Comparing different methods of analysing sewage sludge, dewatered sewage sludge and sewage sludge ash

The following article compares different ways of characterising sewage sludge. Against the background of sludge recycling in agriculture as well as treatment with subsequent phosphorus recovery in mind, the article starts by collating and evaluating the levels of phosphorus, heavy metals, chlorine and sulphur in sludge as reported in the literature. Sewage sludge from the sewage treatment plant at Kaditz in Dresden was analysed using standardised and adjusted methods, which produced different results. In the course of this analysis the results were produced by using elemental analysis, atomic absorption spectroscopy, X-ray fluorescence spectroscopy (X-RFA) and ion chromatography (IC). The second part of the article therefore seeks reasons for the differences in the findings and tries to give solution statements. The article closes by calculating transfer coefficients for selected parameters during the incineration process and solid-liquid separation and weighing up the analysis techniques compared. Basically this article will show significant differences in sludge composition and the effects on the specific elements by ashing or mechanical dewatering of the different sludges. An essential attention obtains the analysis by using the X-RFA.     

Combustion characteristics of sewage sludge in an incineration plant for energy recovery

A new type of sewage sludge incinerator that combines a pressurized fluidized bed combustor and a turbocharger driven by flue gas was proposed. In this study, the operation and combustion characteristics of a demonstration plant were clarified, and the design data for a commercial plant were obtained. The steady operation exceeded 600 h in total. CO, NO_x, and N₂O emissions in the flue gas were less than half those of a conventional plant. At an incineration capacity of 100 t/day, an energy savings of approximately 50% can be achieved compared with a conventional plant because the forced draft fan (FDF), the induced draft fan (IDF) and the feed water pump are unnecessary. Also, pressurization allowed reduction of the combustor volume, so about 25% of supplementary fuel can be reduced. Consequently, CO₂ emissions originating from electric power consumption and supplementary fuel is expected to be reduced by about 40% annually compared with emissions from a conventional plant; in addition, the cost of fuel and electricity can be reduced by 23 million yen. Therefore, this advanced incinerator for sewage sludge can realize energy recovery and savings as well as a low environmental impact.     

Reduction of superheater corrosion by co-firing risky biomass with sewage sludge

Iron and aluminium sulphates are added to processes producing sewage sludge (SWS), and SWS also contains aluminium silicates. These compounds can destroy alkali chlorides and prevent Cl deposition on superheaters. Sulphation of chlorides requires formation of SO₃ in the furnace. Raw and digested SWSs were mixed with a fuel containing bark and recycled fuel (REF). Combustion experiments were conducted with a pilot-scale bubbling bed reactor, and concentrations and deposition of critical elements (Cl, Na, K, S…) in the furnace were measured. Change of the iron and aluminium sulphates added to the SWS to phosphates and hydroxides evidently reduced the power of the sulphur to form SO₃. Nevertheless, addition of SWS to the biomass feedstock effectively decreased alkali chloride concentration and Cl deposition, and the alkali sulphates found in the fine fly ash confirmed the contribution of sulphation to alkali capture. The importance of aluminium silicate reaction in alkali capture was indicated.     

Catalytic effect of metal oxides on pyrolysis of sewage sludge

The effect of metal oxides (Al₂O₃, CaO, Fe₂O₃, TiO₂, and ZnO) on the pyrolysis of sewage sludge was investigated. The experiments were performed in a thermogravimetric analyzer (TGA) to check the pyrolysis behavior of raw sludge, demineralized sludge and demineralized sludge with metal oxides added, respectively. The results showed that the presence of Fe₂O₃ and ZnO probably inhibited the decomposition of organic matters in demineralized sludge samples to generate more solid residues, while Al₂O₃, CaO, and TiO₂ promoted the degradation of organic matters throughout the whole pyrolysis temperature ranges. All the metal oxides studied accelerated the initial decomposition of sludge samples. Al₂O₃ and TiO₂ might decrease the total pyrolysis time, while CaO, Fe₂O₃, and ZnO prolong pyrolysis time. The structure of demineralized sludge samples might be changed due to the addition of CaO, TiO₂, and ZnO. Between 550 K and 750 K, the conversion of organic matters (mainly cellulose and lignin) in sludge samples was enhanced by Al₂O₃ and TiO₂, but inhibited by CaO, Fe₂O₃, and ZnO. The effects of metal oxides on the weight loss rate of cellulose in demineralized sludge samples presented the following decreasing order of DE-ZnO > DE-TiO₂ > DE-SS > DE-Al₂O₃ > DE-Fe₂O₃ > DE-CaO.     

