Self-heating of dried industrial wastewater sludge: Lab-scale investigation of supporting conditions

We studied the reactivity of dried sludge produced by treatment of wastewater, mainly from tanneries. The solids transformations have been first characterized with thermal analysis (TGA and DSC) proving that exothermic transformation takes place at fairly low temperature, before the total organic combustion that occurs in air above 400 °C. The onset of low temperature reactions depends on the heating rate and it can be below 100 °C at very small heating rate.Then, we reproducibly determined the conditions to trigger dried sludge self-heating at the laboratory scale, on samples in the 0.2–0.3 kg size. Thermal insulation, some aeration and addition of water are key factors. Mastering the self-heating at this scale allows more detailed investigations as well as manipulation of conditions, to understand its nature, course and remediation. Here we report proves and discussions on the role of air, water, particle size, porosity and biological activity, as well as proving that also dried sludge from similar sources lead to self-heating.Tests demonstrate that air and water are simultaneously required for significant self-heating to occur. They act in diverging directions, both triggering the onset of the reactions and damping the temperature rise, by supporting heat loss. The higher the O₂ concentration, the higher the solids heating rate. More added water prolongs the exothermic phase. Further additions of water can reactivate the material. Water emphasizes the exothermic processes, but it is not sufficient to start it in an air-free atmosphere. The initial solid moisture concentration (between 8% and 15%) affects the onset of self-heating as intuitive. The sludge particles size strongly determines the strength and extent of the heat release, indicating that surface reactions are taking place. In pelletized particles, limitations to water and air permeability mitigates the reaction course.     

Tar-free fuel gas production from high temperature pyrolysis of sewage sludge

Pyrolysis of sewage sludge was studied in a free-fall reactor at 1000–1400 °C. The results showed that the volatile matter in the sludge could be completely released to gaseous product at 1300 °C. The high temperature was in favor of H₂ and CO in the produced gas. However, the low heating value (LHV) of the gas decreased from 15.68 MJ/N m³ to 9.10 MJ/N m³ with temperature increasing from 1000 °C to 1400 °C. The obtained residual solid was characterized by high ash content. The energy balance indicated that the most heating value in the sludge was in the gaseous product.     

Experimental and kinetic modeling of oxygen-enriched air combustion of paper mill sludge

By thermogravimetric analysis (TGA) study, the characteristics of oxygen-enriched air combustion of paper mill sludge were investigated. Experiments on oxidative of paper mill sludge were performed under different atmospheres at 20 °C/min. There are two distinct decomposition processes were observed from the obtained thermogravimetric curves. One of them centered on 320–350 °C with a weight loss of 50%, the second centered on 780–795 °C with a weight of loss 30%. Shift of oxygen concentration have some influences on decomposition processes, and then the processes of paper mill sludge combustion in oxygen-enriched air can be divided into three stages. The kinetic parameters observed by direct non-linear regressions. At the fixed carbon combustion stage, when oxygen concentration from 20 to 80 vol.%, the apparent activation energy is increased from 52.30 to 123.16 kJ/mol, the reaction order of all runs are around 1.     

Experimental investigation of wood combustion in a fixed bed with hot air

Waste combustion on a grate with energy recovery is an important pillar of municipal solid waste (MSW) management in the Netherlands. In MSW incinerators fresh waste stacked on a grate enters the combustion chamber, heats up by radiation from the flame above the layer and ignition occurs. Typically, the reaction zone starts at the top of the waste layer and propagates downwards, producing heat for drying and devolatilization of the fresh waste below it until the ignition front reaches the grate. The control of this process is mainly based on empiricism.MSW is a highly inhomogeneous fuel with continuous fluctuating moisture content, heating value and chemical composition. The resulting process fluctuations may cause process control difficulties, fouling and corrosion issues, extra maintenance, and unplanned stops. In the new concept the fuel layer is ignited by means of preheated air (T > 220 °C) from below without any external ignition source. As a result a combustion front will be formed close to the grate and will propagate upwards. That is why this approach is denoted by upward combustion.Experimental research has been carried out in a batch reactor with height of 4.55 m, an inner diameter of 200 mm and a fuel layer height up to 1 m. Due to a high quality two-layer insulation adiabatic conditions can be assumed. The primary air can be preheated up to 350 °C, and the secondary air is distributed via nozzles above the waste layer. During the experiments, temperatures along the height of the reactor, gas composition and total weight decrease are continuously monitored. The influence of the primary air speed, fuel moisture and inert content on the combustion characteristics (ignition rate, combustion rate, ignition front speed and temperature of the reaction zone) is evaluated.The upward combustion concept decouples the drying, devolatilization and burnout phase. In this way the moisture and inert content of the waste have almost no influence on the combustion process. In this paper an experimental comparison between conventional and reversed combustion is presented.     

