Sewage sludge ash to phosphorus fertiliser (II): Influences of ash and granulate type on heavy metal removal

Ashes from monoincineration of sewage sludge suggest themselves as an ideal base for inorganic fertiliser production due to their relatively high phosphorus (P)-content. However, previously they need to be detoxified by reducing their heavy metal content. The core process considered in this paper consists of three steps: mixing of the ashes with suitable chlorine-containing additives, granulation of the mixture and thermochemical treatment in a rotary kiln. Here relevant heavy metal compounds are first transformed into volatile species with the help of the additives and then evaporated from the granules.In this study two chemically different ashes and their mixture were agglomerated to two different granulate types, briquettes and rolled pellets. The resulting six different materials were subjected to thermal treatment at different temperatures. The heavy metals examined were Cu and Zn due to their strong dependence on treatment conditions and their relevance concerning thermal treatment of sewage sludge ashes. Besides, the behaviour of Cl and K was monitored and evaluated.The experiments showed that ash type and temperature are more influential on Cl and heavy metal chemistry than granulate type. Temperature is a primary variable for controlling removal in both cases. Cu removal was less dependent on both ash and granulate type than Zn. The Cl utilization was more effective for Cu than for Zn. Depending on the treatment conditions some K could be retained, whereas always all P remained in the treated material. This satisfies the requirement for complete P recycling.     

The behaviour of ashes and heavy metals during the co-combustion of sewage sludges in a fluidised bed

Co-combustion tests of dry sewage sludges with coal were performed in a pilot bubbling FBC aiming at the characterization of ashes and determining the behaviour of heavy metals in the process. The tests showed compliance with the regulatory levels as far as heavy metal emissions were concerned. The bottom ashes, which accounted for about 70% of the total ash production, were obtained in a granular form, with diameters ranging from 0.5 to 4 mm. The heavy metals were distributed in ashes obtained from different locations of the installation and their concentrations were found to vary depending on the location of capture. The increase in heavy metals content in bottom ashes was not found to lead to higher leachability and ecotoxicity compared to sewage sludges, suggesting that there could be opportunities for their further use. Mercury suffered vaporisation inside the reactor, thus leaving bottom ashes free of contamination by it. However, there was observed a strong retention of mercury in cyclone ashes due to the presence of unburned carbon which probably acted as an adsorbent. The effluent mercury was also found to be mostly associated with the particulate fraction, being less than 20% emitted in gaseous forms. The results suggested that the combustion of the sewage sludge could successfully be carried out and the amount of unburned carbon leaving the combustor but captured in cyclone was large enough to ensure substantial retention of mercury at low temperatures, hence could contribute to an improvement of the mercury release which still remains an issue of great concern to resolve during combustion of waste materials.     

电镀污泥处理技术的研究进展

电镀污泥中含有大量的铬、镉、镍、锌等重金属，是一种典型的危险废物。综述了近年来国内外对电镀污泥处理技术的研究进展，包括固化／稳定化技术、热化学处理技术、有价金属回收技术和材料化技术等。对主要处理技术的应用前景进行了分析，认为热化学处理技术将成为未来电镀污泥处理领域内的一个重要研究方向。     

Vitrification as an alternative to landfilling of tannery sewage sludge

Due to high content of heavy metals such as chromium, tannery sewage sludge is a material which is difficult to be biologically treated as it is in the case of organic waste. Consequently, a common practice in managing tannery sewage sludge is landfilling. This poses a potential threat to both soil and water environments and it additionally generates costs of construction of landfills that meet specific environment protection requirements. Vitrification of this kind of sewage sludge with the addition of mineral wastes can represent an alternative to landfilling.The aim of this study was to investigate the possibility of obtaining an environmentally safe product by means of vitrification of tannery sewage sludge from a flotation wastewater treatment process and chemical precipitation in order to address the upcoming issue of dealing with sewage sludge from the tannery industry which will be prohibited to be landfilled in Poland after 2016. The focus was set on determining mixtures of tannery sewage sludge with additives which would result in the lowest possible heavy metal leaching levels and highest hardness rating of the products obtained from their vitrification.The plasma vitrification process was carried out for mixtures with various amounts of additives depending on the type of sewage sludge used. Only the materials of waste character were used as additives.One finding of the study was an optimum content of mineral additives in vitrified mixture of 30% v/v waste molding sands with 20% v/v carbonate flotation waste from the zinc and lead industry for the formulations with flotation sewage sludge, and 45% v/v and 5% v/v, respectively, for precipitation sewage sludge. These combinations allowed for obtaining products with negligible heavy metal leaching levels and hardness similar to commercial glass, which suggests they could be potentially used as construction aggregate substitutes. Incineration of sewage sludge before the vitrification process lead to increased hardness of the vitrificates and reduced leaching of some heavy metals.     