Investigation of ash deposit formation during co-firing of coal with sewage sludge, saw-dust and refuse derived fuel

Blends of a South African bituminous “Middleburg” coal and alternative fuels (sewage sludge, saw-dust and refuse derived fuel) have been fired in the slagging reactor to examine the effect of the added fuel on slagging propensity of the mixtures. Two ceramic deposition probes have been used to investigate the initial stages of slagging at 1300 °C and 1200 °C, at 0.5 s and 2 s residence times, respectively. The deposition rates and the deposit structures have been different for the two probes used.Substantial impact of sewage sludge has been observed. The initially formed deposits have become rapidly molten and they flow around the deposition probes, particularly when the sewage sludge fraction exceeds 15% by thermal input and the gas flow temperature exceeds the ash melting point. A 5% addition of the refuse derived fuel (RDF) has increased the deposition rate by almost a factor of two. Large RDF ash particles have been observed in the deposits.The slagging propensity has been correlated with the slagging index based on the ratio of fluxing oxides to sintering oxides. Intensive slagging has been observed when the index is in the 0.75-2 range. Moving away from this range in either direction has decreased the slagging intensity.     

Correlation between dewatering and hydro-textural characteristics of sewage sludge during drying

The aim of this work consists in analysing the dewatering and the shrinkage of a residual urban sludge during convective drying with the objective to find correlations between dewatering and hydro-textural characteristics of the sludge. Laboratory drying experiments are performed in immobile atmosphere, at a temperature of 30 °C, with various relative humidities. Kinetics curves of dewatering and deformation are obtained. A coupled analysis of dewatering and induced volume shrinkage is proposed. This analysis allows: (i) to distinguish the respective parts played by the intrinsic characteristics of the sludge and the process parameter and (ii) to find correlations between the hydro-textural characteristics of the sludge, and its drying and shrinkage aptitudes. Attention is given to the fact that the process parameter, i.e. relative humidity, controls the first constant rate period of the dewatering and that the hydro-textural state of the sludge determine the transitions between the different dewatering periods. The relationships between the hydro-textural characteristics and the dewatering and shrinkage aptitude allow predicting the sludge behaviour during drying according to its characteristics, which is essential information in the choice of the drying strategy.     

磷在污泥热解过程中的迁移转化

采用SMT方法研究磷在热解产物中的赋存形态和分布。结果发现,热处理促进污泥中有机磷（OP）向无机磷（IP）转化。热解温度在800℃以下时,污泥中的磷富集在热解后的污泥固体中。随热解温度升高,污泥中全磷（TP）、无机磷（IP）和磷灰石无机磷（AP）的含量均表现出逐渐升高的趋势,非磷灰石无机磷（NAIP）含量则表现出先升高再降低的趋势。热解温度升高会促使NAIP向AP转化,800℃时AP含量达到最大。污泥中NAIP的主要存在形式为磷酸铝盐和磷酸铁盐,磷酸钙盐含量随温度的升高逐渐增加。污泥中正磷酸单酯和焦磷酸盐受热转化为正磷酸盐,热解后的污泥中磷基本以正磷酸盐的形式存在。该结论为污泥的无害化、资源化利用提供了理论支持。     

Transformation of mineral and emission of particulate matters during co-combustion of coal with sewage sludge

Co-combustion of coal with sewage sludge was carried out in laboratory-scaled drop tube furnace to understand the interaction between different fuels. The combustion conditions were selected as follows: the raw material feeding rate was 0.2-0.3 g/min, temperature was 1200 °C, the atmosphere of 10% O₂ and N₂ being balance was used to guarantee an air ratio of 1.5, and the residence time varied from 0.6 to 2.4 s. The coal/sewage sludge is kept at 50:50 (wt% to wt%), four fuel pairs were selected with respect to the mineral association within individual fuel. The results showed the obvious interaction between coal and sewage sludge during their co-combustion. For the carbon conversion, the devolatilization of mixing fuel occurred quickly; the combustion of both char and evolved volatile progressed almost completely. As a result, the unburnt carbon was almost zero in the fly ash. In addition, the evolution of both mineral and PM varied with the association of minerals in raw fuels. For both coal and sewage sludge rich in included minerals, they combusted separately in the furnace, less interaction occurred accordingly. Conversely, for both them rich in excluded minerals, the minerals reacted with each other to form much agglomeration, and therefore, the particle size of the fly ash was increased, while the amount of PM was decreased, which changed as the coarse fly ash particles. Finally, for the case of coal rich in excluded mineral and sludge rich in included mineral, their co-combustion led to the interaction of their minerals. As a result, more the fine particles were formed, which in part changed into PM. For the vaporized trace elements, they were adsorbed by the melt CaPO₄/Al-Si in the ash and accordingly, their contents in the particulate matter were reduced whereas their particle size distribution shifted to the large value.     