Batchwise mesophilic anaerobic co-digestion of secondary sludge from pulp and paper industry and municipal sewage sludge

Residues from forest-industry wastewater-treatment systems are treated as waste at many pulp and paper mills. These organic substances have previously been shown to have potential for production of large quantities of biogas. There is concern, however, that the process would require expensive equipment because of the slow degradation of these substances. Pure non-fibrous sludge from forest industry showed lower specific methane production during mesophilic digestion for 19 days, 53 ± 26 Nml/g of volatile solids as compared to municipal sewage sludge, 84 ± 24 Nml/g of volatile solids. This paper explores the possibility of using anaerobic co-digestion with municipal sewage sludge to enhance the potential of methane production from secondary sludge from a pulp and paper mill. It was seen in a batch anaerobic-digestion operation of 19 days that the specific methane production remained largely the same for municipal sewage sludge when up to 50% of the volatile solids were replaced with forest-industry secondary sludge. It was also shown that the solid residue from anaerobic digestion of the forest-industry sludge should be of suitable quality to use for improving soil quality on lands that are not used for food production.     

A new method for evaluating the sewage sludge pyrolysis kinetics

A new method to simplify calculation the kinetics model is applied to sewage sludge pyrolysis based on the assumption that volatile run out as soon as it formed and during temperature arising process in this study. Difference method widely used to solve math problems is conducted to calculate kinetics parameters. Pyrolysis experiments are carried out at heating rates of 10, 15, 20, and 50 °C/min. All the TG curves are divided into three parts which are beginning decomposition temperature range, main decomposition temperature range, and final decomposition temperature range. The second one is employed to determine the parameters for more than 70% of the total mass loss occurs in this range. According to the developed method, the react order, reaction energy and pre-exponential factor are obtained, which are in the range of 3.9–4.1, 82.3–109.2 kJ/mol and 7.7 × 10⁶–2.8 × 10⁹/min, respectively, which are in the range of that reported previously. As a comparison experimental data with calculated data, the well fitting results indicate that this method is appropriate for simulating sludge pyrolysis kinetics.     

Effect of thermochemical pretreatment on sewage sludge and its impact on carboxylic acids production

This paper investigates the potential of converting sewage sludge into a useful product, namely carboxylic acids. To potentially enhance acid yields, the effect of pretreatment using 0.3 g lime/g dry biomass and water at 100 °C for 10–240 min was studied. The pretreated sludges were anaerobically fermented to mixed-acids using a mixed culture of microorganisms; methanogens were suppressed using iodoform. Batch fermentations were performed at 55 °C using ammonium bicarbonate buffer. The first batch experiments compared treated and untreated sludge as the only substrate. The second batch experiments used a mixture of sludge plus lime-treated bagasse (20:80 by weight). Analysis of liquor shows that the pretreatment were effective in solubilizing constituent compounds of sewage sludge. Nitrogen content and carboxylic acids increased with increasing pretreatment time. However, the soluble sugars peaked at 60 min, and then decreased with longer pretreatment time, showing that the solubilised sugars were undergoing intermolecular reactions, such as Maillard reactions. Fermentation experiments were a good indicator of the biodegradability of the pretreated sludges. Results clearly showed that lime-treating sludge, using even the minimum pretreatment time (10 min), negatively impacted acid production. The likely causes of this observation are attributed to the production of recalcitrant complexes and toxic compounds. Batch fermentation of untreated sludge yielded 0.34 g total acids/g VS fed, whereas sludge with 240-min lime pretreatment yielded only 0.20 g total acids/g VS fed. Co-fermentation of untreated sludge with pretreated bagasse gave a yield of 0.23 g total acids/g VS fed.     

