钙钛矿型催化剂催化湿式氧化处理煤气化废水纳滤浓缩液

采用溶胶-凝胶法制备了Mn掺杂钙钛矿型催化剂LaFexMn1-xO3,并以其为催化剂催化湿式双氧水氧化处理煤气化废水纳滤浓缩液。采用XRD,SEM,FTIR技术对催化剂进行了表征。表征结果显示：制备的催化剂均具有标准的钙钛矿型结构,其中,LaFe0.9Mn0.1O3的结构稳定,比表面积大。实验结果表明：制备的催化剂中LaFe0.9Mn0.1O3的催化活性最高,且稳定性好,连续使用5次后催化活性未见明显减弱;在H2O2投加量3.0 g/L、n（H2O2）∶n（LaFe0.9Mn0.1O3）=12∶1、反应温度160 ℃、反应压力1 MPa、浓缩液pH 3、反应时间60 min的最优条件下,COD、UV254和TOC的去除率分别达到80.9%、95.2%和68.0%,BOD5/COD由0.02提升至0.40,可生化性大幅提高。     

A complete mass balance of a complex combined anaerobic/aerobic municipal source-separated waste treatment plant

In this study a combined anaerobic/aerobic full-scale treatment plant designed for the treatment of the source-separated organic fraction of municipal solid waste (OFMSW) was monitored over a period of one year. During this period, full information was collected about the waste input material, the biogas production, the main rejects and the compost characteristics. The plant includes mechanical pre-treatment, dry thermophilic anaerobic digestion, tunnel composting system and a curing phase to produce compost. To perform the monitoring of the entire plant and the individual steps, traditional chemical methods were used but they present important limitations in determining the critical points and the efficiency of the stabilization of the organic matter. Respiration indices (dynamic and cumulative) allowed for the quantitative calculation of the efficiency of each treatment unit. The mass balance was calculated and expressed in terms of Mgy(-1) of wet (total) matter, carbon, nitrogen and phosphorus. Results show that during the pre-treatment step about 32% of the initial wet matter is rejected without any treatment. This also reduces the biodegradability of the organic matter that continues to the treatment process. About 50% of the initial nitrogen and 86.4% of the initial phosphorus are found in the final compost. The final compost also achieves a high level of stabilization with a dynamic respiration index of 0.3±0.1g O(2) per kg of total solids per hour, which implies a reduction of 93% from that of the raw OFMSW, without considering the losses of biodegradable organic matter in the refuse (32% of the total input). The anaerobic digestion process is the main contributor to this stabilization.     

Fenton试剂氧化—SBR工艺处理阿莫西林制药废水生化处理出水

采用Fenton试剂氧化—SBR工艺处理阿莫西林制药废水生化处理出水。实验结果表明:当初始废水pH为3.0、H2O2加入量为10 mL/L、V(H2O2):m(FeSO4.7H2O)为5(mL):1(g)、Fenton试剂氧化反应时间为3 h时,Fenton试剂氧化COD去除率达72.25%,色度由100倍降为2倍,BOD5/COD由0.06提高到0.38,可生化性显著提高。经Fenton试剂氧化—SBR工艺处理后,出水COD为72.7 mg/L,达到国家排放标准。     

Volatility of heavy metals during incineration of tannery sludge in the presence of chlorides and phosphoric acid.

Knowledge of the behaviour of heavy metals in the combustion process is a most important factor in selecting disposal alternatives for waste materials. Accordingly, in this work, the vaporization behaviour of highly concentrated heavy metals (Pb, Zn, Cu and Cr) in tannery sludge were investigated experimentally. The sludge was spiked with various chlorine compounds (i.e. PVC, FeCl3, CaCl2 and NaCl) and pre-treated with phosphoric acid in order to evaluate the capacity of enhancement and weakening of the volatility of the heavy metals contained in tannery sludge. The experimental results show that the vaporization percentages increased with increasing ratio of Cl/sludge and temperature, and the accelerating and increasing effect of the addition of chlorides on the vaporization percentage of heavy metals was dependent on the release capacity of chlorine radicals. The vaporization percentages of lead and zinc increased by 15-20%, whereas those of copper and chromium increased by only about 3 and 10% at 800 degrees C. However, heavy metals were not expected to be completely released in the combustion process in spite of the high ratio of Cl/sludge. Alternately, heavy metals contained in tannery sludge can be immobilized effectively by pre-treatment with phosphoric acid. When the 85% phosphoric acid accounted for 10% of dry basis of tannery sludge, the phosphate-treated sludge showed the lowest vaporization percentage of about 3-15% with formation of Ca18Cu3(PO4)14, Ca9Cr(PO4)7, Ca19Zn2(PO4)14 and PbMgP2O7 in the bottom ash.     

