Sorbents for CO2 capture from high carbon fly ashes

Fly ashes with high-unburned-carbon content, referred to as fly ash carbons, are an increasing problem for the utility industry, since they cannot be marketed as a cement extender and, therefore, have to be disposed. Previous work has explored the potential development of amine-enriched fly ash carbons for CO(2) capture. However, their performance was lower than that of commercially available sorbents, probably because the samples investigated were not activated prior to impregnation and, therefore, had a very low surface area. Accordingly, the work described here focuses on the development of activated fly ash derived sorbents for CO(2) capture. The samples were steam activated at 850 degrees C, resulting in a significant increase of the surface area (1075m(2)/g). The activated samples were impregnated with different amine compounds, and the resultant samples were tested for CO(2) capture at different temperatures. The CO(2) adsorption of the parent and activated samples is typical of a physical adsorption process. The impregnation process results in a decrease of the surface areas, indicating a blocking of the porosity. The highest adsorption capacity at 30 and 70 degrees C for the amine impregnated activated carbons was probably due to a combination of physical adsorption inherent from the parent sample and chemical adsorption of the loaded amine groups. The CO(2) adsorption capacities for the activated amine impregnated samples are higher than those previously published for fly ash carbons without activation (68.6 vs. 45mg CO(2)/g sorbent).     

Coal fly ash based carbons for SO2 removal from flue gases

Two different coal fly ashes coming from the burning of two coals of different rank have been used as a precursor for the preparation of steam activated carbons. The performance of these activated carbons in the SO₂ removal was evaluated at flue gas conditions (100 °C, 1000 ppmv SO₂, 5% O₂, 6% H₂O). Different techniques were used to determine the physical and chemical characteristics of the samples in order to explain the differences found in their behaviour. A superior SO₂ removal capacity was shown by the activated carbon obtained using the fly ash coming from a subbituminous–lignite blend. Experimental results indicated that the presence of higher amount of certain metallic oxides (Ca, Fe) in the carbon-rich fraction of this fly ash probably has promoted a deeper gasification in the activation with steam. A more suitable surface chemistry and textural properties have been obtained in this case which explains the higher efficiency shown by this sample in the SO₂ removal.     

Investigation of MSWI fly ash melting characteristic by DSC-DTA

The melting process of MSWI (Municipal Solid Waste Incineration) fly ash has been studied by high-temperature DSC-DTA experiments. The experiments were performed at a temperature range of 20-1450 degrees C, and the considerable variables included atmosphere (O(2) and N(2)), heating rates (5 degrees C/min, 10 degrees C/min, 20 degrees C/min) and CaO addition. Three main transitions were observed during the melting process of fly ash: dehydration, polymorphic transition and fusion, occurring in the temperature range of 100-200 degrees C, 480-670 degrees C and 1101-1244 degrees C, respectively. The apparent heat capacity and heat requirement for melting of MSWI fly ash were obtained by DSC (Differential Scanning Calorimeter). A thermodynamic modeling to predict the heat requirements for melting process has been presented, and it agrees well with the experimental data. Finally, a zero-order kinetic model of fly ash melting transition was established. The apparent activation energy of MSWI fly ash melting transition was obtained.     

Diopside-based glass-ceramics from MSW fly ash and bottom ash

By utilising MSW fly ash from the Shanghai Yuqiao municipal solid waste (MSW) incineration plant as the main raw material, diopside-based glass-ceramics were successfully synthesized in the laboratory by combining SiO(2), MgO and Al(2)O(3) or bottom ash as conditioner of the chemical compositions and TiO(2) as the nucleation agent. The optimum procedure for the glass-ceramics is as follows: melting at 1500 degrees C for 30 min, nucleating at 730 degrees C for 90 min, and crystallization at 880 degrees C for 10h. It has been shown that the diopside-based glass-ceramics made from MSW fly ash have a strong fixing capacity for heavy metals such as lead (Pb), chromium (Cr), cadmium (Cd) etc.     

