圾渗滤液的处理试验研究

ABR工艺在处理垃圾渗滤液中具有其他厌氧生物反应器所达不到的优点。尤其是对B/C低、氨氮浓度高、COD浓度高的废水处理,通过调节回流比、HRT、碱度等参数后,可以取得很好的处理效果。在本次实验中,HRT控制在18h后明显提高的垃圾渗滤液的可生化性及C/N,使ABR出水CODcr去除率达到75%,C/N为6.72,对后续好氧反应起到了重要作用。在调控一定回流比后,为提供厌氧氨氧化所需的电子受体NO-3和NO-2实现脱氮。反应器在经过120d的培养驯化,氨氮进水为460mg/L,ABR对氨氮的去除率稳定在80%。不同格室的厌氧颗粒污泥都得到很好的驯化并在其合适的环境中发挥各自的功能。     

Degradation of recalcitrant organic contaminants by solar photocatalysis.

Biological pre-treated landfill leachates of Djebel Chakir contains some macromolecular organic substances that are resistant to biological degradation. The aim of the present work is to assess the feasibility of removing refractory organic pollutants in biological pre-treated landfill leachate by solar photocatalyse process. Leachate pollutant contents are studied to assess their contribution to leachate pollution and their treatability by solar photocatalyse process. Phenol is chosen as model of pollutants, to evaluate its removal and the efficiency of the photocatalytic system. The experiments were carried out in suspended photocatalytic reactor, using TiO2 Degussa P25, under sunlight illumination (UV-A: 15-31 W/cm2). Under optimum operational conditions, applied to single reactant (phenol), the system presents a TOC removal of 90% (the degradation follows a first-order kinetic). Based on the TOC removal, the results shows that the degradation of biological pre-treated leachate follows a zero-order kinetic. After 5 h of sunlight exposure, 74% of COT is removed. The TOC removal is the best without any correction of the pH and at the TiO2 concentration of 2.5 g/L. The photocatalytic degradation of organic contaminants as well as the formation and disappearance of the by-products were followed by GC/MS. The solar photocatalysis processes induce several modifications of the matrix leading to more biodegradable forms: all the remaining and new compounds generated after the biological pre-treatment of leachate are degraded and other types of organics appear, mainly carboxylic acid, aliphatic hydrocarbons and phtalic acids.     

Nitrogen removal during leachate treatment: comparison of simple and sophisticated systems.

Membrane bioreactors (MBR) have become common in treating municipal wastewaters. Applied to leachates treatment MBR were also successful with pilot scale experiments and full-scale facilities as well. We succeeded previously in designing an efficient nitrification-denitrification process with an ethylene glycol byproduct as carbon source for denitrification. Moreover, an unexpectedly high inert COD removal efficiency was also observed in the full-scale MBR facility thereby making it possible to increase the operating time of the final GAC (Granulated Activated Carbon) adsorber. Since MBR are very sophisticated systems. Simpler and "lower" cost systems can also be considered. For example it is possible to nitrify leachates from sanitary landfill using a simple infiltration-percolation technique with a low energy cost. To validate previously published laboratory experiments, a semi industrial-scale pilot installation was installed at the Montzen landfill site (Belgium). The process is based on infiltration-percolation through a granular bed. This well known process was modified to increase the load, notably by changing the support medium, adding an electric fan that is run intermittently and maintaining temperatures greater than 15 degrees C. The new material is a type of granular calcium carbonate with a large specific surface area. These technical improvements enabled the system to nitrify up to 0.4 kg NH4+-N/m3 of reactor bed per day at a hydraulic load of 0.35 m.d(-1), with an ammonia removal rate in the range of 80 to 95%. Despite the high ammonia nitrogen inlet concentrations, this system exhibits remarkable nitrification efficiency. Moreover, these performances are achieved in a batch mode system without recirculation or dilution processes. If complete nitrification is needed, it can be obtained in a second in series of bioreactors. The system can be classified as a low cost process. An international patent is pending. Possible performances of those systems were compared with the usual methods for leachates treatment.     