Transformation of phosphorus during drying and roasting of sewage sludge

Sewage sludge (SS), a by-product of wastewater treatment, consists of highly concentrated organic and inorganic pollutants, including phosphorus (P). In this study, P with different chemical fractions in SS under different drying and roasting temperatures was investigated with the use of appropriate standards, measurements, and testing protocol. The drying and roasting treatment of SS was conducted in a laboratory-scale furnace. Two types of SS samples under different treatment temperatures were analyzed by ³¹P NMR spectroscopy. These samples were dried by a vacuum freeze dryer at ?50 °C and a thermoelectric thermostat drying box at 105 °C. Results show that the inorganic P (IP) content increased as the organic P content decreased, and the bio-availability of P increased because IP is a form of phosphorous that can be directly absorbed by plants. ³¹P NMR analysis results indicate the change in P fractions at different temperatures. Non-apatite P was the dominant form of P under low-temperature drying and roasting, whereas apatite P was the major one under high-temperature drying and roasting. Results indicate that temperature affects the transformation of P.     

Pathogen reduction in minimally managed composting of bovine manure

Spread of manure pathogens is of considerable concern due to use of manure for land application. In this study, the effects of four static pile treatment options for bovine manure on die-off of a generic Escherichia coli, E. coli O157:H7 surrogate, Salmonella Senftenberg, Salm. Typhimurium, and Listeria monocytogenes were evaluated. Bovine manure spiked with these bacteria were placed in cassettes at the top, middle, and bottom sections of four static pile treatments that reflect minimal changes in pile construction with and without straw. Temperatures were monitored continuously during the 28 day self-heating period. E. coli and salmonellae were reduced from 8 to 9 log₁₀ CFU g^?1 to undetectable levels (<1.77 log₁₀ MPN g^?1) at 25–30 cm depths within 7 days in all pile sections except for the manure-only pile in which 3–4 logs of reduction were obtained. No L. monocytogenes initially present at 6.62 log₁₀ CFU g^?1 were recovered from straw-amended piles after 14 days, in contrast with manure-only treatment in which this pathogen was recovered even at 28 days. Decline of target bacterial populations corresponded to exposure to temperatures above 45 °C for more than 3 days and amendments of manure with straw to increase thermophilic zones. Use of straw to increase aeration, self-heating capacity, and heat retention in manure piles provides producers a minimal management option for composting that enhances pathogen die-off and thereby reduces risk of environmental spread when manure is applied to land.     

Analysis of the combustion and pyrolysis of dried sewage sludge by TGA and MS

In this study, the combustion and pyrolysis processes of three sewage sludge were investigated. The sewage sludge came from three wastewater treatment plants.Proximate and ultimate analyses were performed. The thermal behaviour of studied sewage sludge was investigated by thermogravimetric analysis with mass spectrometry (TGA-MS). The samples were heated from ambient temperature to 800 °C at a constant rate 10 °C/min in air (combustion process) and argon flows (pyrolysis process). The thermal profiles presented in form of TG/DTG curves were comparable for studied sludges. All TG/DTG curves were divided into three stages. The main decomposition of sewage sludge during the combustion process took place in the range 180–580 °C with c.a. 70% mass loss. The pyrolysis process occurred in lower temperature but with less mass loss. The evolved gaseous products (H₂, CH₄, CO₂, H₂O) from the decomposition of sewage sludge were identified on-line.     

