铜污泥中重金属形态分布及浸出毒性分析

结合目前有色冶金工业上普遍采用的石灰铁盐法工艺特点,首次采用改进的BCR连续提取法与毒性浸出实验相结合的方法对铜污泥（中和渣与铁砷渣污泥）的重金属形态分布与浸出毒性进行了系统的研究。结果表明：采用改进的BCR方法对铜冶炼污泥重金属元素形态进行提取,形态提取具有较高的回收率;As、Zn、Pb与Cd为中和渣与铁砷渣污泥中主要的重金属元素（质量含量As＞Zn＞Pb＞Cd）,其中中和渣含As高达58 566 mg/kg（折合5.85%）,铁砷渣含As为12 582 mg/kg（折合1.26%）;两种重金属形态分布差异主要体现在As的形态分布上,铁砷渣污泥中重金属稳定性较好,特别是砷的稳定性较中和渣高;中和渣污泥中,As主要以弱酸态形式存在（占68.01%）,Zn、Pb与Cd主要以残渣态存在;铁砷渣污泥中,As、Zn、Pb与Cd主要以残渣态存在,其中残渣态As占59.21%;浸出毒性结果显示两种污泥中砷的浸出毒性都远远超过国标GB 5085.3-2007规定值,因此铜冶炼厂污泥属于含高砷危险废弃物,而以弱酸态As为主的中和渣污泥浸出毒性较高,而主要以残渣态As存在的铁砷渣污泥浸出毒性较低。     

铜冶炼污泥形成机理及其特性

运用XRD、ICP-AES、AFS、TG-DSC与毒性浸出试验研究了铜火法冶炼中石灰-铁盐法处理酸性废水（污酸）过程中含重金属及砷的污泥（中和渣）形成机理和特性。结果表明：电石渣乳中主要成分Ca(OH)2与污酸中硫酸反应生成CaSO4?xH2O并成为污泥的主要成分;重金属离子主要通过水解反应被沉淀下来,而砷以砷酸盐及亚砷酸盐沉淀而去除,在pH=12.4时电石渣乳与污酸一次中和反应之后,主要有害元素从103～102 mg/L降低至1 mg/L左右,经过絮凝剂添加、浓缩固-液分离与多次空气氧化步骤后使得主要重金属含量达到10?2 mg/L数量级,实现净化后水质达到GB 4913—85污水排放标准;污泥随着温度的升高而逐渐失重,室温至160 ℃时污泥中自由水与CaSO4?xH2O结晶水依次脱除,温度至400 ℃左右污泥中砷氧化物升华,至600～800 ℃范围内少量碳酸钙发生分解,至1050 ℃以上CaSO4在开始分解为氧化钙并造成明显失重;毒性浸出实验中污泥浸出液中As与Se的浓度明显高于GB 5085.3—2007所允许范围,属于危险废弃物。     

粉煤灰在稳定抗生素废水处理剩余污泥中的应用

进行了利用粉煤灰稳定抗生素废水处理过程中产生的剩余污泥的实验. 粉煤灰与剩余污泥按4种比例、3种搅拌时间混合后,采用毒性特性浸取实验、平衡渗漏实验和长期渗漏实验考察重金属离子的渗漏性能. 考虑混合物的重金属离子浓度和病原菌的含量,粉煤灰和污泥的混合物可以农田利用. 在粉煤灰对重金属离子的固定机制中,表面络合作用在较宽的pH值范围内,尤其是在较低pH值时起主要作用,氢氧化物沉淀作用在较高pH值时是主要的作用机制. 实验还发现,粉煤灰固定金属离子的能力随其负荷的增加而增加. 本实验中,粉煤灰能除掉至少92.6%的微生物,粉煤灰的强碱性是杀死剩余污泥中微生物的主要原因.     

