Leaching characteristics and phytotoxic effects of sewage sludge biochar

Biochar was prepared via the pyrolysis of sewage sludge at temperatures ranging from 300 to 900 °C and the physical–chemical compositions of the biochars obtained were analyzed. Leaching tests were conducted using the biochars to investigate the release of the constituents and their phytotoxic effects on wheat (Triticum aestivum) seeds in a germination test. Multivariate analyses were used to evaluate the contributions of the constituents to the germination index (GI). The results showed that the biochars were rich in micronutrient contents and they improved the germination of wheat. The heavy metal contents were higher in the biochars than the sewage sludge and their levels increased with the pyrolysis temperature, but they were within the acceptable limits for land application, thereby suggesting that sewage sludge is suitable for use as a biochar substrate. The different components of the biochar leachates could promote and inhibit the germination of wheat seeds, where the GI was promoted at lower concentrations but inhibited at higher concentrations. Our results suggest that biochar is an effective and environmentally friendly fixative for the immobilization of heavy metals in sewage sludge when applied to land or disposed of in landfill, but its ecotoxicity needs to be assessed to ensure its environmental safety.     

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.     

薏米壳生物炭的制备及其对Cr（Ⅵ）的吸附性能

采用限氧控温热分解法在不同温度下制备了薏米壳生物炭。研究了薏米壳生物炭对低浓度Cr（Ⅵ）的吸附性能及吸附机理。随碳化温度升高,薏米壳管状通道微孔结构逐渐显现,薏米壳生物炭表面芳香化程度增强。薏米壳生物炭对Cr（Ⅵ）的吸附行为采用Langmuir等温吸附模型吻合度更高,吸附属于单分子层化学吸附,吸附过程是自发的、熵增吸热反应,吸附过程遵循准二级吸附动力学模型,膜扩散和颗粒内扩散共同控制吸附过程。     

污泥基生物炭的制备及其对Hg~(2+)的吸附

在添加乙酸钾的条件下将污泥低温热解制备出污泥基生物炭,并将其用于溶液中Hg~(2+)的吸附,考察了Hg~(2+)吸附效果的影响因素,并对吸附机理进行了分析。表征结果显示:热解对污泥有一定的造孔作用,而乙酸钾对孔隙结构的形成影响更大。实验结果表明:在吸附温度为25℃、溶液p H为6、初始Hg~(2+)质量浓度为15 mg/L、污泥基生物炭投加量为6 g/L的条件下,吸附24 h时的Hg~(2+)去除率达97.08%;污泥基生物炭对Hg~(2+)的吸附过程符合Langmuir等温吸附模型,吸附行为符合Lagergren准二级动力学方程。     

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.     

Pyrolysis of jute dust: effect of reaction parameters and analysis of products

Biowastes are becoming potential feedstocks for direct utilization or conversion to solid, liquid and gaseous fuels via various thermochemical routes. In this regard, jute dust which is a major agro-industrial waste in jute mills was pyrolysed in a fixed-bed reactor with an aim to study the product distribution and their characterization and to identify the optimum condition for bio-oil yield. The investigated process variables were temperature (400–700 °C), heating rate (10 and 40 °C/min) and nitrogen gas flow rate (50–250 ml/min). The yield of bio-oil is found to be maximum at 500 °C with a heating rate of 40 °C/min. However, further increase in temperature leads to decrease in bio-oil yield. Chemical compositions of the bio-oils were investigated using chromatographic and spectroscopic techniques such as ¹H NMR, FTIR and GC–MS. The heating value of the bio-oil is 26.71 MJ/kg. The study shows that jute dust have potential for conversion to bio-oil through the process of pyrolysis to supplement the petro-derived liquid fuel for heating and transportation applications after upgrading. The biochar produced as a co-product of jute dust pyrolysis can be a potential soil amendment with multiple benefits including increased soil fertility and C-sequestration.     

水稻秸秆生物炭-过硫酸盐去除水中p-硝基酚

以水稻秸秆为原料制备了多种生物炭,运用BET和FTIR等技术对其进行了表征,研究了生物炭-过硫酸盐体系对水中p-硝基酚的去除效果。与热解温度和时间相比,供氧量对生物炭活化过硫酸盐性能的影响更为显著,足氧条件下的活化性能显著降低;500℃缺氧条件下热解1 h制备的生物炭(RS500-1)对过硫酸盐具有良好的活化性能,可以实现p-硝基酚的高效去除,生物炭与过硫酸盐之间存在显著的协同作用。初始溶液pH和反应温度对p-硝基酚的去除效果影响很小;在RS500-1投加量1.0 g/L、过硫酸盐投加量5 mmol/L、反应温度25℃、不调节初始溶液pH的优化条件下,240 min时p-硝基酚的去除率可达70%以上。     

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.     