A combined UASB-MBR with shortcut nitrification-denitrification for energy reduction in wastewater reclamation

Shortcut nitrification has been successfully applied in a laboratory scale nitrification-denitrification process consisting of an up-flow anaerobic sludge blanket (UASB) and an aerobic membrane bioreactor (MBR) in treating synthetic and municipal wastewater to simultaneously remove organic carbon and nitrogen. For the treatment of synthetic wastewater, the combined system exhibited a high TOC removal of 98% with a steady ammonia removal efficiency of about 98% in the MBR and a total nitrogen (TN) removal efficiency of 90%. In treating municipal wastewater, due to its low COD concentration, removal efficiencies of TOC, ammonia and TN were 70%, 98% and 60%, respectively. The biogas production was around 76.4 L/m3 wastewater when treating synthetic wastewater. However, little biogas was produced when treating municipal wastewater which was the result of low organic carbon loading to the UASB. Energy analysis has demonstrated that this novel shortcut nitrification process could consume less energy than a conventional process and have the potential of bio-energy generation via biogas production thus helping to achieve a more favorable energy balance.     

Nitrogen removal via ammonia volatilization in maturation ponds.

A simple apparatus was designed to collect ammonia gas coming out from waste stabilization ponds (WSP). The apparatus has a capture chamber and an absorption system, which were optimized under laboratory conditions prior to being used to assess ammonia volatilization rates in a pilot-scale maturation pond during summer 2005. Under laboratory conditions (water temperature = 17.1 degrees C and pH = 10.1), the average ammonia volatilization rate was 2,517 g NH3-N/ha d and the apparatus absorbed 79% of volatilized ammonia. On site, the mean ammonia volatilization rate was 15 g N/ha d, which corresponds to 3% of the total nitrogen removed (531 g N/ha d) in the maturation pond studied. A net nitrogen mass balance showed that ammonia volatilization was not the most important mechanism involved in either total nitrogen or ammonia removal. Nitrogen fractions (suspended organic nitrogen, soluble organic nitrogen, ammonia, nitrite and nitrate) from the M1 influent and effluent showed that ammonia is removed by biological (mainly algal) uptake and total nitrogen removal by sedimentation of dead algal biomass.     

Chemical denitrification for nitrogen removal from landfill leachate.

A new system that removes nitrogen from landfill leachate and other waste waters with similar properties has been proposed with nitritation (i.e. oxidation of ammonium to nitrite) of half of the influent ammonium followed by chemical denitrification with a reaction between equal amounts of ammonium and nitrite to form nitrogen gas. Chemical denitrification occurs at high concentrations and the reactions were studied in combination with a concentration step. Studied concentration methods were freezing/thawing and evaporation/drying. Chemical denitrification is well-known in inorganic chemistry and has been observed in natural systems. Studies in laboratory were focused on chemical denitrification and showed that nearly complete removal of soluble nitrogen can be obtained in evaporation/drying of water solutions or leachate with equal amounts of ammonium and nitrite. Freezing/drying was less efficient with a removal of about 50-60% at high initial concentrations. Chemical denitrification is much influenced by concentration, pH-value, temperature and some compounds in leachate have an inhibiting effect on the reaction. Factors as safety (ammonium nitrite as a salt is explosive above 60 degrees C) and possible side-reactions as formation of ammonia and nitrogen oxides must be carefully evaluated before use in full-scale. Conductivity is a suitable parameter to follow-up the chemical denitrification process.     

Nitrogen removal in maturation ponds: tracer experiments with 15N-labelled ammonia.

A primary maturation pond (M1) was spiked with labelled ammonium chloride (15NH4Cl) to track ammonium transformations associated with algal uptake and subsequent sedimentation. Conventional sampling based on grab samples collected from M1 influent, water column and effluent, and processed for unfiltered and filtered TKN, ammonium, nitrite and nitrate, found low total nitrogen removal (8%) and high ammonium nitrogen removal (90%). Stable isotope analysis of 15N from suspended organic and ammonium nitrogen fractions in M1 effluent revealed that labelled ammonium was mainly found in the organic fraction (69% of the 15N recovered), rather than the inorganic fraction (5%). Algal uptake was the predominant pathway for ammonia removal, even though conditions were favourable for ammonia volatilization (8.9 < pH <10.1 units, 15.2 < temperature <18.8 degrees C). Total nitrogen was removed by ammonia volatilization at 15 g N/ha d (3%), organic nitrogen sedimentation at 105 g N/ha d (20%), and in-pond accumulation due to algal uptake at 377 g N/ha d (71%). Algal uptake of ammonium and subsequent sedimentation and retention in the benthic sludge, after partial ammonification of the algal organic nitrogen, is thus likely to be the dominant mechanism for permanent nitrogen removal in maturation ponds during warm summer months in England.     