亚临界湿式氧化法脱除含油污泥中的重金属

采用亚临界湿式氧化法及金属络合剂协同亚临界湿式氧化法去除含油污泥中的重金属,考察了去除效果,优化了反应条件,并探讨了脱除重金属的含量上限。实验结果表明:在1 L反应釜内加入200 g含油污泥,在反应温度200℃、反应时间60 min、液固比(去离子水与含油污泥的质量比)0.30的优化条件下,Cu和Zn的去除率分别可达67.3%和22.0%;加入金属络合剂后,各重金属的去除率均有明显提高;在金属络合剂加入量为0.05mol/L的优化条件下,应用金属络合剂协同亚临界湿式氧化法可将2.5倍于CJ/T 309—2009《城镇污水处理厂污泥处置农用泥质》B级标准的重金属含量降至标准范围内。     

物化强化预处理对化工园区废水中典型污染物转化的影响

以江苏省某化工园区污水处理厂的原水为研究对象,分别采用臭氧氧化、铁碳微电解、Fenton氧化3种物化法对其进行强化预处理,并运用GC-MS技术对典型污染物进行了分析。实验结果表明:臭氧氧化、Fenton氧化、铁碳微电解3种物化法在最佳条件下对COD的去除率分别为8.0%,51.3%,45.6%;在提高可生化性方面,臭氧氧化法效果最好,使废水的BOD_5/COD从0.112提高到0.184,Fenton氧化法和铁碳微电解法的BOD_5/COD分别为0.150和0.123;经物化预处理后,废水中的环状物质会出现开环,同时直链物质增多,但苯环、脂类及杂环等难生物降解物质依然存在;若要单纯提高废水的可生化性,建议选用臭氧氧化法;若对去除COD及提高可生化性皆有要求,建议选用铁碳微电解法。     

The effect of the addition of fly ash to municipal digested sludge on its electroosmotic dewatering

Effective handling of municipal digested sludge requires that the product cake have low water content. To this end, we investigated the change in sludge dewaterability after the addition of fly ash to municipal digested sludge, dewatering of which is difficult because of its high organic content. The performance of the dewatering is compared with that of electroosmotic dewatering (EDW) and conventional mechanical dewatering (CMD). Fly ash classified by sieving to the size of 25–75 μm and >75 μm is added to the municipal digested sludge by 10, 20, and 50 wt% by wet base. When adding fly ash particles to municipal digested sludge, dewatering efficiency improved with smaller fly ash particle size and with increase in the amount. When sludge was dewatered using an electroosmotic dewatering method, the dewatering efficiency is improved about 40% by adding fly ash of 25–75 μm particle size with 20 wt% when compared with conventional mechanical dewatering method without adding the fly ash. It is concluded that fly ash particles rich in inorganic material are helpful in the dewatering process when added to municipal digested sludge and EDW is more effective than CDW.     

Combining chemical sequential extractions with 3D fluorescence spectroscopy to characterize sludge organic matter

The design and management of anaerobic digestion of sewage sludge (SS) require a relevant characterisation of the sludge organic matter (OM). Methods currently used are time-consuming and often insufficiently informative. A new method combining chemical sequential extractions (CSE) with 3D fluorescence spectroscopy was developed to provide a relevant SS characterisation to assess both OM bioaccessibility and complexity which govern SS biodegradability. CSE fractionates the sludge OM into 5 compartments of decreasing accessibility. First applied on three SS samples with different OM stability, fractionation profiles obtained were in accordance with the latter. 3D fluorescence spectroscopy revealed that the bioaccessible compartments were mainly constituted of simple and easily biodegradable OM while the unaccessible ones were largely made of complex and refractory OM. Then, primary, secondary and anaerobically digested sludge with different biodegradabilities were tested. Complexity revealed by 3D fluorescence spectroscopy was linked with biodegradability and chemical accessibility was correlated with sludge bioaccessibility.     

