Effect of sewage sludge content on gas quality and solid residues produced by cogasification in an updraft gasifier

In the present work, the gasification with air of dehydrated sewage sludge (SS) with 20wt.% moisture mixed with conventional woody biomass was investigated using a pilot fixed-bed updraft gasifier. Attention was focused on the effect of the SS content on the gasification performance and on the environmental impact of the process. The results showed that it is possible to co-gasify SS with wood pellets (WPs) in updraft fixed-bed gasification installations. However, at high content of sewage sludge the gasification process can become instable because of the very high ash content and low ash fusion temperatures of SS. At an equivalent ratio of 0.25, compared with wood pellets gasification, the addition of sewage sludge led to a reduction of gas yield in favor of an increase of condensate production with consequent cold gas efficiency decrease. Low concentrations of dioxins/furans and PAHs were measured in the gas produced by SS gasification, well below the limiting values for the exhaust gaseous emissions. NH(3), HCl and HF contents were very low because most of these compounds were retained in the wet scrubber systems. On the other hand, high H(2)S levels were measured due to high sulfur content of SS. Heavy metals supplied with the feedstocks were mostly retained in gasification solid residues. The leachability tests performed according to European regulations showed that metals leachability was within the limits for landfilling inert residues. On the other hand, sulfate and chloride releases were found to comply with the limits for non-hazardous residues.     

Waste plastics recycling by an entrained-flow gasifier

We studied an entrained-flow gasification process which efficiently converts waste plastics to energy at a high energy recovery rate. Waste plastics, after being shredded to <8 mm or <14 mm, were fed into an entrained-flow gasifier with air and oxygen. In the gasifier, organic substances were pyrolyzed, partially combusted, and then converted into synthetic gas (CO, H₂) at a high temperature (over 1600 K). The clarified gasification characteristics were that the lower heat value (LHV) of the product gas was over 4.2 MJ/Nm³ and the cold gas efficiency was approximately 60%. Other inert substances in the wastes such as ashes and metals were melted into slag and condensed on bag filters. The bag filters and a water scrubber removed impurities such as dusts, heavy metals, and hydrogen halides from the product gases. Solid hydrocarbons, which include char and soot, were removed at a hot cyclone and on the bag filters. Received: July 19, 2000 / Accepted: October 3, 2000     

Clay-sewage sludge co-pyrolysis. A TG-MS and Py-GC study on potential advantages afforded by the presence of clay in the pyrolysis of wastewater sewage sludge

Wastewater sewage sludge was co-pyrolyzed with a well characterized clay sample, in order to evaluate possible advantages in the thermal disposal process of solid waste. Characterization of the co-pyrolysis process was carried out both by thermogravimetric-mass spectrometric (TG-MS) analysis, and by reactor tests, using a lab-scale batch reactor equipped with a gas chromatograph for analysis of the evolved gas phase (Py-GC).Due to the presence of clay, two main effects were observed in the instrumental characterization of the process. Firstly, the clay surface catalyzed the pyrolysis reaction of the sludge, and secondly, the release of water from the clay, at temperatures of approx. 450-500 °C, enhanced gasification of part of carbon residue of the organic component of sludge following pyrolysis.Moreover, the solid residue remaining after pyrolysis process, composed of the inorganic component of sludge blended with clay, is characterized by good features for possible disposal by vitrification, yielding a vitreous matrix that immobilizes the hazardous heavy metals present in the sludge.     

Gasification characteristics of biomass for tar removal by secondary oxidant injection

Gasification experiments for sawdust were conducted using a fixed bed reactor at 900 °C by varying the secondary oxidant injection ratio to determine the optimal conditions for tar removal along with the enhancement of gasification efficiency. Secondary oxidant was injected as an oxidant at the top zone of the gasifier in varying ratios of 10–30% of the total amount of oxidant. This method was based on the primary method of tar removal and gasification efficiency improvement by thermal cracking of tar. Various gasification performance parameters were evaluated and tar content was estimated by measuring the fluctuation of weight of the activated carbon filter. The results showed that the concentration of tar in the producer gas decreased by injecting the secondary oxidant, even though syngas yield decreased. The recycling potential of the char produced in the gasification experiments was also assessed with the purpose of utilizing char as an adsorbent by determining its surface area and pore volume. The results demonstrated that the char produced from the gasification experiment had similar quality to that of the activated carbon used in this experiment.     

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.     

Volatility of heavy metals during incineration of tannery sludge in the presence of chlorides and phosphoric acid.

