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.     

Balancing durability and environmental impact in concrete combining low-grade recycled aggregates and mineral admixtures

This paper investigated the effect of various amounts of low-grade recycled aggregates in concrete containing mineral admixtures at three different water-binder ratios on mechanical and environmental performance. The balance between durability and environmental impact for a given strength level similar to normal-use concrete was also examined using analytic hierarchy process. Results showed that increasing the water-binder ratio and volume of recycled aggregates reduced compressive strength and increased air permeability and drying shrinkage relative to normal aggregates. However, compared to normal-use concrete similar or better performance could be achieved, which was attributed to improvement of low-grade recycled aggregate performance when combined with fly ash. Similarly, CO₂ emissions and volume of raw materials were lower than the normal-use concrete for all mixes. Concrete mixes with low air permeability and low CO₂ footprint had the best balance of durability and environmental impact, as decreasing raw material volume tended to more greatly reduce durability.     

A natural analogue for CO2 mineral sequestration in Miocene basalt in the Kuanhsi-Chutung area, Northwestern Taiwan

In general, CO₂ sequestration by carbonation is estimated by laboratory experimentation and geochemical simulation. In this study, however, estimation is based on a natural analogue study of the Miocene basalt in the Kuanhsi-Chutung area, Northwestern Taiwan. This region has great potential in terms of geological and geochemical environments for CO₂ sequestration. Outcropping Miocene basalt in the study area shows extensive serpentinization and carbonation. The carbon stable isotopes of carbonates lie on the depleted side of the Lohmann meteoric calcite line, which demonstrates that the carbonates most probably precipitate directly from meteoric fluid, and water–rock interaction is less involved in the carbonation process. Oxygen stable isotope examinations also show much depleted ratios, representative of product formation under low temperatures (∼50–90 °C). This translates to a depth of 1–2 km, which is a practical depth for a CO₂ sequestration reservoir. According to petrographic observation and electron microprobe analysis, the diopside grains in the basalt are resistant to serpentinization and carbonation; therefore, the fluid causing alteration is likely enriched with calcium and there must be additional sources of calcium for carbon mineralization. These derived geochemical properties of the fluid support the late Miocene sandstone and enclosed basalts as having high potential for being a CO₂ sequestration reservoir. Moreover, the existing geochemical environments allow for mineralogical assemblages of ultramafic xenoliths, indicating that forsterite, orthopyroxene and feldspar minerals are readily replaced by carbonates. Based on the mineral transformation in xenoliths, the capacity of CO₂ mineral sequestration of the Miocene basalt is semi-quantitatively estimated at 94.15 kg CO₂ chemically trapped per 1 m³ basalt. With this value, total CO₂ sequestration capacity can be evaluated by a geophysical survey of the amount of viable Miocene basalt at the potential sites. Such a survey is required in the near future.     

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.     

Effect of steam hydration on performance of lime sorbent for CO2 capture

Lime is considered a feasible sorbent for the capture of CO₂ from large stationary sources. The positive attributes of a natural source material, low cost and lack of harmful by-products are offset by rapid deterioration in performance and high regeneration temperature. Performance can be improved by hydrating the lime using steam. We investigate a steam hydration process wherein lime is hydrated for 5 min at 300 °C and atmospheric pressure in a mixture of steam and CO₂. The experiments consisted of 10 capture cycles with 60% of the lime active at the end. Extrapolation using a decay model suggests a residual carbonation level of 48%, significantly higher than the 8% achieved by dry lime cycles. The cost of replacement sorbent under these conditions is less than $1/t of CO₂ captured. The hydrated lime process also reduces the thermal load, for heating and cooling, by half as well as the inventory, and therefore solids handling, by a factor 5 over dry lime. The introduction of the hydration reaction provides another exothermic reaction for heat management.     

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.     

Moisture transfer modeling during solar drying of potato cylinders considering shrinkage

In the present work, the thin layer drying kinetics of potato during natural convection solar drying was investigated experimentally. Cylindrical potato samples with length 50 mm and varying diameter of 8, 10 and 13 mm were dried in an in-house designed and fabricated laboratory scale mixed-mode solar dryer. Thirteen different thin-layer mathematical models were fitted to the experimental moisture ratio (MR) data. The obtained results indicated that the Modified Page model could satisfactorily describe the drying curve of potato cylinders with higher value of R² and lower values of RMSE and χ². The shrinkage parameter is incorporated in the analytical diffusion model to study the moisture transfer mechanism of potato cylinders. It was observed that the values of effective diffusion coefficient (D_eff) and convective mass transfer coefficient (h_m) are overestimated in the range of 85.02–90.27% and 39.11–45.11% for the range of sample diameter examined, without considering the shrinkage effect in the mass transfer analysis. A Multiphysics approach was adopted in this study to get insight into the drying behavior of potato cylinders in terms of food-moisture interactions during the solar drying process. The predicted results of MR are in close agreement with the experimental data. Moreover, the anisotropic behavior of shrinkage as well as the moisture distribution inside the potato cylinder was very well described by Multiphysics model.     

