Preparation of activated carbons from heavy-oil fly ashes

The use of heavy oil fly ash with high ash content (45 wt.%) as a precursor for the preparation of activated carbons has been investigated. The raw fly ash and the fly ash with lower ash content, obtained by a HCl/HF washing treatment, have been pyrolyzed at 900 degrees C and then activated with CO(2) in the temperature range of 800-900 degrees C for different times. The activated carbons have been characterised as regards the surface area and the pore volume. The evolution of the porosity has been related to the burn-off degree.     

Chemical sequential extraction of heavy metals and sulphur in bottom ash and in fly ash from a pulp and paper mill complex

A five-stage sequential extraction procedure was used to determine the distribution of 11 metals (Cd, Cr, Cu, Mo, Pb, Zn, As, Co, V, Ni, Ba), and sulphur (S) in bottom ash and in fly ash from a fluidized bed co-combustion (i.e. wood and peat) boiler of Stora Enso Oyj Oulu Mill at Oulu, Northern Finland, into the following fractions: (1) water-soluble fraction (H2O); (2) exchangeable fraction (CH3COOH); (3) easily reduced fraction (NH2OH-HCl); (4) oxidizable fraction (H2O2 + CH3COONH4); and (5) residual fraction (HF + HNO3 + HCl). Although metals were extractable in all fractions, the highest concentrations of most of the metals occurred in the residual fraction. From the environmental point of view, this fraction is the non-mobile fraction and is potentially the least harmful. The Ca concentrations of 29.3 g kg(-1) (dry weight) in bottom ash and of 68.5 g kg(-1) (dry weight) in fly ash were correspondingly approximately 18 and 43 times higher than the average value of 1.6 g kg(-1) (dry weight) in arable land in Central Finland. The ashes were strongly alkaline pH (approximately 12) and had a liming effects of 9.3% (bottom ash) and 13% (fly ash) expressed as Ca equivalents (dry weight). The elevated Ca concentrations indicate that the ashes are potential agents for soil remediation and for improving soil fertility. The pH and liming effect values indicate that the ashes also have a pH buffering capacity. From the environmental point of view, it is notable that the heavy metal concentrations in both types of ash were lower than the Finnish criteria for ash utilization.     

粉煤灰的改性及其对高盐苯胺废水的处理

以盐酸和硫酸作为改性剂,对粉煤灰进行改性。通过正交实验得到最佳改性粉煤灰制备条件为：V（盐酸）∶V（硫酸）=1∶5,浸泡时间6h,活化时间6h,活化温度250℃。在初始苯胺质量浓度为200mg/L、氯化钠质量分数为15%、吸附时间为60min的条件下,采用在最佳条件下制备得到的改性粉煤灰对苯胺进行吸附,吸附量可达4.16mg/g。采用Freundlich方程可更好地对改性粉煤灰吸附苯胺的过程进行拟合。     

Concentrations of heavy metals in fly ash from a coal-fired power plant with respect to the new Finnish limit values

In Finland, the new limit values for heavy metals in fertilizers used in agriculture and in forestry came into force in March 2007, and for materials used as earth construction agents, in June 2006. From the utilization point of view, it was notable that the total heavy metal concentrations (Cd, Cu, Pb, Cr, Mo, Zn, As, Ni, Ba, and Hg) in fly ash from a coal-fired power plant were lower than those limit values. The concentrations of the easily soluble elements Ca, Mg, Na, P, and Zn in the fly ash were between 3.5 and 35 times higher than those found in the coarse mineral soils of Finland. Fly ash is a potential agent for soil remediation and for improving soil fertility. If inorganic materials and by-products are utilized in earthworks, the content of harmful compounds must be low and the harmful components must be tightly bound to the matrix. Therefore, a five-stage sequential extraction procedure was used to evaluate the extractability of different elements in fly ash into the following fractions: (1) the water-soluble fraction, (2) the exchangeable fraction (CH₃COOH), (3) the easily reduced fraction (NH₂OH-HCl), (4) the oxidizable fraction (H₂O₂ + CH₃COONH₄), and (5) the residual fraction (HF + HNO₃ + HCl).     