Knowledge of the behaviour of heavy metals in the combustion process is a most important factor in selecting disposal alternatives for waste materials. Accordingly, in this work, the vaporization behaviour of highly concentrated heavy metals (Pb, Zn, Cu and Cr) in tannery sludge were investigated experimentally. The sludge was spiked with various chlorine compounds (i.e. PVC, FeCl3, CaCl2 and NaCl) and pre-treated with phosphoric acid in order to evaluate the capacity of enhancement and weakening of the volatility of the heavy metals contained in tannery sludge. The experimental results show that the vaporization percentages increased with increasing ratio of Cl/sludge and temperature, and the accelerating and increasing effect of the addition of chlorides on the vaporization percentage of heavy metals was dependent on the release capacity of chlorine radicals. The vaporization percentages of lead and zinc increased by 15-20%, whereas those of copper and chromium increased by only about 3 and 10% at 800 degrees C. However, heavy metals were not expected to be completely released in the combustion process in spite of the high ratio of Cl/sludge. Alternately, heavy metals contained in tannery sludge can be immobilized effectively by pre-treatment with phosphoric acid. When the 85% phosphoric acid accounted for 10% of dry basis of tannery sludge, the phosphate-treated sludge showed the lowest vaporization percentage of about 3-15% with formation of Ca18Cu3(PO4)14, Ca9Cr(PO4)7, Ca19Zn2(PO4)14 and PbMgP2O7 in the bottom ash.     

Biomass waste gasification - can be the two stage process suitable for tar reduction and power generation?

A pilot scale gasification unit with novel co-current, updraft arrangement in the first stage and counter-current downdraft in the second stage was developed and exploited for studying effects of two stage gasification in comparison with one stage gasification of biomass (wood pellets) on fuel gas composition and attainable gas purity. Significant producer gas parameters (gas composition, heating value, content of tar compounds, content of inorganic gas impurities) were compared for the two stage and the one stage method of the gasification arrangement with only the upward moving bed (co-current updraft). The main novel features of the gasifier conception include grate-less reactor, upward moving bed of biomass particles (e.g. pellets) by means of a screw elevator with changeable rotational speed and gradual expanding diameter of the cylindrical reactor in the part above the upper end of the screw. The gasifier concept and arrangement are considered convenient for thermal power range 100-350 kW_th. The second stage of the gasifier served mainly for tar compounds destruction/reforming by increased temperature (around 950 °C) and for gasification reaction of the fuel gas with char. The second stage used additional combustion of the fuel gas by preheated secondary air for attaining higher temperature and faster gasification of the remaining char from the first stage. The measurements of gas composition and tar compound contents confirmed superiority of the two stage gasification system, drastic decrease of aromatic compounds with two and higher number of benzene rings by 1-2 orders. On the other hand the two stage gasification (with overall ER = 0.71) led to substantial reduction of gas heating value (LHV = 3.15 MJ/Nm³), elevation of gas volume and increase of nitrogen content in fuel gas. The increased temperature (>950 °C) at the entrance to the char bed caused also substantial decrease of ammonia content in fuel gas. The char with higher content of ash leaving the second stage presented only few mass% of the inlet biomass stream.     

Reduction of tar using cheap catalysts during sewage sludge gasification

Solid-fuel conversion or gasification study of sewage sludge and energy recovery has become increasingly important because energy recovery and climate change are emerging issues. Various types of catalysts, such as dolomite, steel slag and calcium oxide, were tested for tar reduction during the sewage sludge gasification process. For the experiments on sewage sludge gasification reactions and tar reduction using the catalysts, a fixed bed of laboratory-scale experimental apparatus was set up. The reactor was made of quartz glass using an electric muffle furnace. The sewage sludge samples used had moisture contents less than 6%. The experimental conditions were as follows: sample weight was 20 g and reaction time was 10 min, gasification reaction temperature was from 600 to 800°C, and the equivalence ratio was 0.2. The quantity of catalysts was 2–6 g, and temperatures of catalyst layers were 500–700°C. As the reaction temperature increased up to 800°C, the yields of gaseous products and liquid products increased, whereas char and tar products decreased, showing effects on gas product compositions. These results were considered to be due to the increase of the water-gas reaction and Boudouard reaction. In the case of experiments with catalysts, dolomite (4 g), steel slag (6 g) and calcium oxide (6 g) were used. When the temperature of catalysts increased, the weight of the tar produced decreased with different cracking performances by different catalysts. Reforming reactions were considered to occur on the surface of dolomite, steel slag and calcium oxide, causing cracking of the hydrocarbon structure, which eventually showed reduced tar generation.     