污水污泥水热炭化过程中磷的迁移转化特性

利用SMT方法研究了污水污泥水热炭化固体产物中磷的赋存形态和分布。结果表明,水热炭化处理可以使污泥中的有机磷（OP）转化为无机磷（IP）。在实验条件范围内,污泥中的磷主要富集在水热焦中（R_TP＞70%）,且主要以无机磷（IP）形态存在。延长水热炭化时间或升高水热炭化温度,污泥中无机磷（IP）和非磷灰石无机磷（NAIP）均呈逐渐升高的趋势,而且水热炭化温度的影响程度显著大于水热炭化时间。水热炭化时间对磷灰石无机磷（AP）的影响不明显,但AP含量随水热炭化温度的升高而略微升高。结合XRD谱图分析发现,105℃烘干污泥中主要存在磷酸铝盐和磷酸铁盐两种含磷化合物;水热炭化处理促使焦磷酸盐转化为正磷酸盐,且磷在水热焦中基本以最稳定的正磷酸盐形式存在。该研究结果可为污泥的资源化利用及从污泥中回收磷资源提供理论参考。     

污泥水热碳化中磷的形态变化及金属浸出行为

在不同温度下进行污泥水热碳化实验,利用Hedley顺序提取法探究水热炭中磷的形态变化,并结合钙、铁、铝的浸出行为进一步解释含磷物质的形态分布。结果表明,磷主要富集在水热炭中,水热碳化促进有机磷(P_o)向无机磷(P_i)转化,NaOH溶解态磷(NaOH-P)转化为HCl溶解态磷(HCl-P)和残渣态(Res-P)。污泥和水热炭中Ca、Fe主要以HCl溶解态为主;Al则由NaOH溶解态转化为HCl溶解态。并且水热碳化过程促使污泥中磷形态从磷酸铝盐(Al-P)、磷酸铁盐(Fe-P)向磷酸钙盐(Ca-P)、磷酸镁盐(Mg-P)转化。通过理论分析,水热炭中Al-P可能以Al₂PO₄³⁺和AlHPO₄⁺络合物为主;羟基磷灰石是Ca-P的主要存在形态;部分磷酸盐可能被铁氧化物或氢氧化物固定。为后续水热炭的回收利用提供理论基础。     

Behaviour of dolomite, olivine and alumina as primary catalysts in air-steam gasification of sewage sludge

Sewage sludge gasification assays were performed in an atmospheric fluidised bed reactor using air and air-steam mixtures as the gasifying agents. Dolomite, olivine and alumina are three well known tar removal catalysts used in biomass gasification processing. However, little information is available regarding their performance in sewage sludge gasification. The aim of the current study was to learn about the influence of these three catalysts in the product distribution and tar production during sewage sludge gasification. To this end, a set of assays was performed in which the temperature (750-850 °C), the in-bed catalyst content (0, 10 and 15 wt.%) and the steam-biomass ratio (SB) in the range of 0-1 were varied with a constant equivalence ratio (ER) of 0.3. The results were compared to the results from gasification without a catalyst. We show that dolomite has the highest activity in tar elimination, followed by alumina and olivine. In addition to improving tar removal, the presence of water vapour and the catalysts increased the content of H₂ in the gases by nearly 60%.     

An experimental study of oil recovery from sewage sludge by low-temperature pyrolysis in a fluidised-bed

Pyrolysis of activated sewage sludge was investigated under inert conditions in a fluidised-bed to study the effects of temperature and gas residence time on the product distribution and composition with an aim to maximise the oil yield. The temperature was varied from 300 to 600 °C and the gas residence time from 1.5 to 3.5 s. Three groups of products were produced, namely, a non-condensable gas (NCG) phase, a solid phase (char) and a liquid phase (oil). A maximum of 30% oil yield (wt% daf of sludge fed) was achieved at a pyrolysis temperature of 525 °C and a gas residence time of 1.5 s. Higher temperatures and longer gas residence times favoured the formation of NCG, suggesting that secondary cracking reactions had occurred. The oil obtained was analysed using GC-MS and H NMR to determine the oil's composition and structure, a unit structure of the oil was proposed which consisted of aromatic rings connected by hydrocarbons with -OH functional groups attached.     