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.     

Study on CO2 capture using dry potassium-based sorbents through orthogonal test method

The effect of reaction conditions on the carbonation characteristics of K₂CO₃ calcined from KHCO₃ was investigated with a pressurized thermogravimetric apparatus. Results show that the conversion rate decreased as the reaction temperature and pressure increased, and the effect of CO₂ and H₂O concentration is little. The mean reaction rate maintained constant of 3%/min. The maximum reaction rate increased as the temperature and H₂O concentration increased, and the pressure decreased. The reaction temperature and pressure are the key factors, and it is important to control those carefully for this technique. The optimum reaction condition is 60 °C, 18% CO₂, 18% H₂O, and 1 atm. K₂CO₃ calcined from KHCO₃ showed excellent CO₂ capture capability in this condition.     

Estimation of “environmentally sensitive” dispersal ratios for chemical dispersants used in crude oil spill control

The toxicities of two dispersants (Biosolve and OSD 9460), Forcados light crude oil and their mixtures based on ratios 6:1, 9:1, and 12:1 (v/v) were evaluated against the juvenile stage of African catfish, Clarias gariepinus, in laboratory bioassays. On the basis of the derived toxicity indices, Biosolve (96-h LC₅₀ = 0.211 μl/l) was found to be about 27,284 times more toxic than crude oil (96-h LC₅₀ = 5.757 ml/l) and 6,450 times more toxic than OSD 9460 (96-h LC₅₀ = 1.361 ml/l). OSD 9460 was also found to be four times more toxic than crude oil when acting alone against C. gariepinus. Toxicity evaluations of the mixtures of crude oil/dispersants mixtures varied, depending largely upon the proportion of addition of the mixture components. The interactions between mixture of crude oil and Biosolve at the test ratios of 6:1, 9:1, and 12:1 were found to conform with the model of synergism (SR = 7,655, 14,876, and 8,792, respectively), and the mixtures were therefore more toxic than the crude oil acting singly. Similarly, the interactions between mixture of crude oil and OSD 9460 at the test ratios of 6:1 and 9:1 also conformed to the model of synergism (SR = 2.2 and 1.84, respectively). Interactions between the dispersant OSD 9460 and the crude oil at test ratio 12:1, however, conformed to the model of antagonism (SR = 0.84), indicating that the mixture was less toxic than crude oil acting alone. The results of the emulsification potential of OSD 9460 and Biosolve [measured in terms of optical transmittance (%)] prepared at the dispersal ratios 6:1, 9:1, and 12:1 revealed that the dispersal ratio of 6:1 achieved the highest emulsification of the crude oil with optical transmittance value of 4% and 6%, respectively. Estimation of an “environmentally sensitive” dispersal ratio for OSD 9460 and Biosolve revealed the optimum dispersal ratio for OSD 9460 range between ratios 7.5:1 and 9:1, while for Biosolve such an optimum dispersal ratio was indeterminate within the range of test dispersal ratios. The implications of these results in setting manufacturer’s and regulatory dispersal ratios for chemical dispersants used for oil spill control were discussed.     

The influence of the precursor and synthesis method on the CO2 capture capacity of carpet waste-based sorbents

Adsorption is one of the most promising technologies for reducing CO₂ emissions and at present several different types of sorbents are being investigated. The use of sorbents obtained from low-cost and abundant precursors (i.e. solid wastes) appears an attractive strategy to adopt because it will contribute to a reduction not only in operational costs but also in the amount of waste that is dumped and burned in landfills every year. Following on from previous studies by the authors, in this work several carbon-based adsorbents were developed from different carpet wastes (pre-consumer and post-consumer wastes) by chemical activation with KOH at various activation temperatures (600–900 °C) and KOH:char impregnation ratios (0.5:1 to 4:1). The prepared materials were characterised by chemical analysis and gas adsorption (N₂, −196 °C; CO₂, 0 °C), and tested for CO₂ adsorption at temperatures of 25 and 100 °C. It was found that both the type of precursor and the conditions of activation (i.e. impregnation ratios, and activation temperatures), had a huge influence on the microporosity of the resultant samples and their CO₂ capture capacities. The carbon-based adsorbent that presented the maximum CO₂ capture capacities at 25 and 100 °C (13.8 wt.% and 3.1 wt.%, respectively), was prepared from a pre-consumer carpet waste and was activated at 700 °C using a KOH:char impregnation ratio of 1:1. This sample showed the highest narrow microporosity volume (0.47 cm³ g⁻¹), thus confirming that only pores of less than 1 nm are effective for CO₂ adsorption at atmospheric pressure.     