Sewage sludge ash to phosphorus fertiliser: variables influencing heavy metal removal during thermochemical treatment

The aim of this study was to improve the removal of heavy metals from sewage sludge ash by a thermochemical process. The resulting detoxified ash was intended for use as a raw material rich in phosphorus (P) for inorganic fertiliser production. The thermochemical treatment was performed in a rotary kiln where the evaporation of relevant heavy metals was enhanced by additives. The four variables investigated for process optimisation were treatment temperature, type of additive (KCl, MgCl(2)) and its amount, as well as type of reactor (directly or indirectly heated rotary kiln). The removal rates of Cd, Cr, Cu, Ni, Pb, Zn and of Ca, P and Cl were investigated. The best overall removal efficiency for Cd, Cu, Pb and Zn could be found for the indirectly heated system. The type of additive was critical, since MgCl(2) favours Zn- over Cu-removal, while KCl acts conversely. The use of MgCl(2) caused less particle abrasion from the pellets in the kiln than KCl. In the case of the additive KCl, liquid KCl - temporarily formed in the pellets - acted as a barrier to heavy metal evaporation as long as treatment temperatures were not sufficiently high to enhance its reaction or evaporation.     

Reduction of hazardous elements contained in sewage sludge incineration ash

Research and experimental studies were carried out in relation to reduction of hazardous elements contained in sewage sludge incineration ash. A questionnaire survey was conducted in 69 Japanese municipalities with sewage sludge incineration facilities. Selenium content in bag filter ash and ceramic filter ash was relatively higher than that in ash of cyclone and electrostatic precipitators. It was assumed that selenium vaporized in the furnace was due to adsorb in the fly ash on filter when passing through the low-temperature filter. To reduce high boiling point heavy metals in the ash, sewage sludge and incineration ash were heated up using a small muffle furnace. As the result, the chrome and nickel contents were reduced. A decrease in the surface area of ash and the reduction of elements occurred at the same time in sewage sludge and incineration ashes tested in this study.     

Comparative studies of waste incineration bottom ashes from various grate and firing systems,conducted with respect to mineralogical and geochemical methods of examination

Mineralogical and geochemical techniques can be used successfully to characterize and evaluate bottom ashes produced in waste incineration. At the present time, it is not quite clear to what extent the mineral phase compositions and the content of main elements and heavy metal concentrations of bottom ashes are influenced by the conditions of combustion. Once the location of heavy metals in or with specific minerals is known, it may be considered, in the light of technical possibilities, whether a change in temperature or in the residence time of waste in the combustion chamber could be sufficient to remove these components from their mineral phases.     

The production, use and quality of sewage sludge in Denmark

In Denmark, the production of municipal sewage sludge decreased from approximately 170,000 ton d.m. in 1994 to 140,000 ton d.m. in 2002. The sludge is handled and treated in a number of ways. The quality of Danish sludge has steadily improved since the middle of the 1980s, when the first set of quality criteria for heavy metals was introduced. In 1997, cut-off criteria for the organic pollutants, LAS, DEHP, nonylphenol and PAHs were introduced. Effective control from authorities, voluntary phasing out agreements with industry, improved source identification tools, better handling and after-care methods have in combination with higher waste duties led to a significant reduction in the sludge level of especially cadmium, mercury, chromium, LAS and nonylphenol. The increased quality demand has, nevertheless, also led to a minor reduction in the use of sewage sludge as organic fertiliser on agricultural land.     

Evaluation of the use of a sequential extraction procedure for the characterization and treatment of metal containing solid waste

Metal containing wastes like MSWI fly ashes and blast furnace sludge form a major environmental problem as they are polluted with heavy metals. The ash has to be landfilled or can be used as a construction material, but a pretreatment is in general necessary. Washing of the ashes with water in order to dissolve soluble salts or extracting the heavy metals with chemicals are possibilities. Blast furnace sludge contains large quantities of iron and carbon and could be recycled in the blast furnace, if the zinc content were not that high. Using a hydrometallurgical process the zinc can be removed from the sludge particles. In order to evaluate such treatment methods knowledge of the leaching behaviour of the studied material is very important. One of the factors influencing the leaching behaviour is the composition and mineralogy of the solids. A sequential extraction procedure, whereby the material is sequentially leached with different leaching solutions, can be used as an aid to characterize the material and to determine which chemical conditions are needed to obtain a sufficient extraction efficiency. To verify the accuracy of the sequential extraction procedure, a method is tested on MSWI fly ash and evaluated by comparing the results with those of leaching experiments whereby the final pH of the leaching solutions is varied over a wide range. Based upon this evaluation some suggestions for the use of the sequential extraction procedure are made and an adapted procedure is suggested, and applied to a blast furnace sludge.     