Evaluation of a lime-mediated sewage sludge stabilisation process. Product characterisation and technological validation for its use in the cement industry

This paper describes an industrial process for stabilising sewage sludge (SS) with lime and evaluates the viability of the stabilised product, denominated Neutral, as a raw material for the cement industry. Lime not only stabilised the sludge, raised the temperature of the mix to 80-100 °C, furthering water evaporation, portlandite formation and the partial oxidation of the organic matter present in the sludge.Process mass and energy balances were determined. Neutral, a white powder consisting of portlandite (49.8%), calcite (16.6%), inorganic oxides (13.4%) and organic matter and moisture (20.2%), proved to be technologically apt for inclusion as a component in cement raw mixes. In this study, it was used instead of limestone in raw mixes clinkerised at 1400, 1450 and 1500 °C. These raw meals exhibited greater reactivity at high temperatures than the limestone product and their calcination at 1500 °C yielded clinker containing over 75% calcium silicates, the key phases in Portland clinker. Finally, the two types of raw meal (Neutral and limestone) were observed to exhibit similar mineralogy and crystal size and distribution.     

NaOH强化催化湿式氧化处理制药污泥

采用NaOH强化催化湿式氧化的方法处理制药污泥,考察了各工艺条件对污泥VSS去除率和COD去除率的影响。实验结果表明,在NaOH加入量10 g/L、反应温度260 ℃、初始氧气压力1.0 MPa、反应时间60 min的最佳工艺条件下,污泥VSS去除率和 COD去除率分别达到95%和60%,VSS去除率较高,污泥减量化效果显著。NaOH强化催化湿式氧化反应处理制药污泥的机理是氢氧根在高温条件下促进了微生物细胞的水解,促使污泥固体组分分解转移到液相中,最终有机物被降解为小分子有机物、CO₂和水。     

Treatment of Stormwater using Fibre Filter Media

In this study, a high-rate fibre filter was used as a pre-treatment to stormwater in conjunction with in-line flocculation. The effect of operating the fibre filter with different packing densities (105, 115 and 125 kg/m³) and filtration velocities (20, 40, 60 m/h) with and without in-line flocculation was investigated. In-line flocculation was provided using 5, 10 and 15 mg/L of ferric chloride (FeCl₃·6H₂O). The filter performance was studied in terms of pressure drop (ΔP), solids removal efficiency, heavy metals (total) removal efficiency and total organic carbon (TOC) removal efficiency. It is found that the use of in-line flocculation at a dose of 15 mg/L improved the performance of fibre filter as measured by turbidity removal (95%), total suspended solids reduction (98%), colour removal efficiency (99%), TOC removal (reduced by 30–40 %) and total coliform removal (93%). The modified fouling index reduced from 750–950 to 12 s/L² proving that fibre filter can be an excellent pre-treatment to membrane filtration that may be consider as post-treatment. The removal efficiency of heavy metal was variable as their concentration in raw water was small. Even though the concentration of some of these metals such as iron, aluminium, copper and zinc were reduced, others like nickel, chromium and cadmium showed lower removal rates.     

Recovery of metals from waste printed circuit boards by supercritical water pre-treatment combined with acid leaching process

Waste printed circuit boards (PCBs) contain a large number of metals such as Cu, Sn, Pb, Cd, Cr, Zn, and Mn. In this work, an efficient and environmentally friendly process for metals recovery from waste PCBs by supercritical water (SCW) pre-treatment combined with acid leaching was developed. In the proposed process, waste PCBs were pre-treated by SCW, then the separated solid phase product with concentrated metals was subjected to an acid leaching process for metals recovery. The effect of SCW pre-treatment on the recovery of different metals from waste PCBs was investigated. Two methods of SCW pre-treatment were studied: supercritical water oxidation (SCWO) and supercritical water depolymerization (SCWD). Experimental results indicated that SCWO and SCWD pre-treatment had significant effect on the recovery of different metals. SCWO pre-treatment was highly efficient for enhancing the recovery of Cu and Pb, and the recovery efficiency increased significantly with increasing pre-treatment temperature. The recovery efficiency of Cu and Pb for SCWO pre-treatment at 420 °C was 99.8% and 80%, respectively, whereas most of the Sn and Cr were immobilized in the residue. The recovery of all studied metals was enhanced by SCWD pre-treatment and increased along with pre-treatment temperature. Up to 90% of Sn, Zn, Cr, Cd, and Mn could be recovered for SCWD pre-treatment at 440 °C.     