Treatment of slaughterhouse plant wastewater by using a membrane bioreactor

The use of a membrane bioreactor (MBR) for removal of organic substances and nutrients from slaughterhouse plant wastewater was investigated. The chemical oxygen demand (COD), total nitrogen (TN), and total phosphorus (TP) concentrations of slaughterhouse wastewater were found to be approximately 571 mg O2/L, 102.5 mg/L, and 16.25 mg PO4-P/L, respectively. A submerged type membrane was used in the bioreactor. The removal efficiencies for COD, total organic carbon (TOC), TP and TN were found to be 97, 96, 65, 44% respectively. The COD value of wastewater was decreased to 16 mg/L (COD discharge standard for slaughterhouse plant wastewaters is 160 mg/L). TOC was decreased to 9 mg/L (TOC discharge standard for slaughterhouse plant wastewaters is 20 mg/L). Ammonium, and nitrate nitrogen concentrations of treated effluent were 0.100 mg NH4-N/L, and 80.521 mg NO3-N/L, respectively. Slaughterhouse wastewater was successfully treated with the MBR process.     

Behavior of an Up-flow Anaerobic Sludge Bed (UASB) reactor at extreme salinity.

High salinity is one of the most well known inhibitors and salt concentrations above 1% are reported as highly saline. Salt may be found in the main collectors of municipal sewer systems which carry the risk of seawater infiltration and where domestic wastewaters are treated with landfill leachates such cases in Istanbul. Discharging of leachates into sewerage would also result in additional ammonium loads in Municipal Treatment Plants (MTPs). In this study, synthetic wastewater was fed to a lab-scale Upflow Anaerobic Sludge Bed (UASB) reactor operated at a constant hydraulic retention time (HRT) of 1 day. The salt concentration was increased artificially whereas the ammonium concentration was fixed at 1000 mg/l throughout the study. Results indicated no significant inhibition up to 2% salinity + 1000 mg/l NH4 and TOC removals could reach up to 88%. Besides, effective total biogas productions having methane content of 84% could be achieved. It is obvious that anaerobic microorganisms (especially methanogens) could well adapt to high salinity ratios. No inhibition at high ammonium concentration might have been attributed to the fact that the pH in the system was not high enough for the formation of free ammonia. Investigation of the combined effect of high salinity and ammonium was carried on by increasing the salinity to 3% in the study. Results indicated that TOC removals decreased to around 56% and 3% salinity caused . a sharp decrease both in organic material removal and total biogas production. Thus the critical salinity level was determined as 3% for the methanogens in the mesophilic anaerobic digesters.     

Catalytic wet air oxidation with Ni- and Fe-doped mixed oxides derived from hydrotalcites

Catalytic wet air oxidation of Basic Yellow 11 (BY11), a basic dye, was studied in a batch reactor. Layered double hydroxides with the hydrotalcite-like structure containing nickel or iron cations have been prepared by coprecipitation and subsequently calcined leading to Ni- and Fe-doped mixed oxides, respectively. Compared with the results in the wet air oxidation of BY11, these catalysts showed high activity for total organic carbon (TOC), toxicity and dye removal at 120 degrees C and 50 bars after 120 min. It has been demonstrated that the activity depended strongly on the presence of catalyst. The results show that catalysts containing nickel provide a higher extent of oxidation of the dye whereas the reaction carried out with the iron catalyst is faster. The Ni and Fe dispersion determined from the TPR results was higher for the catalysts with a lower Ni or Fe content and decreased for higher Ni or Fe contents. On the basis of activity and selectivity, the Ni containing catalyst with the medium (3%) Ni content was found to be the best catalyst. Finally, a relationship between metal content of the catalyst and reaction rate has been established.     