钛硅分子筛催化双氧水氧化水中间甲酚

探索催化双氧水氧化去除间甲酚对开发炼油厂碱渣废水处理新技术意义重大。采用钛硅分子筛催化双氧水氧化水中间甲酚,考察了反应时间、反应温度、双氧水加入量、催化剂加入量和初始溶液pH对间甲酚去除率的影响。实验结果表明：钛硅分子筛对双氧水氧化间甲酚具有显著的催化作用;在反应时间为90 min、反应温度为80 ℃、n（H₂O₂）∶n（间甲酚）为4、催化剂加入量为1.5 g/L、初始溶液pH为1.0~11.0的条件下,间甲酚去除率约为94%,间甲酚溶液的BOD₅/COD从氧化前的0.26提高到氧化后的0.38,可生化性显著提高。     

Removal of carbon constituents from hospital solid waste incinerator fly ash by column flotation

Hospital solid waste incinerator (HSWI) fly ash contains a large number of carbon constituents including powder activated carbon and unburned carbon, which are the major source of polychlorinated dibenzo-p-dioxins and dibenzofurans (PCDD/Fs) in fly ash. Therefore, the removal of carbon constituents could reduce PCDD/Fs in fly ash greatly. In this study, the effects of the main flotation parameters on the removal of carbon constituents were investigated, and the characteristics of the final product were evaluated. The results showed that loss on ignition (LOI) of fly ash increased from 11.1% to 31.6% during conditioning process. By optimizing the flotation parameters at slurry concentration 0.05 kg/l, kerosene dosage 12 kg/t, frother dosage 3 kg/t and air flow rate 0.06 m³/h, 92.7% of the carbon constituents were removed from the raw fly ash. Under these conditions, the froth product has LOI of 56.35% and calorific values of 12.5 MJ/kg, LOI in the tailings was below 5%, and the total toxic equivalent (TEQ) of PCDD/Fs decreased from 5.61 ng-TEQ/g in the raw fly ash to 1.47 ng-TEQ/g in the tailings. The results show that column flotation is a potential technology for simultaneous separation of carbon constituents and PCDD/Fs from HSWI fly ash.     

Lead immobilization in mechanochemical fly ash recycling

In previous studies, we focused on a mechanochemical process for recycling fly ash for use in cement; this process was expected to immobilize heavy metals in the fly ash, a desirable outcome in light of the fact that recycled fly ash is commonly used in the synthesis of inorganic materials. Here, we investigated the leaching of lead (Pb) from fly ash treated by a mechanochemical process and from cement prepared from the treated fly ash. We used lead oxide (PbO), a typical Pb compound in fly ash, as a model substance. Mechanochemical treatment of the fly ash inhibited Pb leaching by 93%, and further inhibition (more than 99.9%) was observed in cement produced from the treated fly ash. During the mechanochemical treatment, PbO was reduced to Pb by iron from the stainless-steel mill used for processing, and the lower solubility of Pb in water resulted in immobilization of the Pb.     

加压酸浸法提取粉煤灰中的Al2O3和Fe2O3

采用加压酸浸法提取粉煤灰中的A12O3和Fe2O3.实验研究了粉煤灰粒径、硫酸质量分数、反应时间、反应温度对粉煤灰中Al2O3和Fe2O3浸取率的影响,并通过SEM对粉煤灰酸浸前后的形貌进行了分析.实验结果表明,当粉煤灰粒径为75μm、硫酸质量分数为50％、反应温度为180℃、反应时间为4h时,粉煤灰中的Al2O3浸取率可达82.4％,Fe2O3浸取率为76.1％,经酸浸后粉煤灰的剩余率为72.4％.     