铁碳微电解法处理高盐度有机废水

用铁碳微电解法处理高盐度有机废水,考察了反应初始pH、铁碳质量比、反应时间、曝气及过氧化氢加入量等对该废水处理效果的影响。实验结果表明：在反应初始pH为4.0、铁碳质量比为1、反应时间为60m in、过氧化氢加入量为0.10%（体积分数）、曝气条件下,COD去除率为57.6%,盐去除率为47.0%;处理后废水的可生化性有明显的改善,BOD5/COD可达0.65;对COD的去除基本符合一级动力学规律。     

Thermal and thermo-chemical pre-treatment of four waste residues and the effect on acetic acid production and methane synthesis

In this study four diverse solid waste substrates (coal, Kraft pulp solids, chicken feathers and chicken processing waste) were thermally pre-treated (70, 140 and 200 °C), under an inert (nitrogen) or oxidative (oxygen) atmosphere, and then anaerobically digested. Membrane inlet mass spectrometry during the thermal and thermo-chemical reactions was successfully used to establish oxygen and carbon dioxide gas fluxes and product formation (acetic acid). There was significant solids hydrolysis pre-treatment at 200 °C under an oxidative atmosphere, as indicated by a decrease in the volatile suspended solids and an increase in dissolved organic carbon. Greater concentrations of volatile fatty acids were produced under oxidative conditions at higher temperatures. The methane yield more than tripled for feathers after pre-treatment at 140 °C (under both atmospheres), but decreased after oxidative pre-treatment at 200 °C, due to the destruction of available carbon by the thermo-chemical reaction. Methane yield more than doubled for the Kraft pulp solids with the 200 °C pre-treatment under oxidative conditions. This study illustrated the power of wet oxidation for solids destruction and its potential to improve methane yields generated during anaerobic digestion.     

厌氧氨氧化-反硝化协同脱氮研究

采用厌氧氨氧化（ANAMMOX）工艺的上流式厌氧污泥床（UASB）-生物膜反应器（简称反应器）处理高浓度含氮废水,启动并稳定运行630d后,进行进水浓度负荷实验分析。当进水ρ（NH3-N）,ρ（NO2--N）,ρ（TN）分别为340．0,448．8,788．8mg／L时,其去除率分别为84．0％,93．0％,85．0％。在反应器中连续加入有机物（葡萄糖）,进水ρ（NH3-N）和ρ（NO2--N）分别为240．0,316．8mg／L,进水COD为330．0—380．0mg／L,COD去除率达92．0％。仅用23d,在同一反应器系统中成功实现了ANAMMOX与反硝化协同作用脱氮。葡萄糖的存在对系统去除NH3-N和NO2--N的能力影响不大。     

紫外辐照-催化湿式过氧化氢氧化技术处理酸性大红GR染料废水

采用自制的负载型CuO-ZnO-CeO2/γ-Al2O3催化剂,常温常压下通过紫外辐照-催化湿式氧化技术处理酸性大红GR模拟染料废水。考察了催化剂加入量、H2O2加入量、废水pH、反应时间、初始酸性大红GR质量浓度等对废水脱色率的影响。实验得到最佳工艺条件为初始酸性大红GR质量浓度200mg/L,催化剂加入量10.0g/L,H2O2加入量2.0mL/L,废水pH4,反应时间2h。最佳工艺条件下废水脱色率达99.33%。     

Carbonization of johkasou sludge using batch-type equipment

The carbonization of dehydrated johkasou sludge was examined using batch-type equipment. Based on the temperature changes in the carbonization room and the gas combustion room, the carbonization process was divided into three phases: phase I, drying the sludge; phase II, thermal decomposition of the dried sludge; phase III, after phase II. The times required for phases I and II were strongly correlated with the amounts of water and solid matter, respectively, in dehydrated sludge. The reduction rate of the sludge on completion of phase I was about 90% on average, and the decomposition rate of solid matter increased with time during phase II or phase II plus phase III until it reached about 50%. TOC concentration of the eluate from the carbonized sludge was used as an index to evaluate the progress of the carbonization process, and the highest temperature in the carbonization room was recognized as an important operational factor. The specific surface area and pore volume of carbonized sludge were smaller than those of charcoals and activated carbons by 1–3 orders of magnitude and 1–2 orders of magnitude, respectively. No elution of heavy metals was observed from any of the carbonized sludges examined. The reduced amount of carbon in dehydrated johkasou sludge was estimated to be about 25% of the decomposed organic matter.     

