Validation of an in situ solidification/stabilization technique for hazardous barium and cyanide waste for safe disposal into a secured landfill

The aim of the present study was to devise and validate an appropriate treatment process for disposal of hazardous barium and cyanide waste into a landfill at a Common Hazardous Waste Treatment Storage Disposal Facility (CHWTSDF). The waste was generated during the process of hardening of steel components and contains cyanide (reactive) and barium (toxic) as major contaminants. In the present study chemical fixation of the contaminants was carried out. The cyanide was treated by alkali chlorination with calcium hypochlorite and barium by precipitation with sodium sulfate as barium sulfate. The pretreated mixture was then solidified and stabilized by binding with a combination of slag cement, ordinary Portland cement and fly ash, molded into blocks (5 × 5 × 5 cm) and cured for a period of 3, 7 and 28 days. The final experiments were conducted with 18 recipe mixtures of waste + additive:binder (W:B) ratios. The W:B ratios were taken as 80:20, 70:30 and 50:50. The optimum proportions of additives and binders were finalized on the basis of the criteria of unconfined compressive strength and leachability. The leachability studies were conducted using the Toxicity Characteristic Leaching Procedure. The blocks were analyzed for various physical and leachable chemical parameters at the end of each curing period. Based on the results of the analysis, two recipe mixtures, with compositions – 50% of [waste + (120 g Ca(OCl)₂ + 290 g Na₂SO₄) kg^?1 of waste] + 50% of binders, were validated for in situ stabilization into a secured landfill of CHWTSDF.     

Mechanism for the stabilization/solidification of arsenic-contaminated soils with Portland cement and cement kiln dust

In this study, the mechanism for the stabilization/solidification (S/S) of arsenic (As)-contaminated soils with Portland cement (PC), and cement kiln dust (CKD) using 1 N HCl extraction fluid, X-ray powder diffraction (XRPD), X-ray absorption near edge structure (XANES) and Extended X-ray absorption fine structure (EXAFS) spectroscopy was investigated. The degree of As immobilization after stabilization was assessed using a 1 N HCl extraction on the basis of the Korean Standard Test (KST). After 1 day of curing with 30 wt% PC and 7 days of curing with 50 wt% CKD, the concentration of As leached from the amended soils was less than the Korean countermeasure standard (3 mg L^?1). The As concentrations in the leachate treated with PC and CKD were significantly decreased at pH > 3, indicating that pH had a prevailing influence on As mobility. XRPD results indicated that calcium arsenite (Ca–As–O) and sodium calcium arsenate hydrate (NaCaAsO₄·7.5H₂O) were present in the PC- and CKD-treated slurries as the key phases responsible for As(III) and As(V) immobilization, respectively. The XANES spectroscopy confirmed that the As(III) and As(V) oxidation states of the PC and CKD slurry samples were consistent with the speciated forms in the crystals identified by XRPD. EXAFS spectroscopy showed As–Ca bonding in the As(III)-PC and As(III)-CKD slurries. The main mechanism for the immobilization of As-contaminated soils with PC and CKD was strongly associated with the bonding between As(III) or As(V) and Ca.     

Effects of nano-SiO(2) and different ash particle sizes on sludge ash-cement mortar

The effects of nano-SiO₂ on three ash particle sizes in mortar were studied by replacing a portion of the cement with incinerated sewage sludge ash. Results indicate that the amount of water needed at standard consistency increased as more nano-SiO₂ was added. Moreover, a reduction in setting time became noticeable for smaller ash particle sizes. The compressive strength of the ash–cement mortar increased as more nano-SiO₂ was added. Additionally, with 2% nano-SiO₂ added and a cure length of 7 days, the compressive strength of the ash–cement mortar with 1 μm ash particle size was about 1.5 times better that of 75 μm particle size. Further, nano-SiO₂ functioned to fill pores for ash–cement mortar with different ash particle sizes. However, the effects of this pore-filling varied with ash particle size. Higher amounts of nano-SiO₂ better influenced the ash–cement mortar with larger ash particle sizes.     