Treatment of olive mill waste water with activated carbons from agricultural by-products

A series of activated carbons prepared by a two-step steam activation of olive stone and solvent extracted olive pulp (SEOP) have been used in an attempt to investigate the total phenol removal and chemical oxygen demand (COD) decrease in olive mill waste water (OMWW). The temperature of carbonization and activation were kept constant at 850 and 800 degrees C, respectively. One of the carbons was prepared by a single-step process at 800 degrees C. Activated carbons have been characterized by adsorption of N2 at 77 K and mercury porosimetry. Their iodine values were also determined. Surface oxides of activated carbons were determined using the Boehm's method. The porosity development and the surface chemistry of carbons were correlated to increasing removal ability of organic molecules. Kinetics of adsorption was evaluated by applying the Lagegren model while adsorption isotherm data were fitted to Langmuir model. Mesoporosity seems to be the key factor for total phenol removal while micoporosity controls the adsorption of total organics as expressed by the COD decrease in OMWW. For carbons with similar structure, the adsorption of phenols or total organics might be affected by the presence of carbonyls.     

Physical and chemical properties study of the activated carbon made from sewage sludge

Preparation of activated carbon from sewage sludge is a promising way to produce a useful adsorbent for pollutants removal as well as to dispose of sewage sludge. The objective of this study was to investigate the physical and chemical properties of the activated carbon made from sewage sludge so as to give a basic understanding of its structure. The activated carbon was prepared by activating anaerobically digested sewage sludge with 5 M ZnCl2 and thereafter pyrolyzing it at 500 degrees C for 2 h under nitrogen atmosphere. The properties investigated in the present study included its surface area and pore size distribution, its elemental composition and ash content, its surface chemistry structure and its surface physical morphology. Furthermore, its adsorption capacities for aqueous phenol and carbontetrachloride were examined. The results indicated that the activated carbon made from sewage sludge had remarkable micropore and mesopore surface areas and notable adsorption capacities for phenol and carbon-tetrachloride. In comparison with commercial activated carbons, it displayed distinctive physical and chemical properties.     

Experimental and numerical analysis of metal leaching from fly ash-amended highway bases

A study was conducted to evaluate the leaching potential of unpaved road materials (URM) mixed with lime activated high carbon fly ashes and to evaluate groundwater impacts of barium, boron, copper, and zinc leaching. This objective was met by a combination of batch water leach tests, column leach tests, and computer modeling. The laboratory tests were conducted on soil alone, fly ash alone, and URM-fly ash-lime kiln dust mixtures. The results indicated that an increase in fly ash and lime content has significant effects on leaching behavior of heavy metals from URM-fly ash mixture. An increase in fly ash content and a decrease in lime content promoted leaching of Ba, B and Cu whereas Zn leaching was primarily affected by the fly ash content. Numerically predicted field metal concentrations were significantly lower than the peak metal concentrations obtained in laboratory column leach tests, and field concentrations decreased with time and distance due to dispersion in soil vadose zone.     

Coal fly ash utilization: low temperature sintering of wall tiles

We present here a study of the sintering of fly ash and its mixture with low alkali pyrophyllite in the presence of sodium hexa meta phosphate (SHMP), a complex activator of sintering, for the purpose of wall tile manufacturing. The sintering of fly ash with SHMP in the temperature range 925-1050 degrees C produces tiles with low impact strength; however, the incremental addition of low alkali pyrophyllite improves impact strength. The impact strength of composites with 40% (w/w) pyrophyllite in the fly ash-pyrophyllite mix satisfies the acceptable limit (19.6J/m) set by the Indian Standards Institute for wall tiles. Increasing the pyrophyllite content results in an increase in the apparent density of tiles, while shrinkage and water absorption decrease. The strength of fly ash tiles is attributed to the formation of a silicophosphate phase; in pyrophyllite rich tiles, it is attributed to the formation of a tridymite-structured T-AlPO(4) phase. Scanning electron micrographs show that the reinforcing rod shaped T-AlPO(4) crystals become more prominent as the pyrophyllite content increases in the sintered tiles.     