Technological and environmental behavior of sewage sludge ash (SSA) in cement-based materials

Sewage sludge ash (SSA) is a waste material obtained from the incineration of wastewater sludge. The physical, chemical and mineralogical characteristics of SSA, and the evaluation of its use in cement-based materials, are presented in this paper. Results show that SSA is composed of irregular grains having a high specific surface area and thus leading to a significantly high water demand. A fraction of the ash is rapidly soluble (sulfates, aluminum and silica) and can create new-formed products in presence of lime. SSA induces short delays of cement hydration, probably due to both minor elements of the ash and dilution effect. Compressive strengths of mortars containing 25% and 50% of SSA are always lower than those of reference mortars but it is shown that SSA has a long-term positive effect which might be related to a slight pozzolanic activity. The amount of elements leached from SSA mortars is slightly higher than from the reference mortar without residue but it remains of the same order of magnitude. An extensive literature review was performed in order to compare the residue used in this study with others included in the same category. This analysis highlighted the principal characteristics that must be taken into account to use SSA correctly in cement-based materials.     

污泥与高硫煤共水热碳化过程中硫氮形态转化规律

采用高温高压反应釜进行了污泥(SS)和高硫煤(CS)的共水热碳化实验。分别考察了混合比和温度对水热炭中硫氮元素形态转化规律的影响。研究结果表明,经过水热处理后,SS中蛋白质氮(N-A)转化为杂环类氮,CS中吡咯氮(N-5)和吡啶氮氧化物(N-X)转化为吡啶氮(N-6)和季氮(N-Q);SS与CS中硫元素逐渐转化为噻吩硫和硫酸盐。随着CS混合比例和温度的升高,水热炭中含氮芳族杂环(例如N-6、N-5和N-Q)占比增加。另外,随着CS混合比例和温度升高,水热炭中噻吩硫含量分别逐渐增加至22.61%和24.98%;升高温度提高了水热炭中硫酸盐含量,而增加CS混合比例却降低了硫酸盐含量。本研究可为后续SS和CS的资源化清洁利用提供理论基础。     

钙基添加剂对污水污泥在水热炭化过程中磷形态及生物有效性的影响

在污泥的热处置过程中,添加剂的存在会改变污泥中的磷形态从而对后续磷的回收利用产生重大影响。本文综合利用化学连续提取（SMT方法）、SEM-EDS、XRD和ICP-MS等分析测试方法,系统研究了CaCl₂在水热炭化过程中对污泥中磷形态及其生物有效性的影响。研究结果表明,水热炭化可以使污泥中有机磷（OP）向无机磷（IP）转化,同时促进污泥中非磷灰石无机磷（NAIP）向磷灰石无机磷（AP）的转化,CaCl₂的适量添加可以促进上述转化过程。经过水热炭化处理后,污泥水热炭中IP和AP的浓度分别提升了35.6%和63.4%,当添加质量分数为20%的CaCl₂时,污泥水热炭中IP和AP的浓度同时达到最大值,分别为79.62mg/g和75.61mg/g。此时污泥水热炭中可溶性磷在2%CA溶液中的溶解度也达到最大的57.02mg/g,在此条件下,污泥水热炭中磷的生物有效性也达到最高。     

Preparation of non-sintered sewage sludge based ceramsite by alkali-thermal activation and hydration mechanism

The recycling of sewage sludge (SS) and fly ash (FA) is significant for the disposal of increasing solid waste. In this study, SS and FA were used as raw materials, and sodium hydroxide (NaOH) and calcium oxide (CaO) were used as alkali activators to prepare non-sintered ceramsite under room temperature curing, and the optimal preparation conditions for the ceramsite were determined through single-factor experiments. Alkaline-thermal activation (ATA) was used to enhance the activity of SS and FA, and the results showed that the activities of SS and FA after ATA were largely improved, and composite activation by CaO and NaOH is more effective than that by either CaO or NaOH. The formed abundant sodium silicate hydrate (N-A-S-H) gels and few hydrated calcium silicate (C-A-S-H)/hydrated silicate (C–S–H) gels can bind well with the particles inside the ceramsite to form the denser structure. In addition, the cylindrical compressive strength of the ceramsite can reach 7.43 MPa, while the apparent density, bulk density, and water absorption are 2603 kg/m³, 852 kg/m³, and 8.37%, respectively under the conditions that the ratio of SS to FA is 8: 2, 9 wt% NaOH and 6 wt% CaO and 600 °C thermal activation, which can meet the standard of ceramsite (GB/T 17431.1–2010). This study provides an effective way for the utilization of SS and FA.     