Analysis of the combustion of sewage sludge-derived fuel by a thermogravimetric method in China

The treatment and disposal of sewage sludge are significant environmental problems in China. The reuse of sewage sludge for fuel could be an effective solution. The aim of this study was to characterize the behavior of sludge-derived fuel during combustion by a thermogravimetric method. The combustion profiles obtained showed four obvious weight loss regions. The results of dynamics analysis showed that first-order reactions together with Arrhenius’ law explained reasonably well the different stages of weight loss in the samples. Three temperature regions (162–327 °C, 367–445 °C, and 559–653 °C for sawdust and 162–286 °C, 343–532 °C, and 609–653 °C for coal) in each derivative thermogravimetry (DTG) curve corresponded well with the Arrhenius equation. The reactivity of sludge was lower than that of samples containing sawdust, but higher than that of coal-containing samples. These data demonstrate that sludge-derived fuel has better combustion characteristics than sludge, sawdust, or coal.     

Environmental & economic life cycle assessment of current & future sewage sludge to energy technologies

The UK Water Industry currently generates approximately 800 GW h pa of electrical energy from sewage sludge. Traditionally energy recovery from sewage sludge features Anaerobic Digestion (AD) with biogas utilisation in combined heat and power (CHP) systems. However, the industry is evolving and a number of developments that extract more energy from sludge are either being implemented or are nearing full scale demonstration. This study compared five technology configurations: 1 – conventional AD with CHP, 2 – Thermal Hydrolysis Process (THP) AD with CHP, 3 – THP AD with bio-methane grid injection, 4 – THP AD with CHP followed by drying of digested sludge for solid fuel production, 5 – THP AD followed by drying, pyrolysis of the digested sludge and use of the both the biogas and the pyrolysis gas in a CHP.The economic and environmental Life Cycle Assessment (LCA) found that both the post AD drying options performed well but the option used to create a solid fuel to displace coal (configuration 4) was the most sustainable solution economically and environmentally, closely followed by the pyrolysis configuration (5). Application of THP improves the financial and environmental performance compared with conventional AD. Producing bio-methane for grid injection (configuration 3) is attractive financially but has the worst environmental impact of all the scenarios, suggesting that the current UK financial incentive policy for bio-methane is not driving best environmental practice. It is clear that new and improving processes and technologies are enabling significant opportunities for further energy recovery from sludge; LCA provides tools for determining the best overall options for particular situations and allows innovation resources and investment to be focused accordingly.     

Pilot-scale anaerobic co-digestion of municipal biomass waste and waste activated sludge in China: Effect of organic loading rate

The effects of organic loading rate on the performance and stability of anaerobic co-digestion of municipal biomass waste (MBW) and waste activated sludge (WAS) were investigated on a pilot-scale reactor. The results showed that stable operation was achieved with organic loading rates (OLR) of 1.2–8.0 kg volatile solid (VS) (m³ d)^?1, with VS reduction rates of 61.7–69.9%, and volumetric biogas production of 0.89–5.28 m³ (m³ d)^?1. A maximum methane production rate of 2.94 m³ (m³ d)^?1 was achieved at OLR of 8.0 kg VS (m³ d)^?1 and hydraulic retention time of 15 days. With increasing OLRs, the anaerobic reactor showed a decrease in VS removal rate, average pH value and methane concentration, and a increase of volatile fatty acid concentration. By monitoring the biogas production rate (BPR), the anaerobic digestion system has a higher acidification risk under an OLR of 8.0 kg VS (m³ d)^?1. This result remarks the possibility of relating bioreactor performance with BPR in order to better understand and monitor anaerobic digestion process.     