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.     

Role of aluminous component of fly ash on the durability of Portland cement-fly ash pastes in marine environment

The durability, of mixtures of two kinds of Spanish fly ashes from coal combustion (ASTM class F) with 0, 15 and 35% replacement of Portland cement by fly ash, in a simulated marine environment (Na(2)SO(4)+NaCl solution of equivalent concentration to that of sea water: 0.03 and 0.45 M for sulphate and chloride, respectively), has been studied for a period of 90 days. The resistance of the different mixtures to the attack was evaluated by means of the Koch-Steinegger test. The results showed that all the mixtures were resistant, in spite of the great amount of Al(2)O(3) content of the fly ash. The diffusion of SO(4)(2-), Na+ and Cl- ions through the pore solution activated the pozzolanic reactivity of the fly ashes causing the corresponding microstructure changes, which were characterized by X-ray diffraction (XRD), mercury intrusion porosimetry (MIP) and scanning electron microscopy (SEM). As a result, the flexural strength of the mixtures increased, principally for the fly ash of a lower particle size and 35% of addition.     

Possibility of using waste tire rubber and fly ash with Portland cement as construction materials

The growing amount of waste rubber produced from used tires has resulted in an environmental problem. Recycling waste tires has been widely studied for the last 20 years in applications such as asphalt pavement, waterproofing systems and membrane liners. The aim of this study is to evaluate the feasibility of utilizing fly ash and rubber waste with Portland cement as a composite material for masonry applications. Class C fly ash and waste automobile tires in three different sizes were used with Portland cement. Compressive and flexural strength, dry unit weight and water absorption tests were performed on the composite specimens containing waste tire rubber. The compressive strength decreased by increasing the rubber content while increased by increasing the fly ash content for all curing periods. This trend is slightly influenced by particle size. For flexural strength, the specimens with waste tire rubber showed higher values than the control mix probably due to the effect of rubber fibers. The dry unit weight of all specimens decreased with increasing rubber content, which can be explained by the low specific gravity of rubber particles. Water absorption decreased slightly with the increase in rubber particles size. These composite materials containing 10% Portland cement, 70% and 60% fly ash and 20% and 30% tire rubber particles have sufficient strength for masonry applications.     

Coal fly ash as raw material for the manufacture of geopolymer-based products

In this work coal fly ash has been employed for the synthesis of geopolymers. Two different systems with silica/alumina ratios stoichiometric for the formation of polysialatesiloxo (PSS, SiO2/Al2O3=4) and polysialatedisiloxo (PSDS, SiO2/Al2O3=6) have been prepared. The alkali metal hydroxide (NaOH or KOH) necessary to start polycondensation has been added in the right amount as concentrated aqueous solution to each of the two systems. The concentration of each alkali metal solution has been adjusted in order to have the right liquid volume to ensure constant workability. The systems have been cured at four different temperatures (25, 40, 60, and 85 degrees C) for several different times depending on the temperature (16-672 h at 25 degrees C; 72-336 h at 40 degrees C; 16-120 h at 60 degrees C and 1-6h at 85 degrees C). The products obtained in the different experimental conditions have been submitted to the quantitative determination of the extent of polycondensation through mass increase and loss on ignition, as well as to qualitative characterization by means of FT-IR spectroscopy. Furthermore, physico-structural and mechanical characterization has been carried out through microscopic observations and the determination of unconfined compressive strength, elasticity modulus, apparent density, porosity and specific surface area. The results have indicated that the systems under investigation are suited for the manufacture of pre-formed building blocks at room temperature.     