含砷石膏渣水泥固化/稳定化：预煅烧影响和砷固化机理

提出了一种预煅烧和水泥固化/稳定化相结合的无害化处置含砷石膏渣方法,研究了预煅烧影响及砷固化机理. 含砷石膏渣中砷含量为8.56%,浸出毒性高达1097.5 mg/L,远高于《危险废物鉴别标准GB5085.3-2007》中危废鉴别值5 mg/L. 预煅烧温度为600和700℃时,石膏渣中亚砷酸盐分解导致总砷量和砷迁移性降低,砷浸出毒性可显著降低至较低水平(41.2和4.2 mg/L). 采用水泥固化可降低砷浸出毒性和控制砷泄露风险,较高温度(600和700℃)预煅烧后的石膏渣经水泥固化后抗压强度分别达4.2和5.2 MPa,砷浸出毒性分别达到0.98和0.22 mg/L,低于GB5085.3-2007危废限值. 砷以Ca2As2O7和AlAsO4形式被包裹或吸附在C?S?H水化产物中,降低了砷迁移性;预煅烧可加速石膏渣水泥固化中砷参与水泥水化和化合反应,导致更多且密实的AlAsO4和Ca2As2O7相形成,强化砷固化效果. 该方法有利于含砷量高和毒性高的含砷石膏渣处置,固化体可直接进入垃圾填埋场.     

Improving supercritical water gasification of sludge by oil palm empty fruit bunch addition: Promotion of syngas production and heavy metal stabilization

The co-gasification of sewage sludge and palm oil empty fruit bunch (EFB) in supercritical water (SCW) was conducted at 400℃ with a pressure of over 25 MPa. This study aimed to investigate the influence of EFB addition on the syngas production and its composition. The heavy metal distribution and the leaching potential of the solid residue were also assessed. The results showed that syngas yield significantly increased with the addition of EFB into the feedstock. The cold gas efficiency (CGE) and carbon efficiency (CE) of co-gasification were higher than those of individual gasification. The actual syngas production from co-gasification of sludge and EFB was 45% higher than the theoretical total volume. The results indicated that the addition of EFB to sludge had the synergetic promotion effect on syngas production from sludge and EFB in supercritical water. This enhancement might be due to the dissolution of alkali metals from EFB and the adjustment of organic ratio. In addition, higher percentage of heavy metals were deposited and stabilized in the solid residue after SCWG. The leaching concentration of heavy metals from the solid residues was decreased to a level below the standard limit which enables it to be safely disposed of in landfill. In conclusion, the EFB addition has been proved to promote syngas production, as well as, stabilize the heavy metal in solid residues during co-SCWG.     

Modeling of Boehmite Leaching from Actual Hanford High‐Level Waste Samples

Abstract

The Department of Energy plans to vitrify approximately 60,000 metric tons of high level waste sludge from underground storage tanks at the Hanford Nuclear Reservation. To reduce the volume of high level waste requiring treatment, a goal has been set to remove about 90 percent of the aluminum, which comprises nearly 70 percent of the sludge. Aluminum in the form of gibbsite and sodium aluminate can be easily dissolved by washing the waste stream with caustic, but boehmite, which comprises nearly half of the total aluminum, is more resistant to caustic dissolution, and requires higher treatment temperatures and hydroxide concentrations. In this work, the dissolution kinetics of aluminum species during caustic leaching of actual Hanford high level waste samples is examined. The experimental results are used to develop a shrinking platelet model that provides a basis for the prediction of dissolution dynamics from a known process temperature and hydroxide concentration. This model is further developed to include the effects of particle size polydispersity, which is found to strongly influence the rate of dissolution. Two identical parameters for this model are used to describe leaching data from two sets of leaching results. When compared to other common monodisperse shrinking particle models, this result suggests a more physically meaningful model.     

Compositions and leaching behaviours of combustion residues

Combustion residues generated from different incineration processes create major environmental problems because these materials contain high amounts of toxic substances. In this communication, we report the leaching behaviours of three residues along with their mineralogical compositions. Column leaching experiments at two different pH values were conducted to study the leaching behaviours. Leachants were analyzed to determine the pH, the concentrations of some toxic elements like Pb, Cr, As, Cd, Se, B, Mo and the volume of leachants passing through the columns. Raw and some treated residues were also characterized by XRD and SEM-EPMA techniques. We found that the concentrations of some toxic elements present in the residues as well as in the leachant fractions collected at different time intervals after leaching were very high. The amounts of soluble salts and toxic elements in the municipal solid waste incinerator (MSWI) ash were higher than those in the other two residues. The order of alkalinities of the three residues was: fly ash (FA)>MSWI ash>sewage sludge ash (SS ash). The final pH of the leachant was related to the volume of leachant passing through the column. Some leachant properties were related to the mineralogical compositions of the residues and to the secondary minerals formed during the leaching period.     

