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.     

城市污泥制备水中重金属吸附剂及其吸附特性研究

本实验利用城市污水厂的脱水污泥,通过化学活化法制备活性炭.研究活化温度、活化时间、固液比和活化剂浓度等因素对制备污泥活性炭的影响,确定氯化锌法制备污泥活性炭的最佳工艺为活化温度550 ℃、活化时间30 min、固液比1∶2、氯化剂浓度45％.将制备的污泥活性炭吸附Cu2＋,Cr6＋,Cd2＋3种重金属离子模拟废水,研究pH值、吸附时间、污泥投加量、温度等因素对吸附过程的影响.实验结果表明,剩余污泥对Cu2＋,Cr6＋,Cd2＋3种重金属离子都具有良好的吸附效果,在优化条件下,3种重金属离子去除率分别达到94％,76％,81％,吸附能力大小顺序为Cu2＋＞Cd2＋＞＋Cr6＋.     

Foamed lightweight materials made from mixed scrap metal waste powder and sewage sludge ash.

The porous properties and pozzolanic effects of sewage sludge ash (SSA) make it possible to produce lightweight materials. This study explored the effects of different metallic foaming agents, made from waste aluminium products, on the foaming behaviours and engineering characteristics, as well as the microstructure of sewage sludge ash foamed lightweight materials. The results indicated that aluminium powder and mixed scrap metal waste powder possessed similar chemical compositions. After proper pre-treatment, waste aluminium products proved to be ideal substitutes for metallic foaming agents. Increasing the amount of mixed scrap metal waste by 10-15% compared with aluminium powder would produce a similar foaming ratio and compressive strength. The reaction of the metallic foaming agents mainly produced pores larger than 10 microm, different from the hydration reaction of cement that produced pores smaller than 1 microm mostly. To meet the requirements of the lightweight materials characteristics and the compressive strength, the amount of SSA could be up to 60-80% of the total solids. An adequate amount of aluminium powder is 0.5-0.9% of the total solids. Increasing the fineness of the mixed scrap metal waste powder could effectively reduce the amount required and improve the foaming ratio.     

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.).     

Acidic bioleaching of heavy metals from sewage sludge

The overall objective of this study was to evaluate the use of controlled bio-acidification prior to land application as a decontamination process to remove heavy metals from sludge. The sulfur-oxidizing bacteria were naturally available in the sludge samples and were activated by providing sulfur and aeration at 28°C–30°C. Activation resulted in bio-acidification to pH 2 within 5–11 days. Successive inoculation of fresh sludges with 5% acidified samples reduced the acidification time to 2–3 days in most samples. Bio-acidification resulted in dissolving significant quantities of heavy metals from all sludge types tested. The maximum solubilization results were: 86%–97% for Ni; 48%–98% for Pb; 26%–71% for Cr; 18%–91% for Zn; 16%–90% for Cu; 7%–60% for Cd. Limited metal solubilization results were observed in the various control samples that accompanied the bio-acidified samples. The leaching results in the control samples were limited to 2%–19% for Ni, 0%–7% for Pb, 0%–5% for Cr, 0.3%–4% for Zn, 0.2%–4% for Cu and 0%–3% for Cd. The results confirmed that Ni and Pb were the easiest metals to dissolve from the various sludge types. On the other hand, the lowest solubilization results were observed for Cu and Cd, and moderate solubilization results were achieved for Cr. The bio-acidification process resulted in moderate gains in terms of improving the suitability of tested sludges for land application. Received: April 19, 1999 / Accepted: November 4, 1999     

Lightweight aggregate made from sewage sludge and incinerated ash

In this study, sewage sludge ash (SSA), with similar characteristics to expansive clay, was used as the principal material and sewage sludge (SS) as the admixture to sinter lightweight aggregate and to study the influences of raw material composition on pelletising, sintering effect and aggregate properties. Results showed that both SS and SSA could be sintered to produce synthetic aggregates individually or mixed. Increasing the amount of SS would decrease the pelletising ratio. Under the consideration of energy saving, the mixture of SSA was better for sintering normal weight aggregate. On the contrary, the mixture that added 20-30% of SS was more adequate to make lightweight aggregates. Adding SS would enhance the oxidation-reduction reaction and lower the bulk density and sintering temperature of aggregates to save energy. Sintering temperature affected the properties of sewage sludge ash lightweight aggregate (SSALA) more than retention period did. Prolonging the retention period could improve bloating effect.     

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.     