Thermo-chemical extraction of fuel oil from waste lubricating grease

This study investigated the recovery of oil from waste grease through the process of thermal degradation in an aqueous solution of potassium hydroxide (KOH) followed by solvent extraction. Waste high temperature metal bearing grease was dissolved in a 15 w/w% KOH solution at 80 °C while being agitated at 2000 rpm using a shear action agitator for a period of 15 min. Two distinct layers were observed after 8 min of settling time. The top layer being of dark brown oil and the bottom layer was a heterogeneous mixture. The two layers were separated by decantation. The bottom layer was cooled down to 45 °C followed by slow addition of toluene (C₇H₈) while agitating at 1200 rpm for 15 min to prevent solids settling and minimise rapid volatilisation of the organic compounds in the mixture. Two distinct layers were also formed, the top homogeneous mixture of light brown oil–toluene mixture and the bottom sludge layer. The solvent was recovered from the oil for re-use by fractional distillation of the homogenous mixture. It was observed that 15 w/w% potassium hydroxide solution can chemically degrade the soap matrix in the grease and extract up to 49 w/w% of the fuel oil when subjected to high shear stress at a temperature of 80 °C. The 26 w/w% extraction of oil in the remaining sludge was obtained by solvent extraction process with mass ratios of sludge to solvent of 2:1. Solvent recovery of 88% by mass was obtained via fractional distillation method. The combined extraction processes brought an overall oil yield of 75 w/w% from the waste grease. The fuel oil obtained from this process has similar properties to paraffin oil and can be blended with other oils as an alternative energy source.     

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.).     

Effects of using arsenic–iron sludge wastes in brick making

The arsenic–iron sludge generated in most of the treatment systems around the world is discharged into the nearest watercourse, which leads to accumulative rise of arsenic and iron concentrations in water. In this study, attempts were made to use the arsenic–iron sludge in making bricks and to analyze the corresponding effects on brick properties. The water treatment plant sludge is extremely close to brick clay in chemical composition. So, the sludge could be a potential substitute for brick clay. This study involved the addition of sludge with ratios 3%, 6%, 9% and 12% of the total weight of sludge–clay mixture. The physical and chemical properties of the produced bricks were then determined and evaluated and compared to control brick made entirely from clay. Results of different tests indicated that the sludge proportion and firing temperature were the two key factors in determining the quality of bricks. The compressive strength of 3%, 6%, 9% and 12% sludge containing brick samples were found to be 14.1 MPa, 15.1 MPa, 9.4 MPa and 7.1 MPa, respectively. These results indicate that the compressive strength of prepared bricks initially increased and then decreased with the increase of sludge proportion. Leaching characteristics of burnt bricks were determined with the variation of pH at a constant temperature. The optimum amount of sludge that could be mixed with clay to produce good bonding of clay–sludge bricks was found to be 6% (safely maximum) by weight.     

Greenhouse gases emissions accounting for typical sewage sludge digestion with energy utilization and residue land application in China

About 20 million tonnes of sludge (with 80% moisture content) is discharged by the sewage treatment plants per year in China, which, if not treated properly, can be a significant source of greenhouse gases (GHGs) emissions. Anaerobic digestion is a conventional sewage sludge treatment method and will continue to be one of the main technologies in the following years. This research has taken into consideration GHGs emissions from typical processes of sludge thickening + anaerobic digestion + dewatering + residue land application in China. Fossil CO₂, biogenic CO₂, CH_4, and avoided CO₂ as the main objects is discussed respectively. The results show that the total CO₂-eq is about 1133 kg/t DM (including the biogenic CO₂), while the net CO₂-eq is about 372 kg/t DM (excluding the biogenic CO₂). An anaerobic digestion unit as the main GHGs emission source occupies more than 91% CO₂-eq of the whole process. The use of biogas is important for achieving carbon dioxide emission reductions, which could reach about 24% of the total CO₂-eq reduction.     