Extractability and leachability of heavy metals in Technosols prepared from mixtures of unconsolidated wastes

Mixtures of wastes were prepared to improve on the characteristics of the individual ingredients as Technosols, with special attention given to heavy metal extractability. An anaerobic digested sewage sludge and a CaO-treated aerobic sludge were used. A mixture of the two sludges (50:50 DW basis) was also prepared to provide a third type of sludge. The residues were mixed with other types of waste, such as fly ash, Linz-Donowitz slag, foundry sand, shot blasting machine scrap, fettling and barley straw. Extractability of Cu, Cr, Ni, and Zn by 0.01 M CaCl(2) extraction (Me(CACI(2)) was carried out, and leachability of these elements was estimated by acidification of an aqueous suspension of the mixtures with 0.5 N acetic acid (Me(acetic)). The total concentrations of the metals were also determined (Me(T)). The Me(CACI(2)/Me(T) ratios for Cu and Ni (means: 4.0% and 3.1%) were higher than those for Cr and Zn (means: 0.07% each). The mean Me(acetic)/Me(T) ratios followed the order Ni, Zn, Cu, and Cr (19.5%, 4.1%, 3.7%, and 0.09%, respectively). The results highlight the existence of complex interactions among organic matter solubility, pH and heavy metal extractability.     

Mechanical properties of dewatered sewage sludge

The mechanical properties of dewatered, anaerobically digested sewage sludge were determined from soil laboratory tests. The sludge material is largely composed of organic clay sized-particles, a sizable fraction of which is in an active state of biological digestion which can continue over many years under field conditions. Moderately digested sludge material was found to have a typical specific gravity of solids value of 1.55, and loss on ignition (LOI) value of 70% dry mass. Strongly digested sludge, produced by digesting the liquid sludge further at 35 degrees C in the laboratory, was found to have a lower LOI value of 55% dry mass, and a higher specific gravity of solids value of about 1.72. The maximum dry density of 0.56 tonne/m3 for the dried sludge material was produced using standard Proctor compaction at roughly 85% moisture content (54% solids content). Air-dried, compacted sludge material was tested in quick-undrained triaxial compression and vane shear. Undrained shear strength-moisture content plots are presented. Shear strength values measured in triaxial compression and vane shear were consistent. The effective angle of shearing resistance (phi') was determined from consolidated-undrained, triaxial compression tests on pasteurized, normally consolidated samples of the sludge material. The mechanical properties of the sludge material changed with the level of sludge digestion. The phi' value increased from 32 degrees for moderately digested sludge, to 37 degrees for strongly digested sludge. The effective cohesion of the sludge material remained zero throughout. The shrinkage, swelling and adhesion properties of the sludge material were also studied. Significant shrinkage occurred as the compacted material dried. The sludge material lost its adhesion below about 95% moisture content (51% solids content). Re-hydration of the dry material caused the bulk volume to double.     

Minimisation of N2O emissions from a plant-soil system under landfill leachate irrigation

The irrigation of a plant-soil system with landfill leachate should promote the formation of N2O due to the introduction of organic carbon and mineralized-N and the elevation of the moisture content. Laboratory incubation was performed to minimize N2O emissions from a leachate irrigated plant-soil system by manipulating leachate NH(4)(+)-N loading, moisture content, and soil type. A field investigation, consisting of three plots planted with Cynodon dactylon, Nerium indicum Mill, and Festuca arundinacea Schreb, was then conducted to select plant species. There was almost no difference in N2O emissions between soil moisture contents of 46% and 55% water-filled pore space (WFPS), while a sharp increase occurred at 70% WFPS. N2O fluxes were significantly correlated with leachate NH4(+)-N loading. Amongst the physiochemical characteristics of the selected nine soils, only soil pH was significantly correlated with N2O fluxes. Compared with fertilizers application in other ecosystems, N2O turnover rate from the plant-soil system under leachate irrigation was relatively lower. Therefore, avoiding high NH4(+)-N loadings and excessively wet conditions (<60% WFPS) and cultivating conifer plants of stronger sunlight penetration with less litter deposit on acidic sandy soil could minimize potential N2O emissions under leachate irrigation.