Effectiveness of novel and traditional methods to incorporate industrial wastes in cementitious materials—An overview

Sustainable development and eco-efficiency are urgent and imperative demands for the well-being of our planet, continued growth of a society, and human development. Traditional Portland cement production seems unsustainable due to consumption of huge natural resources and energy and significant CO₂ emissions. The volume of industrial wastes is increasing significantly, leading to a number of economical and ecological problems. Although industrial wastes can be incorporated in cementitious materials by various traditional methods, the substitution ratio of industrial wastes in cementitious materials is relatively low to avoid unacceptable performance loss. Novel methods, such as improving hydraulic activities of metallurgical slags by adding composition adjusting material at high temperature, improving surface cementitious properties of fly ashes by dehydration and rehydration treatment, and arranging cement clinker and industrial wastes in the particle size distribution of blended cements according to their hydraulic activities, are reviewed. These methods provide more effective approach to prepare high performance blended cements with larger amount of industrial wastes, leading to a very significant role in CO₂ emissions reducing, resources and energy conservation of the cement industry.     

Production of Fe2O3 from FeSO4·xH2O formed in galvanizing works

FeSO₄·xH₂O is generated in large amounts in galvanizing workshops. It can be reutilized by conversion to Fe₂O₃. In this study, the recovery of Fe₂O₃ from FeSO₄·xH₂O formed in the galvanizing process has been examined. The experimental work was carried out at various temperatures and times in the oxidizing medium. The reaction temperatures and times were selected as 450, 500, 550, 600, 650, 700, 800 and 900°C, and 15, 30, 45, 60, 90 and 120 minutes, respectively. In order to determine the amount of Fe₂O₃, a titrimetric method was applied. The reaction products were characterized by means of IR and XRD techniques.The extent of conversion is low at temperatures below 650°C. Almost all of the iron (II) sulfate in the original sample was converted to iron(III) oxide at 650°C (120 min), 700°C (90 min), 800°C (60 min) and 900°C (45 min).     

Evaluation of sulfate resistance of cement mortars containing black rice husk ash

In this paper, black rice husk ashes (BRHAs), which are agrowastes from an electricity generating power plant and a rice mill, were ground and used as a partial cement replacement. The durability of mortars under sulfate attack including expansion and compressive strength loss were investigated. For parametric study, BRHA were used as a Portland cement Type 1 replacement at the levels of 0%, 10%, 30%, and 50% by weight of binder. The water-to-binder ratios were 0.55 and 0.65. For the durability of mortar exposed to sulfate attack, 5% sodium sulfate (Na₂SO₄) and magnesium sulfate (MgSO₄) solutions were used. As a result, when increasing the percentage replacement of BRHA, the expansion and compressive strength loss of mortar decreased. At the replacement levels of 30% and 50% of BRHA, the expansion of the mortars was less than those mixed with sulfate-resistant cement. However, the expansion of the mortars exposed to Na₂SO₄ was more than those exposed to MgSO₄. Increasing the replacement level of BRHA tends to reduce the compressive strength loss of mortars exposed to Na₂SO₄ attack. In contrary, under MgSO₄ attack, when increasing the replacement level of BRHA, the compressive strength loss increases from 0% to 50% in comparison to Portland cement mortar. Results show that ground BRHA can be applied as a pozzolanic material to concrete and also improve resistance to sodium sulfate attack, but it can impair resistance to magnesium sulfate attack.     

Experimental investigation of wellbore integrity and CO2–brine flow along the casing–cement microannulus