Measurement and simulation of the contact drying of sewage sludge in a Nara-type paddle dryer

Contact drying experiments were carried out in a Nara-type paddle dryer to study the drying kinetics of sewage sludge in the presence of air. In order to have a better understanding of the sewage sludge drying mechanism, a penetration model developed by Tsotsas and Schlünder is used to simulate the drying kinetics of the pasty, lumpy and granular phase which the sludge experiences during the drying process. The pasty phase is assumed to be a saturated particulate phase, and the granular phase is considered as a mono-dispersed particulate phase whose diameter was experimentally determined. In the lumpy phase, a sludge wall sticking still to the paddle-shaft surface was formed, and the heat transfer resistance from the sludge wall is considered during the model calculation. The influence of the drying parameters (temperature, stirrer speed and air flowrate) on the drying process is investigated experimentally and theoretically. The result indicates that the penetration theory is able to describe the sludge drying kinetics of the three distinct phases. Experimental and calculated drying kinetics are in satisfactory agreement for different drying parameters.     

Sulphur retention during co-combustion of coal and sewage sludge

The aim of this work is the study of the S retention in ashes from combustion of three bituminous coals and a sewage sludge, processed with lime from an urban wastewater treatment plant, that uses FeCl₃ as a coagulant. The effect of the sludge addition during co-combustion of sludge-coal blends in the proportions 10 and 50 wt% of sludge is analysed. The combustion was carried out in an electric furnace at different temperatures (800, 900, and 1100 °C).The results have confirmed that sludge addition to coal enhances S retention at any temperature due to the high CaO contents of the sludge and the formation of CaSO₄. However, the addition of FeCl₃ may be prejudicial, since it produces Na and K volatilisation during co-combustion. Moreover, the presence of Fe₂O₃ from FeCl₃ can reduce the amount of retained sulphur due to its reaction with CaO to produce calcium ferrite. Another element with a similar effect to Fe is Si, since it forms larnite (2CaO·SiO₂) in coal-sludge blends with high Si and Ca contents. Lineal relationships have been found between S retention and the above oxide contents.     

净水厂聚合氯化铝铁污泥对污水中磷的吸附作用

采用控制变量法,逐一研究初始pH值、污泥投加量、初始磷浓度等条件下的聚合氯化铝铁(PAFC)污泥的磷吸附过程。结果表明,在pH值为4.5⁹.0时,污泥对磷的吸附过程稳定,磷的去除率和单位质量污泥对磷的吸附量随pH值的下降而升高。磷的去除率随污泥投加量的增加而增大,随污水的初始磷浓度增大而减小。单位质量污泥磷吸附量随污泥投加量的增加而减小,随污水的初始磷浓度增大而增大。准二级动力学方程可以很好地描述污泥磷吸附过程。通过Langmuir和Freundlich吸附等温线方程发现,PAFC污泥具有较强的磷吸附能力,最大理论磷吸附量为6.049 mg/g。     

Production of ketones from sewage sludge over zirconia-supporting iron oxide catalysts in a steam atmosphere

Recovering useful hydrocarbons from sewage sludge using zirconia-supporting iron oxide catalysts was investigated. Zirconia has activity for decomposing water molecules to generate active oxygen and hydrogen species. These oxygen species spill over to the surface of iron oxide and react with hydrocarbons to produce oxygen-containing organic chemicals such as acetone. Thus, zirconia-supporting iron oxide catalyst has two kinds of active sites on zirconia and on iron oxide. Sewage sludge was hydrothermally liquefied at 573 K in advance, yielding black water containing various hydrocarbons, to enhance the contact of reactant molecules with the catalysts. It was found that the hydrocarbons in the black water converted well to a mixture containing primarily acetone without any carbonaceous residue over zirconia-supporting iron oxide catalysts under the conditions of one atmospheric pressure and superheating steam atmosphere. Furthermore, it was confirmed that acetone was produced continuously from the sewage-derived black water over the catalysts using a bench scale flow reactor.