酸浸出法回收冶金污泥中的有价金属

采用二次酸浸出的方法回收镍钴湿法冶金工业污泥中的有价金属。先采用水和硫酸作为浸出剂浸出Mg和Na,最佳工艺条件为浸出液的pH 7.5、浸出时间5 min、浸出剂体积与干污泥质量的比(ω)为10 mL/g。再采用硫酸作为浸出剂、焦亚硫酸钠作为还原剂进行二次酸浸,在硫酸与污泥质量比为1.3、焦亚硫酸钠与污泥质量比为0.3、ω为5 mL/g、浸出温度85℃、浸出时间20 min的最佳工艺条件下,Co、Ni、Cu、Mn和Zn的浸出率分别达92.45%、93.48%、89.52%、97.78%和94.79%。经XRD表征,浸出后污泥中未见原污泥中的矿物相,说明原污泥中的矿物几乎全部被溶解。     

Gasification characteristics of sewage sludge combined with wood biomass

The gas products from gasification processes have been considered to have some limitations in gas composition and heating value from the previous studies. Gasification characteristics of sewage sludge and wood mixture were investigated using different mixing ratios with the purpose of better quality of gas product suitable for energy/power generation. The gasification experiment was performed by an indirectly heated fluidized bed reactor. As reaction temperature increased from 600 to 900 °C, the yield of gas product increased with higher generation of CO, H₂ and CH₄ by more activated gas conversion reactions. As the equivalence ratio increased from 0.2 to 0.4, composition ratio of CO₂ increased while CO, CH₄, H₂ decreased as expected. Several operating variables including mixing ratio of wood with dried sludge were also tested. From this initial stage of experiment, optimal operating conditions for the bubbling fluidized bed gasifier, could be considered 900 °C in temperature; 0.2 in equivalence ratio and 40 % in wood mixing ratio within test variables range. These results will be more thoroughly investigated for the application to the larger scale pilot system.     

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     

Evaluation of metals in the residue of paper sludge after recovery of pulp components using an ionic liquid

The quantity of sludge produced by the paper industry in Japan in 2011 was estimated to be 27.91 million tons wet weight. This amount is the third largest among all industrial wastes. To explore ways of reusing recovered paper pulp and safely disposing of the residue, we investigated the distribution of metals in the process of recovery of pulp from two types of paper sludge using an ionic liquid. 32 and 46 % of pulp from paper sludge A and B was recovered using ionic liquid, respectively; the resultant weight reduction of the solid mass was comparable to that of incineration. There were virtually no heavy metals but aluminum in the recovered pulp, which makes its reuse viable at present. The characteristics of the metals in the residues differed according to the treatment used and properties of the paper sludge. Copper accounted for ~10 % in the ionic liquid used for recovery of pulp from the paper sludges. This suggests that [bmIm]Cl has the potential to dissolve a specific amount of copper compared to other metals.     

Fate and behavior of selected heavy metals with mercury mass distribution in a fluidized bed sewage sludge incinerator

In this paper, emission and distribution behavior of six heavy metals (As, Cd, Cr, Ni, Pb, and Hg), particulate matter and mass distribution of mercury within the different streams of a fluidized bed sewage sludge incinerator are presented. At the inlet of air pollution control devices (APCDs); Cd, Cr, Ni and Pb were mainly enriched in coarse particles; comparatively As content was higher in fine particles (<PM_2.5). The concentration of heavy metals in total particulate matter and PM_2.5, at the inlet of APCDs, were in the order of Cr > Ni > Pb > As > Cd. Mercury was almost always distributed in flue gas. Metals, other than mercury, were efficiently removed in APCDs and their concentrations in bottom ash, with fly ash being higher, whereas for that in wastewater, then waste sand was lesser. Overall mercury removal efficiency of APCDs was 98.6 %. More than 83.3 % of mercury was speciated into oxidized form at the inlet of APCDs, attributed by higher chlorine content in sludge. Mercury was mainly distributed in wastewater (78.4 %), wastewater from a spray dry reactor (16.8 %), fly ash in a hopper (3.4 %) and flue gas (1.4 %). This result is one of the first for data to be obtained; more experiments are required to control emission from such sources.     