Wellbore integrity is one of the key performance criteria in the geological storage of CO₂. It is significant in any proposed storage site but may be critical to the suitability of depleted oil and gas reservoirs that may have 10’s to 1000’s of abandoned wells. Much previous work has focused on Portland cement which is the primary material used to seal wellbore systems. This work has emphasized the potential dissolution of Portland cement. However, an increasing number of field studies (e.g., Carey et al., 2007), experimental studies (e.g., Kutchko et al., 2006) and theoretical considerations indicate that the most significant leakage mechanism is likely to be flow of CO₂ along the casing–cement microannulus, cement–cement fractures, or the cement–caprock interface.In this study, we investigate the casing–cement microannulus through core-flood experiments. The experiments were conducted on a synthetic wellbore system consisting of a 5-cm diameter sample of cement that was cured with an embedded rectangular length of steel casing that had grooves to accommodate fluid flow. The experiments were conducted at 40 $°$ C and 14 MPa pore pressure for 394 h. During the experiment, 6.2 l of a 50:50 mixture of supercritical CO₂ and 30,000 ppm NaCl-rich brine flowed through 10-cm of limestone before flowing through the 6-cm length cement–casing wellbore system. Approximately 59,000 pore volumes of fluid moved through the casing–cement grooves. Scanning electron microscopy revealed that the CO₂–brine mixture impacted both the casing and the cement. The Portland cement was carbonated to depths of 50–250 $\mu$m by a diffusion-dominated process. There was very little evidence for mass loss or erosion of the Portland cement. By contrast, the steel casing reacted to form abundant precipitates of mixed calcium and iron carbonate that lined the channels and in one case almost completely filled a channel. The depth of steel corroded was estimated at 25– $30\mu$m and was similar in value to results obtained with a simplified corrosion model.The experimental results were applied to field observations of carbonated wellbore cement by Carey et al. (2007) and Crow et al. (2009) to show that carbonation of the field samples was not accompanied by significant CO₂–brine flow at the casing–cement interface. The sensitivity of standard-grade steel casing to corrosion suggests that relatively straight-forward wireline logging of external casing corrosion could be used as a useful indicator of flow behind casing. These experiments also reinforce other studies that indicate rates of Portland cement deterioration are slow, even in the high-flux CO₂–brine experiments reported here.     

Activated fly ash/slag blended cement

This paper presents the results of the preparation of an ecological cementing material from granulated blast-furnace slag (GBFS) and Class C fly ash (CCFA). The desulphurization gypsum, calcined at 600–800 °C for 0.5–1.5 h, works as the main ingredient of the activator in the cementing material. The optimized formulation of the cementing material was obtained with the aid of factorial design method: slag, 70%; CCFA, 18%; activator, 12%. The “partial super-fine grinding process” was adopted to improve the performance, i.e., 85% of the mixture is ground to Blaine fineness of 3500 cm²/g, 15% further ground to around 5000 cm²/g. The compressive strength of 28 days of the cement mortar is up to 49 MPa and flexural strength 8.4 MPa. The hydration products, investigated by SEM and X-ray diffraction, are mainly ettringite and C–S–H gel.     

Water/acid gas interfacial tensions and their impact on acid gas geological storage

Acid gas geological disposal is a promising process to reduce CO₂ atmospheric emissions and an environment-friendly and economic alternative to the transformation of H₂S into sulphur by the Claus process. Acid gas confinement in geological formations is to a large extent controlled by the capillary properties of the water/acid–gas/caprock system, because a significant fraction of the injected gas rises buoyantly and accumulates beneath the caprock. These properties include the water/acid gas interfacial tension (IFT), to which the so-called capillary entry pressure of the gas in the water-saturated caprock is proportional. In this paper we present the first ever systematic water/acid gas IFT measurements carried out by the pendant drop technique under geological storage conditions. We performed IFT measurements for water/H₂S systems over a large range of pressure (up to P = 15 MPa) and temperature (up to T = 120 °C). Water/H₂S IFT decreases with increasing P and levels off at around 9–10 mN/m at high T (≥70 °C) and P (>12 MPa). The latter values are around 30–40% of water/CO₂ IFTs, and around 20% of water/CH₄ IFTs at similar T and P conditions. The IFT between water and a CO₂ + H₂S mixture at T = 77 °C and P > 7.5 MPa is observed to be approximately equal to the molar average IFT of the water/CO₂ and water/H₂S binary mixtures. Thus, when the H₂S content in the stored acid gas increases the capillary entry pressure decreases, together with the maximum height of acid gas column and potential storage capacity of a given geological formation. Hence, considerable attention should be exercised when refilling with a H₂S-rich acid gas a depleted gas reservoir, or a depleted oil reservoir with a gas cap: in the case of hydrocarbon reservoirs that were initially (i.e., at the time of their discovery) close to capillary leakage, acid gas leakage through the caprock will inevitably occur if the refilling pressure approaches the initial reservoir pressure.     

