Thermal behaviour of chromium electroplating sludge

Galvanic sludge is classified as a hazardous waste and incineration is one of the techniques used for its treatment. The aim of this work is to study the thermal behavior of a galvanic sludge which contains only chromium as a restriction metal. Simultaneous DTA/TG coupled with mass spectrometer tests were performed to characterize the thermal behavior of the sludge. Besides thermal analysis, sludge samples were heated in a specially designed furnace and these samples were submitted to X-ray diffraction. Vapor from the heated sludge was condensed and the particles were analyzed by EDS microprobe coupled in a scanning electron microscope. The slag formed after the calcination of the galvanic sludge was mainly composed of a mixture of calcium phosphate and fluoride. and minor concentrations of metals. A total weight loss of 34% was observed. The greatest part of this weight loss corresponds to CO2, H2O and SO2. H2O is liberated in the temperature range of 500-1,250 degrees C. CO2 in the range of 500-750 degrees C and SO2 near 1,000 degrees C. Chromium evaporation was not observed in relevant quantities, about 99.6% of the Cr remained incorporated in the slag.     

Copper stabilization in beneficial use of waterworks sludge and copper-laden electroplating sludge for ceramic materials

A promising strategy for effectively incorporating metal-containing waste materials into a variety of ceramic products was devised in this study. Elemental analysis confirmed that copper was the predominant metal component in the collected electroplating sludge, and aluminum was the predominant constituent of waterworks sludge collected in Hong Kong. The use of waterworks sludge as an aluminum-rich precursor material to facilitate copper stabilization under thermal conditions provides a promising waste-to-resource strategy. When sintering the mixture of copper sludge and the 900 °C calcined waterworks sludge, the CuAl₂O₄ spinel phase was first detected at 650 °C and became the predominant product phase at temperatures higher than 850 °C. Quantification of the XRD pattern using the Rietveld refinement method revealed that the weight of the CuAl₂O₄ spinel phase reached over 50% at 850 °C. The strong signals of the CuAl₂O₄ phase continued until the temperature reached 1150 °C, and further sintering initiated the generation of the other copper-hosting phases (CuAlO₂, Cu₂O, and CuO). The copper stabilization effect was evaluated by the copper leachability of the CuAl₂O₄ and CuO via the prolonged leaching experiments at a pH value of 4.9. The leaching results showed that the CuAl₂O₄ phase was superior to the CuAlO₂ and CuO phases for immobilizing hazardous copper over longer leaching periods. The findings clearly indicate that spinel formation is the most crucial metal stabilization mechanism when sintering multiphase copper sludge with aluminum-rich waterworks sludge, and suggest a promising and reliable technique for reusing both types of sludge waste for ceramic materials.     

焚烧温度对电镀污泥后续处理影响研究

在传统的电镀污泥回收有价金属工艺基础上,提出了焚烧预处理新技术,成功降低了电镀污泥的含水率,使其体积及重量都大幅度的减少,并同时提高了焚烧渣的重金属含量.当焚烧温度适宜时,焚烧对电镀污泥的酸浸过程的影响很小,重金属的浸出率仍保持在较高水平.     

含聚油泥处理工艺参数优化及交互作用分析

采用自制的油泥分离剂通过热化学分离法处理聚驱油田现场产生的含聚油泥。采用正交实验得到的最佳工艺参数为:剂泥比2.0 m L/g,反应温度80℃,反应时间30 min,搅拌转速500 r/min,在此工艺条件下原油回收率为92.08%。利用支持向量机运算法(SVM)建立模型,分析了各工艺参数之间的交互作用,得出优化后的含聚油泥处理工艺参数为:剂泥比2.5 m L/g,反应温度80℃,反应时间34 min,搅拌转速530 r/min,理论上的最高原油回收率为94.76%。对于模型优选出的工艺参数进行了5组验证实验,平均原油回收率达94.50%。采用优选工艺参数处理3种不同来源的含聚油泥,原油回收率均高于90%。     

从电镀污泥中回收有价金属的工艺探究

对电镀污泥资源化现状进行探究,并着重对从电镀污泥中回收有价金属的工艺进行综述。最后对如何在清洁生产条件下回收电镀污泥中有价金属提出设想。     

Hydration and leaching characteristics of cement pastes made from electroplating sludge