Anaerobic digestion of Aegean olive mill effluents with and without pretreatment

BACKGROUND: Olive oil production is an important economical activity in the Aegean region of Turkey. However, the effluents of the olive oil producing mills with their high organic loads and toxic compounds are causing serious environmental problems. The anaerobic biological treatment of olive mill wastewater (OMWW) using the treatment plants of the regional industries could be a method of choice and within the scope of this study floccular and granular sludges were investigated in batch mode for their success in the treatment of OMWW while producing biogas. The major limitation of this treatment is the inhibition of methanogenic bacteria by the phenolic compounds in OMWW. Thus an integrated solution was suggested in which a pre‐treatment step (dephenolization) was also introduced before biological step. RESULTS: The effluents of 27 olive mills out of 47 were found to have total phenolics (TP) less than 3 g L^?1 and could be treated anaerobically after simple dilution. The biogas production for the untreated OMWW was higher for floccular sludge than for the granular sludge (68.5 mL and 45.7 mL respectively). Combined pre‐treatment experiments, first coagulation with polyaluminum chloride, followed by flocculation with cationic polyelectrolyte and finally Fenton's oxidation, could remove 80% of TP and 95% of the total suspended solids. CONCLUSION: OMWW having TP values less than 3 g L^?1 can be treated anaerobically using floccular sludge after simple dilution and biogas can be produced. For OMWW samples having higher TP values pre‐treatment is necessary and the pre‐treatment given in this study may be used effectively. Copyright © 2010 Society of Chemical Industry     

湿化学法回收污泥水热炭中磷的潜能研究

以富含磷的污泥水热炭为研究对象,用SMT法分析磷的形态分布,以盐酸和柠檬酸为浸提剂,探究湿化学法回收磷的潜能。结果表明,污泥经水热碳化后,总磷含量上升,有机磷朝着无机磷转化,非磷灰石无机磷朝着磷灰石无机磷转化,水热炭中磷形态以无机磷和非磷灰石磷为主。适宜酸浸条件下（盐酸浓度0.3 mol/L、液固比50 ml/g、酸浸时间240 min,柠檬酸浓度0.1 mol/L、液固比50 ml/g、酸浸时间600 min）,盐酸和柠檬酸对磷的浸出效率分别可达94.34%、88.78%,准二级动力学模型能较好地拟合磷的浸出过程;同时,金属浸出能力随酸浸时间延长而逐渐上升,与磷浸出能力呈线性相关,由大到小依次为Fe>Ca>Al>Mg;重金属浸出能力由大到小依次为Zn>Mn>Cr>Cu>Pb;酸浸残渣有望成为性能良好的吸附材料。     

Reuse of heavy metal-containing sludges in cement production

The feasibility of the replacement of raw material for cement production by heavy metal-containing sludge from surface finishing and electroplating industries was investigated. The effect of heavy metal content in the cement raw mix on the crystalline formation in cement production was also examined by XRD analyses. It was found that both sludges were applicable for the replacement of raw mix for cement production by moderate conditioning of the sludge compositions with several compositional parameters. As the replacement of raw mix by sludge was within 15%, the formation of tricalcium silicate (C₃S) phase in cement would be enhanced by the introduced heavy metals. While owing to a high level of heavy metals concentration (> 1.5%) in cement raw mix, C₃S crystalline in cement would be inhibited by a large sludge replacement (> 15%). During the sintering process, over 90% of the high volatile elements such as Pb would evaporate in high temperature, yet 90% of the less volatile elements such as Cu, Cr and Ni would be trapped in clinkers. Most of all, the results of leaching test shows that the trapped elements in hydrated samples would not leach out under acidic conditions. The reuse of heavy metal-containing sludges as cement raw material would not cause leaching hazard from sintered clinkers. Heavy metal-containing sludges thus should have the potential to be utilized as alternative raw materials in cement production.     