Phosphate fertilizer from sewage sludge ash (SSA)

Ashes from sewage sludge incineration are rich in phosphorus content, ranging between 4% and 9%. Due to the current methods of disposal used for these ashes, phosphorus, which is a valuable plant nutrient, is removed from biological cycling. This article proposes the possible three-stage processing of SSA, whereby more than 90% of phosphorus can be extracted to make an adequate phosphate fertilizer. SSA from two Swiss sewage sludge incinerators was used for laboratory investigations. In an initial step, SSA was leached with sulfuric acid using a liquid-to-solid ratio of 2. The leaching time and pH required for high phosphorus dissolution were determined. Inevitably, dissolution of heavy metals takes place that would contaminate the fertilizer. Thus in a second step, leach solution has to be purified by having the heavy metals removed. Both ion exchange using chelating resins and sulfide precipitation turned out to be suitable for removing critical Cu, Ni and Cd. Thirdly, phosphates were precipitated as calcium phosphates with lime water. The resulting phosphate sludge was dewatered, dried and ground to get a powdery fertilizer whose efficacy was demonstrated by plant tests in a greenhouse. By measuring the weight of plants after 6 weeks of growth, fertilized in part with conventional phosphate fertilizer, fertilizer made from SSA was proven to be equal in its plant uptake efficiency.     

Comparative assessment of municipal sewage sludge incineration,gasification and pyrolysis for a sustainable sludge-to-energy management in Greece

For a sustainable municipal sewage sludge management, not only the available technology, but also other parameters, such as policy regulations and socio-economic issues should be taken in account. In this study, the current status of both European and Greek Legislation on waste management, with a special insight in municipal sewage sludge, is presented. A SWOT analysis was further developed for comparison of pyrolysis with incineration and gasification and results are presented. Pyrolysis seems to be the optimal thermochemical treatment option compared to incineration and gasification. Sewage sludge pyrolysis is favorable for energy savings, material recovery and high added materials production, providing a ‘zero waste’ solution. Finally, identification of challenges and barriers for sewage sludge pyrolysis deployment in Greece was investigated.     

Agronomic characterisation of different types of sewage sludge: Policy implications

Spain is one of the main municipal sewage sludge producers of Europe. This paper aims to agronomically characterise different types of sewage sludge stabilised by different methods (anaerobically digested, composted, and pelletised) and deliver policy recommendations from the results of this characterisation. Anaerobic sewage sludge quality is found to be better in plants with a lower volume of water processing. Composted sludge shows the best quality from a heavy metal point of view, but its low available nitrogen content increases the input of heavy metals when spread, as compared to digested or pelletised sludge. Pelletised sludge has higher heavy metal content than anaerobically digested sludge. Despite the good quality of the sludges, future regulations, especially with regard to Cd levels, will limit the use of this waste in agriculture.     

Potential benefits and risks of land application of sewage sludge

Sewage sludge, also referred as biosolids, is a byproduct of sewage treatment processes. Land application of sewage sludge is one of the important disposal alternatives. Characteristics of sewage sludge depend upon the quality of sewage and type of treatment processes followed. Being rich in organic and inorganic plant nutrients, sewage sludge may substitute for fertilizer, but availability of potential toxic metals often restricts its uses. Sludge amendment to the soil modifies its physico-chemical and biological properties. Crop yield in adequately sludge-amended soil is generally more than that of well-fertilized controls. Bioavailability of metals increases in sludge amended soil at excessive rates of application for many years. Plants differ in their abilities to absorb sludge-derived metals from the soil. The purpose of this paper is to review the available information on various aspects of sewage sludge application on soil fertility and consequent effects on plant production to explore the possibility of exploiting this byproduct for agronomy and horticulture.     