Preparation,sintering behavior,and expansion performance of ceramsite filter media from dewatered sewage sludge,coal fly ash,and river sediment

The main aim of this study is to assess the preparation, sintering behavior, and expansion performance of ceramsite filter media (CFM) from dewatered sewage sludge, coal fly ash, and river sediment without using any natural resources. The results showed that the investigated physical properties of lab made CFM met with the China’s industrial standard of CJ/T 299-2008 and the concentration of heavy metals in the lixivium was lower than the threshold of GB 5085.3-2007. During the sintering process, the relationships between ignition loss rate, expansion rate, and sintering temperature could be well described simultaneously by the 3-order polynomial fitting curve, with high correlation coefficient values (R ² > 0.999). The fitting curves of the ignition loss rate and expansion rate had one peak and one valley, respectively, and their cut-off point that is the sintering temperatures were the same (700 °C). The whole sintering process could be divided into two stages. The ignition loss rate was gradually increased in both the stages. At the same time, the expansion rate was decreased in the first stage and then increased in the second stage. The significance of this work is to pursue the concept of sustainable development.     

Vacuum pyrolysis of waste tires with basic additives

Granules of waste tires were pyrolyzed under vacuum (3.5-10kPa) conditions, and the effects of temperature and basic additives (Na(2)CO(3), NaOH) on the properties of pyrolysis were thoroughly investigated. It was obvious that with or without basic additives, pyrolysis oil yield increased gradually to a maximum and subsequently decreased with a temperature increase from 450 degrees C to 600 degrees C, irrespective of the addition of basic additives to the reactor. The addition of NaOH facilitated pyrolysis dramatically, as a maximal pyrolysis oil yield of about 48wt% was achieved at 550 degrees C without the addition of basic additives, while a maximal pyrolysis oil yield of about 50wt% was achieved at 480 degrees C by adding 3wt% (w/w, powder/waste tire granules) of NaOH powder. The composition analysis of pyrolytic naphtha (i.b.p. (initial boiling point) approximately 205 degrees C) distilled from pyrolysis oil showed that more dl-limonene was obtained with basic additives and the maximal content of dl-limonene in pyrolysis oil was 12.39wt%, which is a valuable and widely-used fine chemical. However, no improvement in pyrolysis was observed with Na(2)CO(3) addition. Pyrolysis gas was mainly composed of H(2), CO, CH(4), CO(2), C(2)H(4) and C(2)H(6). Pyrolytic char had a surface area comparable to commercial carbon black, but its proportion of ash (above 11.5wt%) was much higher.     

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.     

The important role of microwave receptors in bio-fuel production by microwave-induced pyrolysis of sewage sludge

Microwave receptor plays an important role in the microwave pyrolysis of sewage sludge in view of its significant influence on the yield and property of bio-fuel products. The yield and the chemical compositions of bio-fuels (gases and oils) obtained from sewage sludge mixed with different receptors (graphite, residue char, active carbon or silicon carbide) were investigated in this study by Gas Chromatography (GC), Gas Chromatography-Mass Spectrometry (GC-MS), and Fourier Transform Infrared Spectroscopy (FTIR). The results showed that the use of silicon carbide gave rise to the highest final temperature of 1130 °C, resulting in the highest yield of gas fraction (up to 63.2 wt.%). The low heating rate (200 °C/min) which was attributed to the addition of residue char promoted condensation reactions and resulted in an increase in solid yield. The existence of active carbon could prolong the resistance time of volatiles in the hot zone owing to its porous structure, generating the maximum concentration of H₂ + CO (60%) in the pyrolysis gas. When graphite was used, the final low temperature favoured the cyclization of the alkenes, giving rise to a higher concentration of mononuclear aromatics in the pyrolysis oils. The model established in this study revealed that the quantity and quality of the products obtained from the microwave pyrolysis highly depended on the process conditions, which were influenced by the receptor significantly.     

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.     