Biohythane production from pineapple peel using Methanosarcina mazei enhanced with palm oil mill effluent (POME) sludge in single-stage anaerobic digestion

Biohythane production via single-stage anaerobic digestion (AD) is an effective way for sustainable energy recovery from lignocellulosic biomass. In this paper, biohythane was produced through the AD process from pineapple peel waste substrate using purely cultured Methanosarcina mazei with the enhancement of palm oil mill effluent (POME) sludge as the inoculum. This study focuses on the effects of the lignocellulosic pre-treatment method, the addition of POME sludge into M. mazei culture medium as inoculum, and various operational conditions (food to microorganisms (F/M) ratios, temperature, pH) on gas production performances. The experimental results indicate that these parameters influenced the efficiency of biohythane production by producing the peak maximum biohythane production rate values (HPR_max) and (MPR_max), H₂:CH₄ = 1.93:0.67 L/L-d, and biohythane yield (HY) and (MY), H₂:CH₄ = 1.18:0.55 mL/L-substrate. This study demonstrates that biohythane gas (H₂ + CH₄ + CO₂) production from pineapple waste can be accelerated by M. mazei only with the enhancement of POME sludge through single-stage AD system under mesophilic batch process conditions.     

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.     

Hydrogeochemical Indicators of Groundwater Flow Systems in the Yangwu River Alluvial Fan,Xinzhou Basin,Shanxi, China

Based on analysis of groundwater hydrochemical and isotopic indicators, this article aims to identify the groundwater flow systems in the Yangwu River alluvial fan, in the Xinzhou Basin, China. Groundwater δ²H and δ¹⁸O values indicate that the origin of groundwater is mainly from precipitation, with local evaporative influence. d-excess values lower than 10% in most groundwaters suggest a cold climate during recharge in the area. Major ion chemistry, including rCa/rMg and rNa/rCl ratios, show that groundwater salinization is probably dominated by water–rock interaction (e.g., silicate mineral weathering, dissolution of calcite and dolomite and cation exchange) in the Yangwu River alluvial fan, and locally by intensive evapotranspiration in the Hutuo River valley. Cl and Sr concentrations follow an increasing trend in shallow groundwater affected by evaporation, and a decreasing trend in deep groundwater. ⁸⁷Sr/⁸⁶Sr ratios reflect the variety of lithologies encountered during throughflow. The groundwater flow systems (GFS) of the Yangwu River alluvial fan include local and intermediate flow systems. Hydrogeochemical modeling results, simulated using PHREEQC, reveal water–rock interaction processes along different flow paths. This modeling method is more effective for characterizing flow paths in the intermediate system than in the local system. Artificial exploitation on groundwater in the alluvial fan enhances mixing between different groundwater flow systems.     

Experimental validation of in situ CO2 capture with CaO during the low temperature combustion of biomass in a fluidized bed reactor

A novel concept for capturing CO₂ from biomass combustion using CaO as an active solid sorbent of CO₂ is discussed and experimentally tested. According to the CaO/CaCO₃ equilibrium, if a fuel could be burned at a sufficiently low temperature (below 700 °C) it would be possible to capture CO₂ “in situ” with the CaO particles at atmospheric pressure. A subsequent step involving the regeneration of CaCO₃ in a calciner operating at typical conditions of oxyfired-circulating fluidized combustion would deliver the CO₂ ready for purification, compression and permanent geological storage. Several series of experiments to prove this concept have been conducted in a 30 kW interconnected fluidized bed test facility at INCAR-CSIC, made up of two interconnected circulating fluidized bed reactors, one acting as biomass combustor-carbonator and the other as air-fired calciner (which is considered to yield similar sorbent properties than those of an oxyfired calciner). CO₂ capture efficiencies in dynamic tests in the combustor-carbonator reactor were measured over a wide range of operating conditions, including different superficial gas velocities, solids circulation rates, excess air above stoichiometric, and biomass type (olive pits, saw dust and pellets). Biomass combustion in air is effective at temperatures even below the 700 °C, necessary for the effective capture of CO₂ by carbonation of CaO. Overall CO₂ capture efficiencies in the combustor-carbonator higher than 70% can be achieved with sufficiently high solids circulation rates of CaO and solids inventories. The application of a simple reactor model for the combined combustion and CO₂ capture reactions allows an efficiency factor to be obtained from the dynamic experimental test that could be valuable for scaling up purposes.     