A new pH‐based procedure to model toxic effects on nitrifiers in activated sludge

A combination of a titration experiment and a biokinetic parameter estimation procedure is proposed as an experimental tool to study the kinetics of NH₄⁺‐oxidizing bacteria in activated sludge. The method was used to quantify the effect of low concentrations of a toxic compound on the maximum substrate removal capacity and the substrate affinity constant (K_NH) of NH₄⁺‐oxidizing bacteria in activated sludge samples. Experiments in the presence of increasing concentrations of a toxic compound (CN⁻, 3,5‐DCP, Cu²⁺ and phenol) were performed with nitrifying activated sludge samples obtained from two full‐scale wastewater treatment plants. The repeatability of the proposed procedure was found to be sufficient to deduce trends in the behavior of the NH₄⁺‐N‐oxidizing bacteria based on one series of experiments with increasing toxicant concentrations. The experimental results showed that the two sludge samples reacted completely differently in the presence of a certain concentration of the same toxic compound. For phenol, the shape of the titration curves did not correspond any longer to a simple Monod model. In this case, titration curves could be described by a model including both nitrification inhibition by phenol and degradation of the phenol by heterotrophic bacteria. © 1999 Society of Chemical Industry     

Leaching characteristics of boron and selenium for various coal fly ashes

The leaching characteristics of B and Se for coal fly ash (CFA) were examined. Twenty-one CFA samples were subjected to a leaching test, in which CFA was shaken with pure water in a liquid to solid ratio (L/S) of 100 for 24 h at room temperature. The correlation between the leaching amount and the concentration of element in CFA was investigated. The leaching amounts of B, Ca, S, and Se were essentially dependent upon their concentrations in CFA. As the degree of % leaching was higher, the leaching amount was more dependent upon the concentration. Also, the leaching test was performed under constant pH conditions. The leaching of Se tended to increase as the pH in the aqueous phase was raised. For CFA samples, which gave large degree of Ca leaching amount, the leaching of B and Se was decreased especially under high alkaline conditions. The effects of pH and the presence of leached Ca ion in the aqueous phase upon the leaching behavior were discussed.     

模拟酸雨对污泥焚烧灰渣砖中重金属浸出影响

用不同pH的模拟酸雨浸泡掺杂污泥焚烧灰渣自制的混凝土路面砖,探讨了相同浸泡时间时,模拟酸雨pH对自制路面砖中重金属浸出的影响。结果表明,在相同浸泡时间时,铬、锰、铜、铁的浸出浓度都随着模拟酸雨pH的增大而下降。在pH为4.4的模拟酸雨中,浸泡时间大于8小时后,铬、锰、铜、铁浸出浓度的大小关系是铬>锰>铜>铁。而镉、镍、铅的浸出浓度在各种模拟酸雨中都小于0.1 ppb。     

复合硅酸盐水泥固化含氟污泥的试验研究

采用复合硅酸盐水泥对含氟污泥进行固化处理并制取了不同污泥掺量的水泥标准试块，考察了掺量对试块抗压强度、氟离子浸出量、物相转变和晶体形态的影响。结果表明，当含氟污泥掺量为10％时，试块强度高，氟离子浸出量低，是较为适宜的污泥掺加比例。10％掺量试块28天抗压强度达到22.2 MPa，满足一般垫层、基础、地坪及受力不大的结构强度要求；10％掺量试块在地下水和酸雨作用下的氟离子浸出量分别为0.16 mg/L和0.39 mg/L，远小于危险废物100 mg/L的标准限值，安全性较高；机理研究表明，氟化钙污泥的加入加快了水泥中C3A的水化速度，增加了早期AFt生成量，提高了试块早期强度。     

Removal of cadmium in leachate from waste alumina beads using electrochemical technology

US Air Force uses alumina beads (aluminum oxide) as a blast media in routine maintenance operations. These spent alumina beads fail to pass the TCLP test for their cadmium contents. A chemical process consisting of leaching and electrochemical methods is investigated for the feasibility of treating the alumina beads. Dilute nitric acid was found the most effective solution for cadmium leaching. Electrochemical reduction was able to reduce cadmium content in the leachate from 180 mg/L to 15 mg/L. With consumable aluminum electrodes, electrochemical coagulation reduced the cadmium concentration to less than 1 mg/L. Electroflotation was effective for metal sludge, ferric, aluminum, and ferrous hydroxide separations with the assistance of commercial surfactants.     