The reuse of municipal solid waste incinerator fly ash slag as a cement substitute

The results of the treatment of fly ash from a municipal solid waste incinerator (MSWI) by melting are described, and the safety and the effectiveness of using the slag produced by this melting treatment are studied. The properties of the MSWI fly ash slag were analyzed, to evaluate the feasibility of its reuse as a substitute for part of the cement required in mortar preparation. This MSWI fly ash slag was found to be comprised mainly of SiO₂ and CaO, which can be substituted for up to 20% of the cement content in mortar, without sacrificing the quality of the resultant concrete. In fact, the concrete thus produced has greater compressive strength, 10% higher than that without the substitution. The setting time of the fresh mortar becomes lengthens as increasing amounts of cement are replaced; while the spread flow value increases with the increasing percentage of cement substitution. X-ray diffraction analysis reveals that when the W/C=0.38 and the curing AGE=28 days, the crystal patterns in the mortar samples, prepared with different amounts of cement having been replaced by MSWI fly ash slag are similar. According to the results of the toxic characteristic leaching procedure analysis, MSWI fly ash slag should be classified as general non-hazardous industrial waste, that meets the effluent standard. Therefore, the reuse of MSWI fly ash slag is feasible, and will not result in pollution due to the leaching of heavy metals.     

Effect of oxygenated liquid additives on the urea based SNCR process

An experimental investigation was performed to study the effect of oxygenated liquid additives, H₂O₂, C₂H₅OH, C₂H₄(OH)₂ and C₃H₅(OH)₃ on NO_x removal from flue gases by the selective non-catalytic reduction (SNCR) process using urea as a reducing agent. Experiments were performed with a 150 kW pilot scale reactor in which a simulated flue gas was generated by the combustion of methane operating with 6% excess oxygen in flue gases. The desired levels of initial NO_x (500 ppm) were achieved by doping the fuel gas with ammonia. Experiments were performed throughout the temperature range of interest, i.e. from 800 to 1200 °C for the investigation of the effects of the process additives on the performance of aqueous urea DeNO_x. With H₂O₂ addition a downward shift of 150 °C in the peak reduction temperature from 1130 to 980 °C was observed during the experimentation, however, the peak reduction efficiency was reduced from 81 to 63% when no additive was used. The gradual addition of C₂H₅OH up to a molar ratio of 2.0 further impairs the peak NO_x reduction efficiency by reducing it to 50% but this is accompanied by a downward shift of 180 °C in the peak reduction temperature. Further exploration using C₂H₄(OH)₂ suggested that a 50% reduction could be attained for all the temperatures higher than 940 °C. The use of C₃H₅(OH)₃ as a secondary additive has a significant effect on the peak reduction efficiency that decreased to 40% the reductions were achievable at a much lower temperature of 800 °C showing a downward shift of 330 °C.     

Cement replacement by sugar cane bagasse ash: CO2 emissions reduction and potential for carbon credits

This paper presents a study of cement replacement by sugar cane bagasse ash (SCBA) in industrial scale aiming to reduce the CO₂ emissions into the atmosphere. SCBA is a by-product of the sugar/ethanol agro-industry abundantly available in some regions of the world and has cementitious properties indicating that it can be used together with cement. Recent comprehensive research developed at the Federal University of Rio de Janeiro/Brazil has demonstrated that SCBA maintains, or even improves, the mechanical and durability properties of cement-based materials such as mortars and concretes. Brazil is the world’s largest sugar cane producer and being a developing country can claim carbon credits. A simulation was carried out to estimate the potential of CO₂ emission reductions and the viability to issue certified emission reduction (CER) credits. The simulation was developed within the framework of the methodology established by the United Nations Framework Convention on Climate Change (UNFCCC) for the Clean Development Mechanism (CDM). The State of São Paulo (Brazil) was chosen for this case study because it concentrates about 60% of the national sugar cane and ash production together with an important concentration of cement factories. Since one of the key variables to estimate the CO₂ emissions is the average distance between sugar cane/ethanol factories and the cement plants, a genetic algorithm was developed to solve this optimization problem. The results indicated that SCBA blended cement reduces CO₂ emissions, which qualifies this product for CDM projects.     