Thermocatalytic Degradation of High Density Polyethylene into Liquid Product

Thermocatalytic degradation of high density polyethylene (HDPE) was carried out using acid activated fire clay catalyst in a semi batch reactor. Thermal pyrolysis was performed in the temperature range of 420–500 °C. The liquid and gaseous yields were increased with increase in temperature. The liquid yield was obtained 30.1 wt% with thermal pyrolysis at temperature of 450 °C, which increased to 41.4 wt% with catalytic pyrolysis using acid activated fire clay catalyst at 10 wt% of catalyst loading. The composition of liquid products obtained by thermal and catalytic pyrolysis was analyzed by gas chromatography-mass spectrometry and compounds identified for catalytic pyrolysis were mainly paraffins and olefins with carbon number range of C₆–C₁₈. The boiling point was found in the range of commercial fuels (gasoline, diesel) and the calorific value was calculated to be 42 MJ/kg.     

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.     

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.     

热解温度对青霉素菌渣热解产物的影响

将青霉素菌渣在400~700 ℃进行热解,研究了产物中热解炭、热解油及气体的产率,以及热解油的组成变化。实验结果表明：600 ℃时热解油产率最高,随着温度升高,热解炭的产率降低,气体的产率升高;热解油中含量最高的是含氧化合物,在400 ℃时质量分数达到最高值69.69%,含氧化合物的含量随着热解温度的升高而降低,酸和醇类是热解油中含量最多的含氧化合物;含氮有机化合物的质量分数随着热解温度的升高而升高,在700 ℃时达到最高值30.64%,酰胺、吡啶、吲哚、含氮杂环是主要的含氮有机化合物。     

Characteristics of products and PCDD/DF emissions from a pyrolysis process of urethane/styrofoam waste from electrical home appliances

A plastic fraction consisting mainly of polyurethane/styrofoam waste is generated after separating valuable spare parts and metals from used electrical home appliances. In Korea, such waste is currently incinerated in cement kilns or is landfilled. However, owing to its high volatile matter content, conversion into gaseous or liquid pyrolysis products is a preferable alternative. A pyrolysis process of polyurethane and styrofoam waste from electrical home appliances was evaluated by characterizing the products generated at 500°–800°C. The para meters determined were the yields of gas, oil, and char; the characteristics of the remaining char; and the con centration of polychlorinated dibenzo-p-dioxins/polychlorinated dibenzo-furans in the product gas. As expected, the char yield decreased at higher temperatures, whereas gas and oil yields showed increasing tendency. The oil products could be used as storable fuels with a calorific value of 6000–8000 kcal/kg. Fine pores were observed in the char. The adsorption and decolorizing ability of the char were almost the same as those of activated carbon, so that pyrolysis char has potential for use as a sorbent. Further feasibility studies will be needed before utilizing pyrolysis technology to recover either fuels or usable products from polyurethane/styrofoam waste.     

Development of a high-efficiency rotary dryer for sewage sludge

A rotary drum dryer having an internal rotating body was designed and tested in this study. It was shown that the developed dryer is effective for drying sewage sludge. The best operating conditions in the dryer were low energy input and almost 10% moisture content. The conditions are 255°C for the rotary drum temperature, 17 min for the sludge residence time, and 55 kg/m³ h for the dryer load. Under these conditions, the drying efficiency was 84.8%. The average diameter of dried sludge was less than 8 mm, and the weight reduction rate was 80%. Parametric screening studies achieved the following results. The drying efficiency increased with the increase of the internal temperature and the sludge residence time in the rotary drum, while the drying efficiency decreased when increasing the dryer load. In addition, it was shown that NH₃ and CO₂ were the primary components released from the sewage sludge drying process. The amounts of both of these components increased when the rotary drum temperature was increased.     

Pilot study of intense dewatering of urban sewage sludge

Urban sewage sludge treatment has become a severe problem due to its large quantities and enrichment with heavy metals, refractory organic contaminants and pathogenic bacteria. Accordingly, it is essential to develop an effective and low-cost intense dewatering technique to decrease sludge water content so that it can be easily treated by subsequent incineration, landfilling or composting. In this study, a new intense sludge dewatering technique using conditioner of coagulant and flocculant (polyacrylamide) mixture and the diaphragm filter press was developed and investigated systematically by measuring the water content, calorific value and coliform bacteria in the sludge and investigating the dewatering efficiency under different conditions. The results showed that the water content of the sludge was effectively reduced from 80 % to the minimum of 43.6 % by adding conditioners and subsequent dewatering using the diaphragm press. Moreover, the low calorific value of dewatered sludge increased significantly from that of the original sludge, and was conducive to subsequent incineration. The water content of the dewatered sludge cake decreased to less than 25 % after being kept in the open air for 9 days. Therefore, it is proposed that this technique be applied to large-scale engineering applications.