Sequenced anaerobic-aerobic treatment of high strength, strong nitrogenous landfill leachates.

As a first step in treatment of high strength, strong nitrogenous landfill leachates (total COD--9.66-20.56 g/l, total nitrogen 780-1,080 mg/l), the performance of laboratory UASB reactors has been investigated under sub-mesophilic (19+/-3 degrees C) and psychrophilic (10+/-2 degrees C) conditions. Under hydraulic retention time (HRT) of around 1.2 days, when the average organic loading rate (OLR) was around 8.5 g COD/l/day, the total COD removal accounted for 71% (on average) for sub-mesophilic regime. The psychrophilic treatment conducted under the average HRT of 2.44 days and the average OLR of 4.2 g COD/l/day showed an average total COD removal of 58% giving effluents more suitable for subsequent biological nitrogen removal. Both anaerobic regimes were quite efficient for elimination of heavy metals by concomitant precipitation in the form of insoluble sulphides inside the sludge. The subsequent submesophilic aerobic-anoxic treatment of submesophilic anaerobic effluents led to only 75% of total inorganic N removal due to COD deficiency for denitrification created by too efficient anaerobic step. On the contrary, psychrophilic anaerobic effluents (richer in COD compared to the submesophilic ones) were more suitable for subsequent aerobic-anoxic treatment giving the total N removal of 95 and 92% at 19 and 10 degrees C, respectively.     

Effect of advanced oxidation processes on the toxicity of municipal landfill leachates.

The aim of the present study was to assess the effect of advanced oxidation processes (AOPs) (oxidation ozone and peroxide/ozone) on the toxicity of leachates from municipal landfill for Warsaw, Poland, using a battery of tests. AOPs used to pre-treat leachates were carried out in laboratory conditions after their coagulation with the use of FeCl3. The effects of the pre-treatment of leachates using the method of coagulation with FeCl3 depended on the concentration of organic compounds and with optimal conditions of the process ranged from 40 to 70%. Further pre-treatment of the leachates after coagulation, involving the use of oxidation with 03 and H2O2/O3, did not cause significant decrease of leachate toxicity. The data of this study demonstrated the usefulness of the battery of tests using Daphnia magna, Artemia franciscana, Scenedesmus quadricauda and Vibrio fischeri for the toxicity evaluation of raw and pre-treated leachates.     

城市污水脱氮除磷SBR在线控制系统研究

SBR采用进水—厌氧—好氧—缺氧—好氧—沉淀—出水的运行方式处理城市污水。反应器装备有DO、ORP和pH等在线检测传感器。DO、ORP和pH变化的一些特征点可以用来判断和控制SBR中污水脱氮除磷过程的各个步骤。这包括:厌氧时,ORP和pH的转折点对应磷的释放;一次好氧时,DO、ORP的氨肘和pH的氨谷对应硝化结束;缺氧时,ORP的硝酸盐膝和pH的硝酸盐峰对应反硝化结束;二次好氧时,DO、ORP碳肘对应剩余碳的氧化结束,pH的转折点对应聚磷结束。控制系统能进行全自动运行来完成污水的脱氮除磷。     

ANAMMOX工艺在生活污水深度处理中的应用研究

随着水环境质量的恶化,高能低耗的污水深度处理技术成为当前研究热点,尤其是对于低C/N比的城市生活污水脱氮技术的研究。试验以城市生活污水的二级出水为研究对象,采用ANAMMOX下向流生物滤池,当二级出水NH3-N=15-35mg/L,CODCr=25-45mg/L,TOC=9-12mg/L,水温=25-28℃时,ANAMMOX下向流生物滤池脱氨率达80%-100%,不仅适用于处理高氨废水,也可用于城市生活污水深度处理中。试验发现pH可以用来指示ANAMMOX反应的进行,同时也可以用来指示ANAMMOX反应进程的快慢。试验中还发现,厌氧氨氧化反应速率与NO2--N含量有关,原水中NO2--N含量的增多有利于ANAMMOX工艺处理效果。     

Nitrogen removal in an upflow sludge blanket (USB) reactor combined by aerobic biofiltration systems.