Catalytic detoxification of polychlorinated dibenzo-p-dioxins and polychlorinated dibenzofurans in fly ash

An efficient catalytic detoxification method for polychlorinated dibenzo-p-dioxins and polychlorinated dibenzofurans (PCDD/Fs) in fly ash produced by municipal waste incinerator has been studied using palladium on carbon (Pd/C) catalyst. As one of the trace components in fly ash, the detoxification of PCDD/Fs is very difficult because of the interferences of other persistent components with higher concentrations. However, the detoxification reaction of PCDD/Fs shows higher activity in water/isopropanol solution using commercial Pd/C catalyst at 40 degrees C under normal pressure. The results indicated that the catalytic degradation of PCDFs has been found to be easier than that of PCDDs. Moreover, the dechlorination ratios were higher for octa- and hepta-chlorinated congeners than those for tetra- and penta-chlorinated ones. The detoxification process worked well in water. The dechlorination efficiencies of almost all of the PCDD/Fs congeners can reach over 99% within a shorter reaction time.     

The potential of SO2 for reducing corrosion in WtE plants

Due to the high-temperature boiler corrosion induced by chloride-rich fly ash deposits, steam generation in today’s Waste-to-Energy (WtE) plants is typically designed only for 40 bar/400 °C as an economic compromise between acceptable corrosion rate and maximum power generation. The high-corrosive metal chlorides in the fly ash can react with SO₂ forming low-corrosive sulfates. The sulfation efficiency is enhanced by high SO₂ levels and sufficient residence time of the flue gas at high-temperatures (700–900 °C). The fly ash sulfation was tested in full scale in a Swedish WtE plant by applying the economic sulfur recirculation method. Probes of several alloys (16Mo3, Inconel 625, Sanicro 28) were exposed for 1000 h at controlled material temperatures in the superheater position, at normal and during sulfating operation respectively. Analyses of the fly ash showed that the molar Cl/S was decreased to values well below 1 and the corresponding corrosion rates of the individual material samples were less than half when sulfur recirculation was in operation. These positive findings demonstrate that the sulfur recirculation process has high potential for low-corrosive high-temperature steam generation (T ≈ 500 °C) and improved electricity production. Further steam superheating can be realized by staged superheating using small amounts of secondary fuel.     

Heavy metal speciation in various types of fly ash from municipal solid waste incinerator

Fly ash (FA) from municipal solid waste incinerators has been known as hazardous waste, which is mostly because of the high content of heavy metal and dioxins. Besides the content, the form of the heavy metals in fly ash is also very important, because it is tightly related with the leaching behavior of fly ash in diverse circumstances. To evaluate the environment potential risk of fly ash, the Tessier chemical extraction method was adopted. In this study, four kinds of fly ash were examined, one sample from China (CFA) and the other three from Japan (RFA, CaFA and NaFA). Five metal elements were detected and they were Ni, Cr, Cd, Pb, and Cu. The result of total heavy metals’ concentration showed CFA has the lowest content. As to the Tessier chemical extraction experiments, the results show that Cd, Pb, and Cu have higher leaching risk in the environment than other heavy metals. The result of leaching test experiment showed that the more exchangeable speciation of Cd, Cr and Pb in FA, the more it could leach out in natural environment.     

Physical-mechanical and environmental properties of sintered municipal incinerator fly ash

A step-wise treatment of Municipal Solid Waste (MSW) incinerator fly ash including washing, milling and sintering was investigated in order to manufacture ceramic materials with improved physical, mechanical and environmental properties and, possibly, to reduce the power input of the sintering process. An interpretation of the test results based on the microstructure of sintered products and sintering kinetic modeling was also attempted to identify the densification mechanisms. It was found that milling of washed fly ash represents a basic step for manufacturing high-density ceramic materials with very high compressive strengths (up to 500 N/mm2). A significant reduction in the power input of the sintering process (reduction of firing temperature from 1210 degrees C for washed fly ash to 1140 degrees C for milled-washed fly ash) is also achieved. A dense, well-sintered microstructure is formed through an intermediate-stage, liquid-phase sintering mechanism controlled by liquid-phase diffusion and grain shape accommodation. Such a microstructure is able to strongly immobilise heavy metals, thus giving good environmental properties to sintered product.     