Steam gasification of epoxy circuit board in the presence of carbonates

To recover useful metals from end-of-life electronic devices and to convert plastic components from these devices into clean fuel gas, steam gasification of epoxy board samples was carried out at 600–700?°C and 0.1?MPa pressure in the presence of a ternary eutectic carbonate (lithium carbonate, sodium carbonate, and potassium carbonate). Hydrogen and carbon dioxide were the main products, and methane and carbon monoxide were detected as minor products. The gasification proceeded in two steps: an initial rapid pyrolysis followed by secondary steam gasification of char produced from the pyrolysis. The ternary eutectic carbonate accelerated not only the latter steam gasification but also the initial rapid pyrolysis. The activation energy for the steam gasification of epoxy board samples in the presence of the carbonate was 122?kJ/mol.     

Sequential extraction of metals from mixed and digested sludge from aerobic WWTPs sited in the south of Spain

The content of heavy metals is the major limitation to the application of sewage sludge in soil. However, assessment of the pollution by total metal determination does not reveal the true environmental impact. It is necessary to apply sequential extraction techniques to obtain suitable information about their bioavailability or toxicity. In this paper, sequential extraction of metals from sludge before and after aerobic digestion was applied to sludge from five WWTPs in southern Spain to obtain information about the influence of the digestion treatment in the concentration of the metals. The percentage of each metal as residual, oxidizable, reducible and exchangeable form was calculated. For this purpose, sludge samples were collected from two different points of the plants, namely, sludge from the mixture (primary and secondary sludge) tank (mixed sludge, MS) and the digested-dewatered sludge (final sludge, FS). Heavy metals, Al, Cd, Co, Cr, Cu, Fe, Hg, Mn, Mo, Ni, Pb, Ti and Zn, were extracted following the sequential extraction scheme proposed by the Standards, Measurements and Testing Programme of the European Commission and determined by inductively-coupled plasma atomic emission spectrometry. The total concentration of heavy metals in the measured sludge samples did not exceed the limits set out by European legislation and were mainly associated with the two less-available fractions (27-28% as oxidizable metal and 44-50% as residual metal). However, metals as Co (64% in MS and 52% in FS samples), Mn (82% in MS and 79% in FS), Ni (32% in MS and 26% in FS) and Zn (79% in MS and 62% in FS) were present at important percentages as available forms. In addition, results showed a clear increase of the concentration of metals after sludge treatment in the proportion of two less-available fractions (oxidizable and residual metal).     

Fixation and partitioning of heavy metals in slag after incineration of sewage sludge

Fixation of heavy metals in the slag produced during incineration of sewage sludge will reduce emission of the metals to the atmosphere and make the incineration process more environmentally friendly. The effects of incineration conditions (incineration temperature 500-1100°C, furnace residence time 0-60min, mass fraction of water in the sludge 0-75%) on the fixation rates and species partitioning of Cd, Pb, Cr, Cu, Zn, Mn and Ni in slag were investigated. When the incineration temperature was increased from 500 to 1100°C, the fixation rate of Cd decreased from 87% to 49%, while the fixation rates of Cu and Mn were stable. The maximum fixation rates for Pb and Zn and for Ni and Cr were reached at 900 and 1100°C, respectively. The fixation rates of Cu, Ni, Cd, Cr and Zn decreased as the residence time increased. With a 20min residence time, the fixation rates of Pb and Mn were low. The maximum fixation rates of Ni, Mn, Zn, Cu and Cr were achieved when the mass fraction of water in the sludge was 55%. The fixation rate of Cd decreased as the water mass fraction increased, while the fixation rate of Pb increased. Partitioning analysis of the metals contained in the slag showed that increasing the incineration temperature and residence time promoted complete oxidation of the metals. This reduced the non-residual fractions of the metals, which would lower the bioavailability of the metals. The mass fraction of water in the sludge had little effect on the partitioning of the metals. Correlation analysis indicated that the fixation rates of heavy metals in the sludge and the forms of heavy metals in the incinerator slag could be controlled by optimization of the incineration conditions. These results show how the bioavailability of the metals can be reduced for environmentally friendly disposal of the incinerator slag.     