Influence of calcium chloride on the thermal behavior of heavy and alkali metals in sewage sludge incineration

In order to separate and reuse heavy and alkali metals from flue gas during sewage sludge incineration, experiments were carried out in a pilot incinerator. The experimental results show that most of the heavy and alkali metals form condensed phase at temperature above 600 degrees C. With the addition of 5% calcium chloride into sewage sludge, the gas/solid transformation temperature of part of the metals (As, Cu, Mg and Na) is evidently decreased due to the formation of chloride, while calcium chloride seems to have no significant influence on Zn and P. Moreover, the mass fractions of some heavy and alkali metals in the collected fly ash are relatively high. For example, the mass fractions for Pb and Cu in the fly ash collected by the filter are 1.19% and 19.7%, respectively, which are well above those in lead and copper ores. In the case of adding 5% calcium chloride, the heavy and alkali metals can be divided into three groups based on their conversion temperature: Group A that includes Na, Zn, K, Mg and P, which are converted into condensed phase above 600 degrees C; Group B that includes Pb and Cu which solidify when the temperature is above 400 degrees C; and Group C that includes As, whose condensation temperature is as low as 300 degrees C.     

Controlled combustion tests and bottom ash analysis using household waste with varying composition

The influence of the co-combustion of household waste with either sewage sludge, shredder fluff, electronic and electrical waste (WEEE) or PVC on the bottom ash quality and content was investigated under controlled laboratory conditions using a pot furnace. This laboratory approach avoids the interpretation problems related to large variations in input waste composition and combustion conditions that are observed in large scale MSW incinerators. The data for metals content, transfer coefficients and leaching values are presented relative to data for a base household waste composition that did not contain any of the added special wastes. The small WEEE invited direct measurement of precious metals content in the ashes, where measurement accuracy is facilitated by using only mobile phone scrap for small WEEE. The analyses were carried out for different particle size ranges that are of relevance to the recyclability of metals and minerals in the ashes. Positive correlations were found between elements content of the input waste and the bottom ashes, and also between increased levels of Cl, Mo and Cu in the input waste and their leaching in the bottom ashes. These correlations indicate that addition of PVC, small WEEE and shredder fluff in input waste can have a negative influence on the quality of the bottom ashes. Enrichment of Au and Ag occurred in the fractions between 0.15 and 6 mm. The precious metals content represents an economically interesting intrinsic value, even when the observed peak values are properly averaged over a larger volume of ashes. Overall, it has been shown that changes in quality and content of bottom ashes may be traced back to the varied input waste composition.     

Heavy metal removal from contaminated sludge for land application: a review

In recent years, various methods for heavy metal removal from sewage sludge have been extensively studied in order to minimize the prospective health risks of sludge during land application. In this paper, a comparative review and critical analysis of the application of chemical extraction, bioleaching, electroreclamation, and supercritical fluid extraction (SFE), in removing heavy metals from contaminated sludges is presented. Moreover, speciation studies, which can indicate ease of leachability of the different forms of heavy metals in sludge, are also presented. Experimental studies revealed a broad range in metal extraction efficiencies of the different extraction technologies. Acid treatment seemed to effectively remove Cd, attaining as much as 100% removal for some studies, as compared to bioleaching. SFE also gave higher removal efficiency than bioleaching. Cr, Pb and Ni seemed to be also effectively removed by the acid treatment. For the removal of Cu, Mn and Zn, the bioleaching process seemed to be appropriate with maximum removal efficiencies of 91%, 93% and 96% for the three metals, respectively, and as high as 64% minimum removal efficiency for Zn. The SFE process also gave good results for Cu, Mn and Zn removal. Electroreclamation exhibited better removal efficiency for Mn, but is still inferior to acid treatment and bioleaching processes. For chemical extraction, because of the adverse impacts that can result from the use of inorganic acids and complexing agents, interest can be directed more toward utilizing organic acids as extracting agents because of their biodegradability and capability to remove metals at mildly acidic condition, hence requiring less acid. The bioleaching process, although it seems to give a higher yield of metal extraction with lower chemical cost than chemical extraction, may be limited by the inability of the system to cope with the natural environmental conditions, requires strict monitoring of aeration rate and temperature and has applicability to only low sludge solids concentration. A full-scale study would be useful to better assess the efficiency of the process. The electroreclamation technology is limited by its relatively higher energy consumption and limited applicability to sludge. The SFE method, on the other hand, is limited by the complexity of the process and the cost of ligands suitable for effective metal extraction. Both of these technologies are still in their early stage of application and hence there is a need for further basic and applied studies. Finally, the common advantage for almost all treatment technologies studied is that the extraction efficiencies for some metals are high enough to remove metals from sludge to levels suitable for land application.     