Gypsum treated fly ash as a liner for waste disposal facilities

Fly ash has potential application in the construction of base liners for waste containment facilities. While most of the fly ashes improve in the strength with curing, the ranges of permeabilities they attain may often not meet the basic requirement of a liner material. An attempt has been made in the present context to reduce the hydraulic conductivity by adding lime content up to 10% to two selected samples of class F fly ashes. The use of gypsum, which is known to accelerate the unconfined compressive strength by increasing the lime reactivity, has been investigated in further improving the hydraulic conductivity. Hydraulic conductivities of the compacted specimens have been determined in the laboratory using the falling head method. It has been observed that the addition of gypsum reduces the hydraulic conductivity of the lime treated fly ashes. The reduction in the hydraulic conductivity of the samples containing gypsum is significantly more for samples with high amounts of lime contents (as high as 1000 times) than those fly ashes with lower amounts of lime. However there is a relatively more increase in the strengths of the samples with the inclusion of gypsum to the fly ashes at lower lime contents. This is due to the fact that excess lime added to fly ash is not effectively converted into pozzolanic compounds. Even the presence of gypsum is observed not to activate these reactions with excess lime. On the other hand the higher amount of lime in the presence of sulphate is observed to produce more cementitious compounds which block the pores in the fly ash. The consequent reduction in the hydraulic conductivity of fly ash would be beneficial in reducing the leachability of trace elements present in the fly ash when used as a base liner.     

Textural and surface chemical characteristics of activated carbons prepared from cattle manure compost

Two activated carbons (ACs) prepared from cattle manure compost (CMC) by ZnCl(2) activation were selected and out-gassed in a helium flow at various temperatures for 2h. The pore structure and surface chemical properties of the two selected ACs and their out-gassing treated ACs were characterized using N(2) adsorption-desorption, elements analysis, SEM and Boehm titration. A basic dye, methylene blue (MB), was chosen as an adsorbate to investigate the adsorption capacity for organic contaminant onto the activated carbons. It was found that the out-gassing treatment at 400 degrees C had little effect on the textural characteristics of the carbons but significantly changed the surface chemical properties such as surface functional groups concentration, pH and pH(PZC). The CMC-based activated carbons exhibited excellent performance for MB adsorption due to their high surface area, large mesopore volume and high nitrogen content. The kinetics of MB adsorption onto the activated carbons followed a pseudo-second-order equation, and the equilibrium data agreed well with the Langmuir model under the experimental conditions. The highest adsorption rate constant of k(ad) and the largest adsorption capacity of q(m) were found be 1.44x10(-4)g/mgmin and 519mg/g, respectively. The results suggested that the CMC-based activated carbons were effective adsorbents for the removal of methylene blue from aqueous solution.     

Comparative study on the characteristics of fly ash and bottom ash geopolymers

This research was conducted to compare geopolymers made from fly ash and ground bottom ash. Sodium hydroxide (NaOH) and sodium silicate (Na(2)SiO(3)) solutions were used as activators. A mass ratio of 1.5 Na(2)SiO(3)/NaOH and three concentrations of NaOH (5, 10, and 15M) were used; the geopolymers were cured at 65 degrees C for 48 h. A Fourier transform infrared spectrometer (FT-IR), differential scanning calorimeter (DSC), and scanning electron microscope (SEM) were used on the geopolymer pastes. Geopolymer mortars were also prepared in order to investigate compressive strength. The results show that both fly ash and bottom ash can be utilized as source materials for the production of geopolymers. The properties of the geopolymers are dependent on source materials and the NaOH concentration. Fly ash is more reactive and produces a higher degree of geopolymerization in comparison with bottom ash. The moderate NaOH concentration of 10 M is found to be suitable and gives fly ash and bottom ash geopolymer mortars with compressive strengths of 35 and 18 MPa.     

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。