The purpose of this study was to investigate the hydration and leaching characteristics of the pastes of belite-rich cements made from electroplating sludge. The compressive strength of the pastes cured for 1, 3, 7, 28, and 90 days was determined, and the condensation of silicate anions in hydrates was examined with the ²⁹Si nuclear magnetic resonance (NMR) technology. The leachabilities of the electroplating sludge and the hardened pastes were studied with the multiple toxicity characteristic leaching procedure (MTCLP) and the tank leaching test (NEN 7345), respectively. The results showed that the electroplating sludge continued to leach heavy metals, including nickel, copper, and zinc, and posed a serious threat to the environment. The belite-rich cement made from the electroplating sludge was abundant in hydraulic β-dicalcium silicate, and it performed well with regard to compressive-strength development when properly blended with ordinary Portland cements. The blended cement containing up to 40% the belite-rich cement can still satisfy the compressive-strength requirements of ASTM standards, and the pastes cured for 90 days had comparable compressive strength to an ordinary Portland cement paste. It was also found that the later hydration reaction of the blended cements was relatively more active, and high fractions of belite-rich cement increased the chain length of silicate hydrates. In addition, by converting the sludge into belite-rich cements, the heavy metals became stable in the hardened cement pastes. This study thus indicates a viable alternative approach to dealing with heavy metal bearing wastes, and the resulting products show good compressive strength and heavy-metal stability.     

某电镀厂污泥酸浸除杂提磷试验

探讨了武汉某工业园电镀厂污泥酸浸、除杂提磷的工艺及条件。当H2SO4（浓度为72％）用量为4mL/g污泥,在液固比为5：1,常温搅拌浸出时间为1h,用碱液调节浸出液pH为4后沉淀1h,过滤,磷的浸出率为86％,铁的沉淀率达到94．2％,除铁后的浸出液进一步用NH4HCO3净化,并制取磷铵产品,总养分（N＋P2O5）为52％。产品达到国家合格品的标准。     

Thermochemical treatment of sewage sludge ashes for phosphorus recovery

Phosphorus (P) is an essential element for all living organisms and cannot be replaced. Municipal sewage sludge is a carrier of phosphorus, but also contains organic pollutants and heavy metals. A two-step thermal treatment is suggested, including mono-incineration of sewage sludge and subsequent thermochemical treatment of the ashes. Organic pollutants are completely destroyed by mono-incineration. The resulting sewage sludge ashes contain P, but also heavy metals. P in the ashes exhibits low bioavailability, a disadvantage in farming. Therefore, in a second thermochemical step, P is transferred into mineral phases available for plants, and heavy metals are removed as well. The thermochemical treatment was investigated in a laboratory-scale rotary furnace by treating seven different sewage sludge ashes under systematic variation of operational parameters. Heavy metal removal and the increase of the P-bioavailability were the focus of the investigation. The present experimental study shows that these objectives have been achieved with the proposed process. The P-bioavailability was significantly increased due to the formation of new mineral phases such as chlorapatite, farringtonite and stanfieldite during thermochemical treatment.     

Novel fry-drying method for the treatment of sewage sludge

The purpose of this study is to introduce an efficient drying method named “fry-drying technology” for the treatment of sewage sludge. The basic principle of this method lies in the rapid escape of moisture from sludge material through its pores into the oil medium driven by the strong pressure gradient formed between sludge and oil media. This beneficial pressure distribution for moisture transfer can be established by the subtle combination of the difference of physical properties of specific heat and boiling temperature between water and oil. In order to determine the physical characteristics of this fry-drying technology, a series of experiments were performed in which important parameters, such as heating oil temperature, drying time, oil type, and sludge size, were varied. Numerical calculations using a single solid spherical particle model without any porosity were used to resolve the particle size effect associated with sludge drying.     