A new nitrogen removal process (up-flow sludge blanket and aerobic filter, USB-AF) was proposed and tested with real sewage. In the USB reactor, the larger part of influent organic and nitrogen matters were removed, and ammonia was effectively oxidized in the subsequent aerobic filter. The role of the aerobic filter was to convert ammonia into nitrate, an electron acceptor that could convert soluble organic matters into volatile suspended solid (VSS) in the USB. The accumulated as well as influent VSS in the USB was finally degraded to fermented products that were another good carbon source for denitrification. Total COD, settleable COD and soluble COD in the raw sewage were 325, 80 and 140 mg/l, respectively. Most unsettleable COD as well as some SCOD in the influent was successfully removed in the USB. TCOD removal in the anoxic filter was by denitrification with the recycled nitrate. Low COD input to the aerobic filter could increase nitrification efficiency, reduce the start-up period and save the aeration energy in the USB-AF system. About 95% of ammonia was nitrified in the aerobic filter with no relation to the influent ammonia concentration. Denitrification efficiency of the recycled nitrate in the anoxic filter was about 85, 83, and 72% at recycle ratios of 100, 200, and 300%, respectively. T-N removal efficiency was 70% at recycle ratio of 300%.     

生物接触氧化流化床处理氨氮污水的实验研究

为了提高生物接触氧化流化床处理氨氮污水的脱氮效果,采用生物接触氧化流化床在自然温度下处理人工配制模拟生活污水实验的方法,研究了氨氮污水脱氮处理的可行性、方法与效果。实验结果表明:氨氮被氧化成硝酸可由两类独立的细菌分别催化完成;反应的适宜温度为20~35℃;亚硝酸菌的最适pH值为7~8.5之间,硝酸菌为6~7.5;亚硝酸菌和硝酸菌溶解氧质量浓度在0.5 mg/L以上才能取得较好的硝化效果。反应器内填料粒径在10 mm左右有利于提高氨氮的去除效率;间歇式进水方式使活性污泥具有良好的沉降性,可为氨氮的去除提供良好的环境条件。     

Aerobic granulation in a mechanical stirred SBR: treatment of low organic loads

Aerobic granular sludge was produced in a sequencing batch reactor (SBR) characterized by a height to diameter ratio of 2.5 and the use of mechanical stirring. Compact and regular aerobic granules of up to 1.75 mm of average diameter were formed in the reactor with an organic loading rate of 1.75 kg COD/(m3 d). Settling properties of the obtained aggregates were: sludge volumetric index of 30-40 mL/g VSS and settling velocity higher than 8 m/h. The effects of different carbon to nitrogen ratios (TOC/N) in the feeding on the organic matter oxidation and nitrification process were studied. The concentration of organic matter in the feeding was stepwise reduced (from 190.0 to 37.5 mg TOC/L) and ammonium increased (from 25 to 50 mg NH4+ -N/L). TOC/N ratios of 7.50, 3.00, 1.50 and 0.75 g/g in the feeding were tested. The TOC removal percentage was around 80-95% during the whole operational period and the N removal percentages obtained in the reactor were up to 40%, however, physical properties of the granules were not maintained.     

Ozone catalysed with solids as an advanced oxidation process for landfill leachate treatment.

Heterogeneous catalytic ozonation (HCO) of wastewater is gaining both research and industrial interests. It is proved to be an advanced oxidation process since it involves hydroxyl radicals as oxidation species. Few studies have been carried out to test HCO in the treatment of landfill leachates. This work has been carried out to test three types of catalysts: activated carbon (AC), expanded perlite (EP) and titanium dioxide (TiO2) combined with ozone at 80 g/m3 gas concentration for the treatment of a leachate generated by Jebel Chakir landfill site near Tunis-capital of Tunisia. The work has shown a reduction in COD of about 45% and an increase in biodegradability (BOD5/COD) from 0.1 to 0.34. A catalyst concentration of 0.7 g/L was found optimal for the treatment of the leachate.