Filterability of activated sludge in membrane bioreactors

The filterability of activated sludge is an important factor for the economical operation of membrane bioreactors (MBR). In the literature mainly investigations on sludge dewaterability in respect to further disposal are published. In this study, a procedure for determining filterability in a crossflow test cell is introduced. Its features are: no increase in sludge concentration during batch trials, crossflow conditions, and little impact on the sludge structure. The activated sludge filterability is given as the ratio of permeate flux after 40 min of operation to clear water flux. Sludge samples of eight different MBR and one conventional wastewater treatment plant (wwtp) have been examined and compared. Contrary to the literature, no impact of suspended solids (SS) concentration, sludge viscosity, or extractable extracellular polymer substances (EPS) concentration on the filterability was found. Instead, the composition of the liquid phase was found to effect most the filterability of activated sludge, a major influence being the concentration of suspended EPS: the higher the suspended EPS concentration, the lower the filtration index. Suspended EPS concentration increases with high mechanical stress in the MBR and high F/M ratios, if the treated wastewater contains considerable amounts of proteins or polysaccharides.     

污水污泥裂解油中多环芳烃的分析

引言在一些发达国家,污水污泥热裂解技术作为能量回收型污泥处理技术已经进入商业应用阶段,其裂解产生的液体燃料能直接用于柴油机车,并与石油提炼厂生产出来的石油低级馏出液相似     

REMOVAL OF CADMIUM IN LEACHATE FROM WASTE ALUMINA BEADS USING ELECTROCHEMICAL TECHNOLOGY

US Air Force uses alumina beads (aluminum oxide) as a blast media in routine maintenance operations. These spent alumina beads fail to pass the TCLP test for their cadmium contents. A chemical process consisting of leaching and electrochemical methods is investigated for the feasibility of treating the alumina beads. Dilute nitric acid was found the most effective solution for cadmium leaching. Electrochemical reduction was able to reduce cadmium content in the leachate from 180 mg/L to 15 mg/L. With consumable aluminum electrodes, electrochemical coagulation reduced the cadmium concentration to less than 1 mg/L. Electroflotation was effective for metal sludge, ferric, aluminum, and ferrous hydroxide separations with the assistance of commercial surfactants.     

Solubilization of hydrocarbons from oil sludge by synthetic surfactants

Disposal of oil sludges poses an environmental pollution problem due to the presence of high molecular weight hydrocarbons which are hydrophobic and hence non-biodegradable in nature. In-situ transformation of hydrophobic hydrocarbons into hydrophilic moieties using surfactants and further degradation of solubilized hydrocarbons by microorganisms could be the viable solution for disposal of these sludges. Treatment of oil sludge with the synthetic surfactant polyoxyethylene sorbitan monooleate indicated the release of hydrocarbons in the aqueous phase. Increase in soluble chemical oxygen demand with increase in concentration of surfactant and contact time was observed indicating enhancement in solubility of hydrocarbons in the aqueous phase. The optimum ratio of sludge to surfactant was found to be 10: 1. While a two-fold increase in solubility of hydrocarbons was observed due to agitation of sludge samples, variation in pH did not affect the solubilization.     

Effect of classic sterilization on lipid oxidation in model liquid milk‐based infant and follow‐on formulas

The objective of this study was to evaluate the effect of classic sterilization on lipid oxidation of liquid infant and follow‐on formulas by analyzing formation of oxidized and dimeric TAGs. Model systems containing similar components and proportions to those normally found in manufactured samples and a mixture of high‐oleic sunflower oil, rapeseed oil, and fish oil were used to obtain a fatty acid composition profile in accordance with the EU regulations. For comparative purposes, some samples were prepared with high‐oleic sunflower or fish oil and others without the protein components and added Tween‐20. Quantification of total oxidized TAGs provided complete information of the oxidation state and showed clear advantages versus the other methods used, i.e., loss of PUFA and peroxide value. The results showed that the heat treatment used for sterilization did not lead to significant lipid oxidation, but the tocopherol concentration decreased significantly. The marked tocoherol losses found in protein‐free formulas together with the significantly lower tocopherol concentrations in infant formulas (80% whey in protein fraction) compared to follow‐on formulas (80% caseinate in protein ratio) showed the protective effect of the protein fraction, specially sodium caseinate. Practical applications: This study provides useful information on the utility of different methods used to evaluate oxidation in infant and follow‐on formulas. Quantification of total oxidized TAGs standed out because it is a direct and sensitive method and provides complete information at any stage of the oxidative process. Also, this study shows that important decreases of tocopherols may occur during formula processing and special cautions should therefore be taken during storage and commercialization to avoid additional antioxidant losses.