Optimization of co-digestion of various industrial sludges for biogas production and sludge treatment: Methane production potential experiments and modeling

Optimal biogas production and sludge treatment were studied by co-digestion experiments and modeling using five different wastewater sludges generated from paper, chemical, petrochemical, automobile, and food processing industries situated in Ulsan Industrial Complex, Ulsan, South Korea. The biomethane production potential test was conducted in simplex-centroid mixture design, fitted to regression equation, and some optimal co-digestion scenarios were given by combined desirability function based multi-objective optimization technique for both methane yield and the quantity of sludge digested. The co-digestion model incorporating main and interaction effects among sludges were utilized to predict the maximum possible methane yield. The optimization routine for methane production with different industrial sludges in batches were repeated with the left-over sludge of earlier cycle, till all sludges have been completely treated. Among the possible scenarios, a maximum methane yield of 1161.53 m³ is anticipated in three batches followed by 1130.33 m³ and 1045.65 m³ in five and two batches, respectively. This study shows a scientific approach to find a practical solution to utilize diverse industrial sludges in both treatment and biogas production perspectives.     

Reductive hydrothermal treatment of sewage sludge

The United States and the European Union each generate around 6900 million dry tons of sewage sludge annually. This is disposed of by land application, landfilling, incineration and other approaches. Reductive hydrothermal (HT) treatment refers here to simple aqueous systems heated and pressurized above 300 degrees C/100bar under anoxic and/or reducing conditions. The purpose of this study was to examine the HT treatment of municipal sewage sludge and infectious fecal microbial cultures with respect to waste volume reduction, biological sterilization, and the generation of usable hydrocarbon product mixtures. These endpoints from HT treatment also were compared to those from pyrolysis. HT at 400 degrees C/150bar transformed sewage sludge solids into complex gas phase (4%) and liquid (6%) hydrocarbon mixtures (approximately 11% combined yield), along with similar amounts (5%) of solid residues. HT products in the aqueous phase (e.g., alcohols) were present but not analysed. Viable mixed fecal cultures (10(9) colony forming units/mL) were completely sterilized by HT treatment, and a hydrocarbon mixture also was generated from the cells, but it was markedly different from that resulting from HT of the sludge. The hydrocarbon assemblage generated from the sludge included n-hydrocarbons (C(9)-C(20)) and alkyl substituted benzenes, phenols, and related compound series of higher mass (e.g., indanes, naphthalenes). Light aromatic parent compounds were significantly less abundant than their substituted C(1)-C(5) alkyl series and there was a paucity of N-, O- and S-heterocycles and polycyclic systems with more than three fused rings. This was different from the products of pyrolysis which were dominated by a relatively simple mixture of linear and branched hydrocarbons and their oxidized homologues (e.g., aldehydes).     

Performance characteristics of a low sludge bioreactor for wastewater treatment

An immobilized microbial cell system was developed and tested for the treatment of industrial wastewater. A consortium of selected aerobic microorganisms was immobilized onto several different support matrices in a packed bed reactor configuration and operated in a continuous process mode. Comparison of the support matrices showed only small differences in treatment efficiency, but significant differences in sludge production and process stability. Porous polymer supports were highly resistant to feedstream upsets and produced 80% lower sludge solids as compared with non-porous supports. These results were seen at both the benchtop and pilot plant scale for treatment of complex industrial waste streams. This technology was applied, in preliminary experiments, to the treatment of a model waste stream simulating wastewater from a Controlled Ecological Life-Support System (CELSS).     

Impacts of microwave pretreatments on the semi-continuous anaerobic digestion of dairy waste activated sludge

Microwave (MW) irradiation is one of the new and possible methods used for pretreating the sludge. Following its use in different fields, this MW irradiation method has proved to be more appropriate in the field of environmental research. In this paper, we focused on the effects of MW irradiation at different intensities on solubilization, biodegradation and anaerobic digestion of sludge from the dairy sludge. The changes in the soluble fractions of the organic matter, the biogas yield, the methane content in the biogas were used as control parameters for evaluating the efficiency of the MW pretreatment. Additionally, the energetic efficiency was also examined. In terms of an energetic aspect, the most economical pretreatment of sludge was at 70% intensity for 12 min irradiation time. At this, COD solubilization, SS reduction and biogas production were found to be 18.6%, 14% and 35% higher than the control, respectively. Not only the increase in biogas production was investigated, excluding protein and carbohydrate hydrolysis was also performed successfully by this microwave pretreatment even at low irradiation energy input. Also, experiments were carried out in semi continuous anaerobic digesters, with 3.5 L working volume. Combining microwave pretreatment with anaerobic digestion led to 67%, 64% and 57% of SS reduction, VS reduction and biogas production higher than the control, respectively.     