Gasification and its emission characteristics for dried sewage sludge utilizing a fluidized bed gasifier

Various research has attempted to determine the proper treatment of sewage sludge, including thermal technologies. Efficient thermal technologies have been focused on because of their energy saving/energy recovery. Gasification technology can be considered one of these approaches. In this study, the characteristics of gasification reactions were investigated with the aim of finding fundamental data for utilizing sewage sludge as an energy source. For the experiments on sewage sludge gasification reaction characteristics, a laboratory-scale experimental apparatus was set up with a fluidizing bed reactor of 70-mm inner diameter and 600-mm total height using an electric muffle furnace. The experimental materials were prepared from a sewage treatment plant located in Seoul. The reaction temperature was varied from 630 to 860°C, and the equivalence ratio from 0.1 to 0.3. The gas yields, compositions of product gas, and cold gas efficiencies of product gas were analyzed by GC/TCD and GC/FID installed with a carboxen-1000 column. The experimental results indicated that 800°C, ER 0.2 was an optimum condition for sewage sludge gasification. The maximum yield of product gas was about 44%. Producer gas from experiments was mainly composed of hydrogen, carbon monoxide, carbon dioxide, and methane. The cold gas efficiency of sewage sludge gasification was about 68%. The H₂/CO ratio and CO/CO₂ ratio were about 1.1 and 1.4, respectively, in optimum reaction conditions. Gaseous pollutants such as SO₂, HCl, NH₃, H₂S, and NO₂ were also analyzed at various gasification/combustion conditions, and their gaseous products were compared, showing significantly different oxidized product distributions.     

A study of heavy metals and their fate in the composting of tannery sludge

Tannery waste is categorized as toxic and hazardous in Malaysia due to its high content of Cr (in excess of 500 mg/kg) and other heavy metals. Heavy metals, when in high enough concentrations, have the potential to be both phytotoxic and zootoxic. Heavy metals are found as contaminants in tannery sludge. This investigation aimed to identify the fate of chromium, cadmium, copper, lead, and zinc concentrations in tannery sludge throughout a 50-day composting cycle. The results of this study showed a general increase in the removal of Cr, Cd, Pb, and to a much smaller extent Zn and Cu, manifested by a decrease in their overall concentrations within the solid fraction of the final product (the decreases were likely the result of leaching). Furthermore, in using a sequential extraction method for sludge composting at different phases of treatment, a large proportion of the heavy metals were found to be associated to the residual fraction (70-80%) and fractions more resistant to extraction, X-NaOH, X-EDTA, X-HNO3 (12-29%). Less than 2% of the metals were bound to bioavailable fractions X-(KNO3+H2O).     

Determining heavy metals in spent compact fluorescent lamps (CFLs) and their waste management challenges: Some strategies for improving current conditions

From environmental viewpoint, the most important advantage of compact fluorescent lamps (CFLs) is reduction of green house gas emissions. But their significant disadvantage is disposal of spent lamps because of containing a few milligrams of toxic metals, especially mercury and lead. For a successful implementation of any waste management plan, availability of sufficient and accurate information on quantities and compositions of the generated waste and current management conditions is a fundamental prerequisite. In this study, CFLs were selected among 20 different brands in Iran. Content of heavy metals including mercury, lead, nickel, arsenic and chromium was determined by inductive coupled plasma (ICP). Two cities, Tehran and Tabriz, were selected for assessing the current waste management condition of CFLs. The study found that waste generation amount of CFLs in the country was about 159.80, 183.82 and 153.75 million per year in 2010, 2011 and 2012, respectively. Waste generation rate of CFLs in Iran was determined to be 2.05 per person in 2012. The average amount of mercury, lead, nickel, arsenic and chromium was 0.417, 2.33, 0.064, 0.056 and 0.012 mg per lamp, respectively. Currently, waste of CFLs is disposed by municipal waste stream in waste landfills. For improving the current conditions, we propose by considering the successful experience of extended producer responsibility (EPR) in other electronic waste management. The EPR program with advanced recycling fee (ARF) is implemented for collecting and then recycling CFLs. For encouraging consumers to take the spent CFLs back at the end of the products’ useful life, a proportion of ARF (for example, 50%) can be refunded. On the other hand, the government and Environmental Protection Agency should support and encourage recycling companies of CFLs both technically and financially in the first place.     

污泥热解气化技术的研究进展

通过热解气化等热化学转化方式将污泥转变为液体或气体燃料是极具前景的污泥利用方式之一。从污泥的资源化利用方面着手,阐述了污泥热解气化技术的研究进展,分析了现有污泥热解气化工艺的优缺点和主要影响因素,并对该技术的发展趋势进行了展望。指出:高湿污泥与生物质混合进行共热解可以提高原料的转化率和整个系统的热效率;高效污泥热解气化装置的研发是目前污泥热解气化技术领域亟待解决的问题。