An innovative example of herb residues recycling by gasification in a fluidized bed

A utilization way of herb residues is designed to convert herb residues to gas fuel in industrial-scale by a circulating fluidized bed gasifier in this paper. The product gas is used in the production of Chinese medicine, and the heat of the flue gas from the boiler can be used in herb residues drying to realize the energy recycling and no herb residues discharge. The gasification characteristics of herb residues in the circulating fluidized bed of 300 kg/h were investigated for about 200 h. The results indicated that the gas composition and tar yield were affected by biomass flow rate, equivalence ratio (ER), moisture content and char circulating. The lower heating value of product gas was 4–5 MJ/m³ using herb residues as feedstock. When mean biomass flow rate was at 5.5 kg m^?2 s^?1 and ER at 0.35, the product gas reached a good condition with lower heating value of 4.89 MJ/m³ and cold gas efficiency of 62.36%. When the moisture content changed from 12.5% to 18.7%, the concentrations of H₂, CO and CO₂ changed from 4.66% to 6.92%, 11.23% to 10.15%, and 16.55% to 17.82% respectively, and the tar content in gas decreased from 15.1 g/m³ to 14.4 g/m³ when the moisture content increased from 12.5% to 15.4%. There are metal oxides in the ash of herb residues, especially CaO, MgO, K₂O, Al₂O₃, and Fe₂O₃ which have obvious function on tar catalytic decomposition. The ash that attaches to the char particles can decrease the tar yield and improve the quality of gas after returning to the gasifier.     

Managing compost stability and amendment to soil to enhance soil heating during soil solarization

Soil solarization is a method of soil heating used to eradicate plant pathogens and weeds that involves passive solar heating of moist soil mulched (covered) with clear plastic tarp. Various types of organic matter may be incorporated into soil prior to solarization to increase biocidal activity of the treatment process. Microbial activity associated with the decomposition of soil organic matter may increase temperatures during solarization, potentially enhancing solarization efficacy. However, the level of organic matter decomposition (stability) necessary for increasing soil temperature is not well characterized, nor is it known if various amendments render the soil phytotoxic to crops following solarization. Laboratory studies and a field trial were performed to determine heat generation in soil amended with compost during solarization. Respiration was measured in amended soil samples prior to and following solarization as a function of soil depth. Additionally, phytotoxicity was estimated through measurement of germination and early growth of lettuce seedlings in greenhouse assays. Amendment of soil with 10% (g/g) compost containing 16.9 mg CO₂/g dry weight organic carbon resulted in soil temperatures that were 2–4 °C higher than soil alone. Approximately 85% of total organic carbon within the amended soil was exhausted during 22 days of solarization. There was no significant difference in residual respiration with soil depth down to 17.4 cm. Although freshly amended soil proved highly inhibitory to lettuce seed germination and seedling growth, phytotoxicity was not detected in solarized amended soil after 22 days of field solarization.     

Processing of poultry feathers by alkaline keratin hydrolyzing enzyme from Serratia sp. HPC 1383

The present study describes the production and characterization of a feather hydrolyzing enzyme by Serratia sp. HPC 1383 isolated from tannery sludge, which was identified by the ability to form clear zones around colonies on milk agar plates. The proteolytic activity was expressed in terms of the micromoles of tyrosine released from substrate casein per ml per min (U/mL min). Induction of the inoculum with protein was essential to stimulate higher activity of the enzyme, with 0.03% feathermeal in the inoculum resulting in increased enzyme activity (45 U/mL) that further increased to 90 U/mL when 3 d old inoculum was used. The highest enzyme activity, 130 U/mL, was observed in the presence of 0.2% yeast extract. The optimum assay temperature and pH for the enzyme were found to be 60 °C and 10.0, respectively. The enzyme had a half-life of 10 min at 60 °C, which improved slightly to 18 min in presence of 1 mM Ca²⁺. Inhibition of the enzyme by phenylmethyl sulfonyl fluoride (PMSF) indicated that the enzyme was a serine protease. The enzyme was also partially inhibited (39%) by the reducing agent β-mercaptoethanol and by divalent metal ions such as Zn²⁺ (41% inhibition). However, Ca²⁺ and Fe²⁺ resulted in increases in enzyme activity of 15% and 26%, respectively. The kinetic constants of the keratinase were found to be 3.84 μM (K_m) and 108.7 μM/mL min (V_max). These results suggest that this extracellular keratinase may be a useful alternative and eco-friendly route for handling the abundant amount of waste feathers or for applications in other industrial processes.