免烧结粉煤灰陶粒BAF对乙烯化工废水的深度处理效果

以粉煤灰为主要原料制备了免烧结粉煤灰陶粒,并将其作为曝气生物滤池(BAF)的填料用于深度处理乙烯化工厂二级生化出水。实验结果表明,在平均进水COD为54.62mg/L、平均SS为33.93mg/L、平均ρ(NH3-N)为1.33mg/L的条件下,自制免烧结粉煤灰陶粒BAF平均COD去除率为57.14%,平均SS去除率为68.64%,平均NH3-N去除率为74.89%,均略高于普通商业陶粒BAF。自制免烧结粉煤灰陶粒BAF最佳反冲洗周期为2d,并具有反冲洗耗水量小、反冲洗效果好的优势。     

粉煤灰及其制备沸石对高浓度氨氮的去除比较

以粉煤灰为原料,采用改进的水热合成法制备了粉煤灰沸石,并将粉煤灰和粉煤灰沸石用于高浓度氨氮的吸附去除。实验结果表明:在粉煤灰和粉煤灰沸石的投加量分别为0.10 g/m L和0.04 g/m L、反应体系p H为5~7、初始氨氮质量浓度为500 mg/L的条件下,分别吸附660 min和60 min,粉煤灰和粉煤灰沸石对氨氮的去除率分别约为20.1%和50.7%左右,粉煤灰沸石对高浓度氨氮的去除效果明显优于粉煤灰;粉煤灰和粉煤灰沸石对氨氮的吸附动力学行为符合准二级动力学方程;Langmuir和Freundlich等温吸附模型能较好地描述粉煤灰对氨氮的等温吸附过程,而粉煤灰沸石对氨氮的等温吸附过程则更适宜用线性模型和Freundlich模型描述。     

Effects of fly ash addition on physical properties of porous clay-fly ash composites via polymeric replica technique

The porous composites of clay and fly ash have the potential to be used in many fields, such as catalyst support and gas adsorbents. In this study, various ratios of fly ash (1–2) with different percentage of suspension (50–70 wt%) were applied to produce porous clay-fly ash composites via polymeric replica technique. Fabrication process starts by mixing clay and fly ash in distilled water to form slurry. The process is followed by fully immersing polymer sponge in slurry. The excess slurry is then removed through squeezing. Finally, the sponge coated with slurry is sintered at 500 and 1250 °C for 1 h. It is found that the compressive strength of porous composites improves significantly (0.178–1.28 MPa) when the amount of clay-fly ash suspension mixture (50–70 wt%) increases. The compressive strength of porous composites is mainly attributed to the mullite, quartz and amorphous phase formations. These results are supported by X-ray diffraction analysis. On the other hand, increase in the amount of suspension reduces the apparent density (from 2.44 to 2.32 g/cm³) and porosity (from 97 to 85 %). The reduction in apparent density is believed to be caused by the presence of high fly ash content in porous composites. The melted fly ash cenospheres have closed the internal pores and increased density of samples. Higher suspension level not only reduces porosity, but also increases close pores of the porous composites. The results are justified through the observation from the structures of porous clay-fly ash composites.     

Improvements of nano-SiO2 on sludge/fly ash mortar

Sewage sludge ash has been widely applied to cementitious materials. In this study, in order to determine effects of nano-SiO(2) additives on properties of sludge/fly ash mortar, different amounts of nano-SiO(2) were added to sludge/fly ash mortar specimens to investigate their physical properties and micro-structures. A water-binding ratio of 0.7 was assigned to the mix. Substitution amounts of 0%, 10%, 20%, and 30% of sludge/fly ash (1:1 ratio) were proposed. Moreover, 0%, 1%, 2%, and 3% of nano-SiO(2) was added to the mix. Tests, including SEM and compressive strength, were carried out on mortar specimens cured at 3, 7, and 28 days. Results showed that sludge/fly ash can make the crystals of cement hydration product finer. Moreover, crystals increased after nano-SiO(2) was added. Hence, nano-SiO(2) can improve the effects of sludge/fly ash on the hydration of mortar. Further, due to the low pozzolanic reaction active index of sludge ash, early compressive strengths of sludge/fly ash mortar were decreased. Yet, nano-SiO(2) could help produce hydration crystals, which implies that the addition of nano-SiO(2) to mortar can improve the influence of sludge/fly ash on the development of the early strength of the mortar.     