Crystalline phase analysis and phosphorus availability after thermochemical treatment of sewage sludge ash with sodium and potassium sulfates for fertilizer production

Phosphorus rich sewage sludge ash is a promising source to produce phosphorus recycling fertilizer. However, the low plant availability of phosphorus in these ashes makes a treatment necessary. A thermochemical treatment (800–1000 °C) with alkali additives transforms poorly plant available phosphorus phases to highly plant available calcium alkali phosphates (Ca,Mg)(Na,K)PO₄. In this study, we investigate the use of K₂SO₄ as additive to produce a phosphorus potassium fertilizer in laboratory-scale experiments (crucible). Pure K₂SO₄ is not suitable as high reaction temperatures are required due to the high melting point of K₂SO₄. To overcome this barrier, we carried out series of experiments with mixtures of K₂SO₄ and Na₂SO₄ resulting in a lower economically feasible reaction temperature (900–1000 °C). In this way, the produced phosphorus potassium fertilizers (8.4 wt.% K, 7.6 wt.% P) was highly plant available for phosphorus indicated by complete extractable phosphorus in neutral ammonium citrate solution. The added potassium is, in contrast to sodium, preferably incorporated into silicates instead of phosphorus phases. Thus, the highly extractable phase (Ca,Mg)(Na,K)PO₄ in the thermochemical products contain less potassium than expected. This preferred incorporation is confirmed by a pilot-scale trial (rotary kiln) and thermodynamic calculation.

     

Comparative goal-oriented assessment of conventional and alternative sewage sludge treatment options

Phosphorous (P) is a limited and non-substitutable resource. Sewage sludge contains significant amounts of P and is therefore a widely applied fertilizer. Due to its organic and inorganic contaminants, sewage sludge is also combusted in industrial facilities as well as in waste incinerators. This study compares five common methods and one novel alternative based on a thermo-chemical process to treat and dispose of sewage sludge with regard to environmental impact, resource recovery, and materials dissipation. The comparison is based on material flow analysis, energy balances, selected LCA impact analysis, and statistical entropy analysis. This work shows that the novel technology combines both advantages of the established practices: organic and inorganic pollutants are either destroyed or removed from the P containing material, and the P returned to the soil exhibits high plant-availability. The novel method also has low emissions. The additional energy requirements should be reduced. However, with regards to sewage sludge P recovery is more important than energy recovery.     

Phosphorus recovery from sewage sludge ash through an electrodialytic process

The electrodialytic separation process (ED) was applied to sewage sludge ash (SSA) aiming at phosphorus (P) recovery. As the SSA may have high heavy metals contents, their removal was also assessed. Two SSA were sampled, one immediately after incineration (SA) and the other from an open deposit (SB). Both samples were ED treated as stirred suspensions in sulphuric acid for 3, 7 and 14 days. After 14 days, phosphorus was mainly mobilized towards the anode end (approx. 60% in the SA and 70% in the SB), whereas heavy metals mainly electromigrated towards the cathode end. The anolyte presented a composition of 98% of P, mainly as orthophosphate, and 2% of heavy metals. The highest heavy metal removal was achieved for Cu (ca. 80%) and the lowest for Pb and Fe (between 4% and 6%). The ED showed to be a viable method for phosphorus recovery from SSA, as it promotes the separation of P from the heavy metals.     

Characteristic of heavy metals in biochar derived from sewage sludge

This study investigates the characteristic of heavy metals (Pb, Zn, Cu, Cd, Cr, Ni and As) in biochar derived from sewage sludge at different pyrolysis temperatures (300, 400, 500, 600 and 700 °C). The heavy metal concentrations, chemical speciation distribution, leaching toxicity, and bio-available contents were investigated using ICP-OES after microwave digestion, a sequential extraction procedure recommended by the Community Bureau of Reference (BCR), an improved nitric acid–sulphuric acid method, and diethylenetriamine pentaacetic acid (DTPA) extraction method, respectively. The results showed that a great percentage of the heavy metals remained in biochar, the concentrations of heavy metals in biochar (except Cd in B7) were higher than that in sludge, and the enrichment of the heavy metals in biochar enhanced with the pyrolysis temperature. Although the effect of pyrolysis temperature on the chemical speciation distribution, the leaching toxicity and the bio-available contents of heavy metals in biochar was inconsistent, the potential risk of biochar on soil and groundwater contamination was lower than sewage sludge.