Priority and emerging pollutants in sewage sludge and fate during sludge treatment

This paper aims at characterizing the quality of different treated sludges from Paris conurbation in terms of micropollutants and assessing their fate during different sludge treatment processes (STP). To achieve this, a large panel of priority and emerging pollutants (n = 117) have been monitored in different STPs from Parisian wastewater treatment plants including anaerobic digestion, thermal drying, centrifugation and a sludge cake production unit. Considering the quality of treated sludges, comparable micropollutant patterns are found for the different sludges investigated (in mg/kg DM – dry matter). 35 compounds were detected in treated sludges. Some compounds (metals, organotins, alkylphenols, DEHP) are found in every kinds of sludge while pesticides or VOCs are never detected. Sludge cake is the most contaminated sludge, resulting from concentration phenomenon during different treatments. As regards treatments, both centrifugation and thermal drying have broadly no important impact on sludge contamination for metals and organic compounds, even if a slight removal seems to be possible with thermal drying for several compounds by abiotic transfers. Three different behaviors can be highlighted in anaerobic digestion: (i) no removal (metals), (ii) removal following dry matter (DM) elimination (organotins and NP) and iii) removal higher than DM (alkylphenols – except NP – BDE 209 and DEHP). Thus, this process allows a clear removal of biodegradable micropollutants which could be potentially significantly improved by increasing DM removal through operational parameters modifications (retention time, temperature, pre-treatment, etc.).     

Limitations for heavy metal release during thermo-chemical treatment of sewage sludge ash

Phosphate recycling from sewage sludge can be achieved by heavy metal removal from sewage sludge ash (SSA) producing a fertilizer product: mixing SSA with chloride and treating this mixture (eventually after granulation) in a rotary kiln at 1000 ± 100 °C leads to the formation of volatile heavy metal compounds that evaporate and to P-phases with high bio-availability. Due to economical and ecological reasons, it is necessary to reduce the energy consumption of this technology. Generally, fluidized bed reactors are characterized by high heat and mass transfer and thus promise the saving of energy. Therefore, a rotary reactor and a fluidized bed reactor (both laboratory-scale and operated in batch mode) are used for the treatment of granulates containing SSA and CaCl₂. Treatment temperature, residence time and - in case of the fluidized bed reactor - superficial velocity are varied between 800 and 900 °C, 10 and 30 min and 3.4 and 4.6 m s⁻¹. Cd and Pb can be removed well (>95 %) in all experiments. Cu removal ranges from 25% to 84%, for Zn 75-90% are realized. The amount of heavy metals removed increases with increasing temperature and residence time which is most pronounced for Cu.In the pellet, three major reactions occur: formation of HCl and Cl₂ from CaCl₂; diffusion and reaction of these gases with heavy metal compounds; side reactions from heavy metal compounds with matrix material. Although, heat and mass transfer are higher in the fluidized bed reactor, Pb and Zn removal is slightly better in the rotary reactor. This is due the accelerated migration of formed HCl and Cl₂ out of the pellets into the reactor atmosphere. Cu is apparently limited by the diffusion of its chloride thus the removal is higher in the fluidized bed unit.     