RecoPhos: Full-scale fertilizer production from sewage sludge ash

The substitution potential of sewage sludge for German primary phosphate imports has been estimated as 40%. Yet, a marketable option for the full scale recovery has been lacking. This study focuses on a full-scale process for the manufacture of a P-fertilizer from sewage sludge ash (SSA) adapted from the production of Triple Superphosphate. Given (i) conformity of the input with phosphate ores mined from sedimentary deposits, (ii) comparability of the product with a commercially available P-fertilizer regarding contaminant levels, P-fractionation and yield effects, and (iii) compliance of the output with the German Fertilizer Ordinance the RecoPhos P 38 fertilizer was discharged from the waste legislation regime. The fertilizer is currently being produced at a rate of 1000 tonnes per month and sold at a competitive price.     

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.     

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.     

Variations of metal distribution in sewage sludge composting

In the study, the variations of heavy metal distributions (of Cu, Mn, Pb, and Zn) during the sewage sludge composting process were investigated by sequential extraction procedures. The total content of Cu and Zn in the composted mixture increased after the composting process. Mn and Zn were mainly found in mobile fractions (exchangeable fraction (F1), carbonate fraction (F2), and Fe/Mn oxide fraction (F3)). Cu and Pb were strongly associated with the stable fractions (organic matter/sulfides fraction (F4) and residual fraction (F5)). These five metal fractions were used to calculate the metal mobility (bioavailability) in the sewage sludge and composted mixture. The mobility (bioavailability) of Mn, Pb, and Zn (but not Cu) increased during the composting process. The metal mobility in the composted mixture ranked in the following order: Mn>Zn>Pb>Cu.     

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.     

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).     

Mechanical and physical properties of cement blended with sewage sludge ash

The aim of this paper is to evaluate the compatibility of sewage sludge ash (SSA) with various types of commercially available cements (CEM I and CEM II types, cements with several proportions of clinker). The behaviour of mortars fabricated with various percentages (10-30% by weight) of the cement replaced by SSA has been analyzed in terms of workability, mechanical strength, porosity and shrinkage/expansion. SSA exhibits moderate pozzolanic activity; the highest compressive strengths were obtained with 10% of the cement replaced by SSA. The CEM II/B-M (V-LL) 42.5R cement is considered ideal for preparing mortars containing SSA. Shrinkage data demonstrate that sulphates present in SSA are not reactive towards cement.     

Development of lightweight aggregate from dry sewage sludge and coal ash

In this study, dry sewage sludge (DSS) as the principal material was blended with coal ash (CA) to produce lightweight aggregate. The effects of different raw material compositions and sintering temperatures on the aggregate properties were then evaluated. In addition, an environmental assessment of the lightweight aggregate generated was conducted by analyzing the fixed rate of heavy metals in the aggregate, as well as their leaching behavior. The results indicated that using DSS enhanced the pyrolysis–volatilization reaction due to its high organic matter content, and decreased the bulk density and sintering temperature. However, the sintered products of un-amended DSS were porous and loose due to the formation of large pores during sintering. Adding CA improved the sintering temperature while effectively decreasing the pore size and increasing the compressive strength of the product. Furthermore, the sintering temperature and the proportion of CA were found to be the primary factors affecting the properties of the sintered products, and the addition of 18–25% of CA coupled with sintering at 1100 °C for 30 min produced the highest quality lightweight aggregates. In addition, heavy metals were fixed inside products generated under these conditions and the As, Pb, Cd, Cr, Ni, Cu, and Zn concentrations of the leachate were found to be within the limits of China’s regulatory requirements.     

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.     

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.     

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.     

Recycling and recovery routes for incinerated sewage sludge ash (ISSA): A review

The drivers for increasing incineration of sewage sludge and the characteristics of the resulting incinerated sewage sludge ash (ISSA) are reviewed. It is estimated that approximately 1.7 million tonnes of ISSA are produced annually world-wide and is likely to increase in the future. Although most ISSA is currently landfilled, various options have been investigated that allow recycling and beneficial resource recovery. These include the use of ISSA as a substitute for clay in sintered bricks, tiles and pavers, and as a raw material for the manufacture of lightweight aggregate. ISSA has also been used to form high density glass–ceramics. Significant research has investigated the potential use of ISSA in blended cements for use in mortars and concrete, and as a raw material for the production of Portland cement. However, all these applications represent a loss of the valuable phosphate content in ISSA, which is typically comparable to that of a low grade phosphate ore. ISSA has significant potential to be used as a secondary source of phosphate for the production of fertilisers and phosphoric acid. Resource efficient approaches to recycling will increasingly require phosphate recovery from ISSA, with the remaining residual fraction also considered a useful material, and therefore further research is required in this area.