A review on the use of waste glasses in the production of cement and concrete

The use of recycled waste glasses in Portland cement and concrete has attracted a lot of interest worldwide due to the increased disposal costs and environmental concerns. Being amorphous and containing relatively large quantities of silicon and calcium, glass is, in theory, pozzolanic or even cementitious in nature when it is finely ground. Thus, it can be used as a cement replacement in Portland cement concrete. The use of crushed glasses as aggregates for Portland cement concrete does have some negative effect on properties of the concrete; however, practicle applicability can still be produced even using 100% crushed glass as aggregates. The main concerns for the use of crushed glasses as aggregates for Portland cement concrete is the expansion and cracking caused by the glass aggregates. This paper summarizes the progresses and points out the directions for the proper uses of waste glasses in Portland cement and concrete.     

Ammonium removal from waste solutions by precipitation of MgNH4PO4 I. Ammonium removal with use of commercial reagents

The method of ammonium ion removal from industrial waste solutions was investigated and parameters for MgNH₄PO₄ precipitation were determined. A solution laden with NH₄⁺ ions was brought to pH 1–2 by the use of H₃PO₄; MgO was then added and the pH adjusted to 9–10 with the use of NaOH solution. Stirring of the suspension was carried out during a prolonged period of time ( 3 hours), with final filtration or sedimentation. By this method the ammonium ion content in the filtrate may be reduced to concentrations below 1 mg/l. The MgNH₄PO₄·6H₂O sediment produced is considered to be a long-term fertilizer, suitable for agricultural use.     

Durability of conventional concretes containing black rice husk ash

In this study, black rice husk ash (BRHA) from a rice mill in Thailand was ground and used as a partial cement replacement. The durability of conventional concretes with high water–binder ratios was investigated including drying shrinkage, autogenous shrinkage, depth of carbonation, and weight loss of concretes exposed to hydrochloric (HCl) and sulfuric (H₂SO₄) acid attacks. Two different replacement percentages of cement by BRHA, 20% and 40%, and three different water–binder ratios (0.6, 0.7 and 0.8) were used. The ratios of paste volume to void content of the compacted aggregate (γ) were 1.2, 1.4, and 1.6. As a result, when increasing the percentage replacement of BRHA, the drying shrinkage and depth of carbonation reaction of concretes increased. However, the BRHA provides a positive effect on the autogenous shrinkage and weight loss of concretes exposed to hydrochloric and sulfuric acid attacks. In addition, the resistance to acid attack was directly varied with the (SiO₂ + Al₂O₃ + Fe₂O₃)/CaO ratio. Results show that ground BRHA can be applied as a pozzolanic material and also improve the durability of concrete.     

The comparative study of the effects of 4 Hz Electromagnetic Fields-, Infrasound-treated and hydrogen peroxide containing physiological solutions on Na pump-induced inhibition of heart muscle contractility

The effects of 4 Hz extremely low frequency Electromagnetic Fields (ELF EMF), Infrasound (IS) and hydrogen peroxide (H₂O₂) on Na⁺–K⁺ pump-induced transient inhibition of heart muscle contractility was studied. It was documented that EMF-treated and H₂O₂-containing physiological solution had synergic depressing effect on Na⁺–K⁺ pump-induced inhibition of muscle contractility, while the IS had elevation effect on it. On the basis of the obtained data the H₂O₂ could be suggested as the messenger through which the stimulation effect of EMF on heart muscle is realised, while the relaxing effect of IS on heart contractility is due to the decrease of CO₂ solubility of muscle bathing aqueous medium.     

Study on the failure mechanism of potassium-based sorbent for CO2 capture and the improving measure

With thermogravimetric apparatus (TGA), X-ray diffraction (XRD) and barium sulfate gravimetric methods, the carbonation reactivities of K₂CO₃ and K₂CO₃/Al₂O₃ in the simulated flue gases with SO₂ are investigated and the reaction equations are inferred. Results show that there are KHCO₃ and K₂SO₃ generated. The generation K₂SO₃ reduces the utilization ratio of the sorbent. H₂O may accelerates the sulfation reaction of AR K₂CO₃ as K₄H₂(CO₃)₃·1.5H₂O is generated in the reaction among K₂CO₃, SO₂ and H₂O. K₂SO₃ is directly generated from sulfation reaction of K₂CO₃/Al₂O₃, because there are K₂CO₃·1.5H₂O and K₂SO₃ generated in the reaction among K₂CO₃/Al₂O₃, SO₂ and H₂O. K₂CO₃·1.5H₂O does not react with SO₂, and K₂CO₃·1.5H₂O/Al₂O₃ reacts with SO₂ slowly. Compare with the reaction process without H₂O pretreatment, the reaction rates of KAl30 increased after H₂O pretreatment and the failure ratio is about a half of that without H₂O pretreatment. So, K₂CO₃/Al₂O₃ shows good carbonation and anti-sulfation characteristic after H₂O pretreatment.     