The important role of microwave receptors in bio-fuel production by microwave-induced pyrolysis of sewage sludge

Microwave receptor plays an important role in the microwave pyrolysis of sewage sludge in view of its significant influence on the yield and property of bio-fuel products. The yield and the chemical compositions of bio-fuels (gases and oils) obtained from sewage sludge mixed with different receptors (graphite, residue char, active carbon or silicon carbide) were investigated in this study by Gas Chromatography (GC), Gas Chromatography-Mass Spectrometry (GC-MS), and Fourier Transform Infrared Spectroscopy (FTIR). The results showed that the use of silicon carbide gave rise to the highest final temperature of 1130 °C, resulting in the highest yield of gas fraction (up to 63.2 wt.%). The low heating rate (200 °C/min) which was attributed to the addition of residue char promoted condensation reactions and resulted in an increase in solid yield. The existence of active carbon could prolong the resistance time of volatiles in the hot zone owing to its porous structure, generating the maximum concentration of H₂ + CO (60%) in the pyrolysis gas. When graphite was used, the final low temperature favoured the cyclization of the alkenes, giving rise to a higher concentration of mononuclear aromatics in the pyrolysis oils. The model established in this study revealed that the quantity and quality of the products obtained from the microwave pyrolysis highly depended on the process conditions, which were influenced by the receptor significantly.     

Influence of sludge characteristics on coagulant recovery from water treatment sludge: a preliminary study

Journal of Material Cycles and Waste Management - This study investigated the effect of raw water quality and coagulant type and dosage on the efficiency of aluminium recovery from water treatment...     

零价铁活化过硫酸钠深度处理电镀添加剂生产废水

采用零价铁(ZVI)活化过硫酸钠(PS)产生·SO_4~-,以·SO_4~-为氧化剂深度处理电镀添加剂生产废水。考察了废水p H、n(ZVI)∶n(PS)、c(S_2O_8~(2-))和反应温度对废水COD去除率的影响。实验得出废水处理的最佳工艺条件:废水p H为5.0,n(ZVI)∶n(PS)=1.00,c(S_2O_8~(2-))=15 mmol/L,反应温度为50℃。在此最佳工艺条件下反应60 min,COD去除率达到76.8%,出水COD约为42 mg/L,满足GB 18918—2002《城镇污水处理厂污染物排放标准》的一级标准要求。     

Elutriation characteristics of fine particles from bubbling fluidized bed incineration for sludge cake treatment

In this study, measurements of elutriation rate were carried out in a bench scale bubbling fluidized bed incinerator, which was used to combust sludge cake. The particle size distribution and ignition loss were analyzed to study the elutriation characteristics of bubbling fluidized bed incineration. Drawn from the experimental data, the elutriation rate constant K(i)* for fine particles were obtained and correlated with parameters. It was found that most of the solid particles (about 95%) elutriated came from the fluidized medium (inorganic matters), but few came from unburned carbon particles or soot (about 5%). Finally, this paper lists a comparison of K(i)* between this study and the published prediction equations derived or studied in non-incineration modes of fluidized bed. A new and modified correlation is proposed here to estimate the elutriation rate of fine particles emitted from a bubbling fluidized bed incinerator. Primary operation variables (superficial gas velocity and incineration temperature) affecting the elutriation rate are also discussed in the paper.     

Environmental and economic life cycle assessment for sewage sludge treatment processes in Japan

Life cycle assessment for sewage sludge treatment was carried out by estimating the environmental and economic impacts of the six alternative scenarios most often used in Japan: dewatering, composting, drying, incineration, incinerated ash melting and dewatered sludge melting, each with or without digestion. Three end-of-life treatments were also studied: landfilling, agricultural application and building material application. The results demonstrate that sewage sludge digestion can reduce the environmental load and cost through reduced dry matter volume. The global warming potential (GWP) generated from incineration and melting processes can be significantly reduced through the reuse of waste heat for electricity and/or heat generation. Equipment production in scenarios except dewatering has an important effect on GWP, whereas the contribution of construction is negligible. In addition, the results show that the dewatering scenario has the highest impact on land use and cost, the drying scenario has the highest impact on GWP and acidification, and the incinerated ash melting scenario has the highest impact on human toxicity due to re-emissions of heavy metals from incinerated ash in the melting unit process. On the contrary, the dewatering, composting and incineration scenarios generate the lowest impact on human toxicity, land use and acidification, respectively, and the incinerated ash melting scenario has the lowest impact on GWP and cost. Heavy metals released from atmospheric effluents generated the highest human toxicity impact, with the effect of dioxin emissions being significantly lower. This study proved that the dewatered sludge melting scenario is an environmentally optimal and economically affordable method.