Application of large volume injection GC-MS to analysis of organic compounds in the extracts and leachates of municipal solid waste incineration fly ash

Organic solvent and water extracts of fly ash from a Milan (Italy) municipal solid waste incinerator (MSWI) were analyzed by large volume injection-gas chromatography-mass spectrometry (LVI-GC-MS) with programmable temperature vaporizer (PTV). Using injection volumes of 10-100 microl, typically over a hundred compounds were detected in organic solvent extracts and ca. 35% of them could be tentatively identified from their electron impact ionization mass spectra. A protocol for the determination of the maximum amount of a potential environmental pollutant available for leaching (availability test) was developed for four selected target compounds: pentachlorobenzene (PeCB), hexachlorobenzene (HxCB), o-terphenyl (o-TPH) and m-terphenyl (m-TPH). Key parameters, extraction time and liquid-to-solid ratio (L/S), were studied in more detail. Recoveries of PeCB, HxCB and o-TPH spiked into the fly ash samples at two concentration levels ranged from 38% to 53% for freshly spiked and from 14% to 40% for 40-day aged fly ash. Recoveries of m-TPH were 8% to 11% from freshly spiked and less than 3% from aged spiked fly ash. The native amounts in Milan MSWI fly ash, determined in an interlaboratory exercise using the developed protocol, were 31 ng/g PeCB, 34 ng/g HxCB, 72 ng/g o-TPH and 4.4 ng/g m-TPH. A separate methodology was developed for the determination of compounds extracted from fly ash by water (leaching test). Following 8-h sonication at L/S 20, the leached amounts of PeCB, HxCB and o-TPH were 1.1, 3.1 and 6.0 ng/g fly ash, respectively.     

Removal of unburned carbon from municipal solid waste fly ash by column flotation

Unburned carbon (UC) is the major source of organic contaminants in municipal solid waste (MSW) fly ash. So most organic contaminants can be removed by the removal of the UC from the MSW fly ash. In this paper, we first used a technique of column flotation to remove UC from MSW fly ash. The influences of column flotation parameters on the recovery efficiency of UC were systematically studied. It was found that the UC recovery efficiency was greatly influenced by the gas flow rate, pH value, collector kerosene's concentration and the types of fly ash. By optimizing the above parameters, we have successfully removed 61.2% of the UC from MSW fly ash having 5.24% UC content. The removal mechanism was well accounted for the kinetic theory of column flotation and surface-chemistry theory. The results indicate that the column flotation technique is effective in removing the UC from MSW fly ash, and show that there is a strong possibility for practical application of this technique in removing the organic contaminants from MSW fly ash.     

High fire resistance in blocks containing coal combustion fly ashes and bottom ash

Fire resistance recycled blocks, containing fly ash and bottom ash from coal combustion power plants with a high fire resistance, are studied in this paper by testing different compositions using Portland cement type II, sand, coarse aggregate and fly ash (up to 50% of total weight) and bottom ash (up to 30% of total weight). The fire resistance, physical-chemical (density, pH, humidity, and water absorption capacity), mechanical (compressive and flexural strength), and leaching properties are measured on blocks made with different proportions of fly ash and bottom ash. The standard fire resistance test is reproduced on 28 cm-high, 18 cm-wide and 3 cm-thick units, and is measured as the time needed to reach a temperature of 180 °C on the non-exposed surface of the blocks for the different compositions.The results show that the replacement of fine aggregate with fly ash and of coarse aggregate with bottom ash have a remarkable influence on fire resistance and cause no detriment to the mechanical properties of the product. Additionally, according to the leaching tests, no environmental problems have been detected in the product. These results lead to an analysis of the recycling possibilities of these by-products in useful construction applications for the passive protection against fire.     