Strategies for meeting Tanzania's future cement needs

This paper discusses the options for the development of Tanzania's cement industry to meet the country's growing cement needs. It evaluates possible options and supports the use of dispersed small-scale vertical kiln plants to increase the capacity for Portland cement production. It also encourages the use of alternative cementitious materials in the many applications where this is possible.     

Gasification of Inferior Coal with High Ash Content under CO2 and O2/H2O Atmospheres

The gasification reaction of Nantong inferior coal was investigated in a laboratory fixed-bed reactor under CO₂ and O₂/H₂O atmospheres. The effects of the bed temperature and inlet-gas concentration on the yields of CO, H₂, and CH₄ were studied. The effects of coal ash and particle size on the fixed-carbon conversion were also investigated, and kinetic analysis was conducted with a homogeneous model. The product-gas-heating value and fixed-carbon conversion increased when the temperature was increased from 950 °C to 1100 °C under CO₂ atmosphere. When the inlet-CO₂ concentration was increased from 50 to 100 vol.%, the low heating value of the product gas and carbon conversion ratio slightly increased. During the gasification of inferior coal under the O₂/H₂O atmosphere, the CO concentration increased rapidly with increasing temperature. The H₂ and CH₄ concentrations increased initially and then decreased. The maximum gas heating value of 7934 kJ/m³ was obtained under the O₂ concentration of 70 vol.% at a bed temperature of 1050 °C. The cold-gas efficiency increased with increasing temperature and became 40.6% and 86.4% at 1100 °C under the CO₂ and O₂/H₂O atmospheres, respectively. The gasification reaction of the Nantong inferior coal strongly depended on the content of inherent inorganic matter. The gasification rates for both the CO₂ and O₂/H₂O atmospheres were independent of the particle size. The activation energy for the CO₂ and O₂/H₂O gasification reactions were 137 and 81 kJ/mol, respectively. The gasification reactions of the Nantong coal, which was performed under two different atmospheres, were compared and the reaction activity of the gasification reaction under CO₂ atmosphere was found to be much lower than that under the O₂/H₂O atmosphere.     

Ash and deposit formation from oxy-coal combustion in a 100 kW test furnace

Ash deposition is still an unresolved problem when retrofitting existing air-fired coal power plants to oxy-fuel combustion. Experimental data are quite necessary for mechanism validation and model development. This work was designed to obtain laboratory combustor data on ash and deposits from oxy-coal combustion, and to explore the effects of oxy-firing on their formation. Two bituminous coals (Utah coal and Illinois coal) and one sub-bituminous coal (PRB coal) were burned on a down-fired combustor under both oxy- and air-firing. Two oxy-fired cases, i.e., 27 vol% O₂/73 vol% CO₂ and 32 vol% O₂/68 vol% CO₂, were selected to match the radiation flux and the adiabatic flame temperature of air combustion, respectively. Once-through CO₂ was used to simulate fully cleaned recycled flue gas. The flue gas excess oxygen was fixed at 3 vol%. For each case, both size-segregated fly ash and bulk fly ash samples were obtained. Simultaneously, ash deposits were collected on an especially designed un-cooled deposition probe. Ash particle size distributions and chemical composition of all samples were characterized. Data showed that oxy-firing had insignificant impacts on the tri-modal ash particle size distributions and composition size distributions in the size range studied. Bulk ash compositions also showed no significant differences between oxy- and air-firing, except for slightly higher sulfur contents in some oxy-fired ashes. The oxy-fired deposits were thicker than those from air-firing, suggesting enhanced ash deposition rates in oxy-firing. Oxy-firing also had apparent impacts on the deposit composition, especially for those components (e.g., CaO, Fe₂O₃, SO₃, etc.) that could contribute significantly to ash deposition. Based on these results, aerodynamic changes in gas flow and changes in combustion temperature seemed more important than chemical changes of ash particles in determining deposit behavior during oxy-coal combustion.