粉煤灰的改性、成型及深度除磷应用

选择合适的改性剂对粉煤灰进行改性,通过有机高分子交联方法对改性粉煤灰进行成型处理,并采用静态吸附法评价改性粉煤灰的深度除磷效果。采用1 g氢氧化铝改性粉煤灰处理100 mL磷质量浓度为10.0 mg/L的模拟废水,磷去除率可达99.70％,处理后模拟废水中磷质量浓度低于0.50 mg/L, 达到GB8978-1996《污水综合排放标准》。成型处理可提高粉煤灰的沉降速率,改善灰水分离效果。经超声再生后的成型氢氧化铝改性粉煤灰的磷去除率仍可达67.9％。     

双掺粉煤灰再生骨料对混凝土强度影响研究

通过试验研究再生骨料混凝土中粉煤灰和再生骨料对混凝土强度的影响。采用粉煤灰替代部分水泥、再生骨料替代部分天然粗骨料的方法,通过正交试验测定混凝土立方体抗压强度的方法,来研究粉煤灰对再生骨料混凝土强度的影响。试验得出:当再生骨料掺量为20%~30%时,粉煤灰的最佳掺量为20%左右;当再生骨料掺量高于40%、粉煤灰掺量高于20%时,其混凝土拌合物搅拌时间不小于240 s,且当粉煤灰在20%~30%时,可获得较理想的混凝土抗压强度;当粉煤灰的掺入量分布在20%~30%、再生骨料的最佳掺量为50%时,可获得较理想的混凝土抗压强度。由此得出,合理的再生骨料、粉煤灰掺量对混凝土的抗压强度影响并不明显且有提高的趋势,对降低混凝土成本,提高建筑垃圾的再生利用,有一定的经济效益和社会效益。     

Effects of the type of sintering atmosphere on the chromium leachability of thermal-treated municipal solid waste incinerator fly ash

The sintering process offers an opportunity to combine detoxification and resource recovery for the treatment of municipal solid waste (MSW) incinerator fly ash. However, the chromium (Cr) in the sintered fly ash becomes more readily leachable with increasing sintering time and temperature, thus posing severe threats to the environment and human health when the sintered ash is recycled or reused. This study investigated the enhanced leachability of fly ash containing Cr, by heating the chromium (III) oxide (Cr2O3)-spiked fly ash to 800 degrees C in atmospheres containing air, nitrogen gas (N2), and 5% H2 + 95% N2, respectively. The results indicated that trivalent chromium was converted to its soluble hexavalent form during sintering in the air atmosphere; whereas sintering in a nitrogen atmosphere significantly reduced the leachability of Cr due to lack of oxygen (O2) to oxidize. The effects of the sintering temperature on the total chromium content and the leaching concentration in the toxicity characteristic leaching procedure (TCLP) extract are also discussed.     

Comparison of two types of municipal solid waste incinerator fly ashes with different alkaline reagents in washing experiments

In this study, we propose a "washing-calcination-conversion of washed fly ash into cement material with bottom ash" (WCCB) system to reduce the amount of fly ash that must be specially treated so it can be used as raw cement material. Calcium hydroxide (Ca(OH)2) is widely used in air-pollution control devices of incinerators while sodium bicarbonate (NaHCO3) is not. We conducted single-, double-, and triple-washing experiments to compare the washing characteristics of two types of fly ash. Unlike NaHCO3 fly ash, Ca(OH)2 fly ash has almost twice as much washed residue and almost 2.5 times more chlorine after the same washing procedure. After washing once, the washing frequency is also important for NaHCO3 fly ash, while the mixing time and liquid/solid ratio are more critical for Ca(OH)2 fly ash. The use of NaHCO3 is more suitable for the WCCB system.     

Dioxin emissions: Possible techniques for maintaining the limit of 0.1 ng TE m−3 (as of 1990/91)

Processes which will achieve up to 100-fold reduction of exhaust gas emissions of dioxin as proposed for the new German Standards are reviewed. A combination of processes which remove fly ash, NO_x, SO_x, HCl and other pollutants will also remove dioxins. Reduction of chlorinated compounds fed to the incinerator is not likely to make any significant difference. Good turbulence with elimination of cold spots in the firebox will ensure initial thermal destruction. Dioxins are synthesized on fly ash particles at temperatures between 200 and 400° C. Rapid temperature reduction across this range by water injection will greatly reduce dioxin levels. Catalytic inhibitors can also be used. Since dioxin is adsorbed on fly ash, efficient scrubbing is essential for high removal efficiency. Sorption on active carbon beds is also being evaluated.