CO2 recycling by reaction with renewably-generated hydrogen

A laboratory-scale reactor system was built and operated to demonstrate the feasibility of catalytically reacting carbon dioxide (CO₂) with renewably-generated hydrogen (H₂) to produce methane (CH₄) according to the Sabatier reaction: CO₂ + 4H₂ → CH₄ + 2H₂O. A cylindrical reaction vessel packed with a commercial methanation catalyst (Haldor Topsøe PK-7R) was used. Renewable H₂ produced by electrolysis of water (from solar- and wind-generated electricity) was fed into the reactor along with a custom blend of 2% CO₂ in N₂, meant to represent a synthetic exhaust mixture. Reaction conditions of temperature, flow rates, and gas mixing ratios were varied to determine optimum performance. The extent of reaction was monitored by real-time measurement of CO₂ and CH₄. Maximum conversion of CO₂ occurred at 300–350 °C. Approximately 60% conversion of CO₂ was realized at a space velocity of about 10,000 h^?1 with a molar ratio of H₂/CO₂ of 4/1. Somewhat higher total CO₂ conversion was possible by increasing the H₂/CO₂ ratio, but the most efficient use of available H₂ occurs at a lower H₂/CO₂ ratio.     

Recovery of phosphate from calcinated bone by dissolution in hydrochloric acid solutions

In this study, the optimum conditions of dissolution of calcinated bone in HCl solutions with different concentrations are investigated. Recovery of phosphate from calcinated bone by dissolution with hydrochloric acid solutions was investigated in a batch reactor, it was observed that a 32% hydrochloric acid solution can dissolve the calcinated bone effectively. Using the Taguchi fractional design method, it was found that the optimum process conditions, at which 67.2% P₂O₅ dissolution was reached, were as follows: Reaction temperature: 318 K, solid-to-liquid ratio: 1/5 (g ml⁻¹), acid concentrations:32 (% w/v), stirring speed:400 min⁻¹ and reaction time: 60 min.     

Effect of gas composition in Chemical-Looping Combustion with copper-based oxygen carriers: Fate of light hydrocarbons

Chemical-Looping Combustion (CLC) is an emerging technology for CO₂ capture because separation of this gas from the other flue gas components is inherent to the process and thus no energy is expended for the separation. Natural or refinery gas can be used as gaseous fuels and they may contain different amounts of light hydrocarbons. This paper presents the combustion results obtained with a Cu-based oxygen carrier using mixtures of CH₄ and light hydrocarbons (LHC) (C₂H₆ and C₃H₈) as fuel. The effect on combustion efficiency of the fuel reactor temperature, solid circulation flow rate and gas composition was studied in a continuous CLC plant (500 W_th). Full combustions were reached at 1073 and 1153 K working at oxygen to fuel ratios, ? higher than 1.5 and 1.2 respectively. Unburnt hydrocarbons were never detected at any experimental conditions at the fuel reactor outlet. Carbon formation can be avoided working at 1153 K or at ? values higher than 1.5 at 1073 K. After 30 h of continuous operation, the oxygen carrier exhibited an adequate behavior regarding attrition and agglomeration. It can be concluded that no special measures should be taken in a CLC process with Cu-based OC with respect to the presence of LHC in the fuel gas.     

Kinetics of carbon dioxide absorption into mixed aqueous solutions of MDEA and MEA using a laminar jet apparatus and a numerically solved 2D absorption rate/kinetics model

New comprehensive numerically solved 1D and 2D absorption rate/kinetics models have been developed, for the first time, to interpret the experimental kinetic data obtained with a laminar jet apparatus for the absorption of carbon dioxide (CO₂) in CO₂ loaded mixed solutions of mixed amine system of methyldiethanolamine (MDEA) and monoethanolamine (MEA). Three MDEA/MEA weight ratios ranging from 27/03 to 23/07, over a concentration range of 2.316–1.996 kmol/m³ for MDEA and of 0.490–1.147 kmol/m³ for MEA were studied. The models take into account the coupling between chemical equilibrium, mass transfer, and the chemical kinetics of all possible chemical reactions involved in the CO₂ reaction with MDEA/MEA solvent. The partial differential equations of the 1D model were solved by two numerical techniques; the finite difference method (FDM) based on in-house coded Barakat–Clark scheme and the finite element method (FEM) based on COMSOL software. The FEM comprehensive model was then used to solve the set of partial differential equations in the 2D cylindrical coordinate system setting. Both FDM and FEM produced very accurate results for both the 1D and 2D models, which were much better than our previously published simplified model. The reaction rate constant obtained for MEA blended into MDEA at 298–333 K was k_MEA = 5.127 × 10⁸ exp(−3373.8/T). In addition, the 2D model, for the first time, has provided the concentration profiles of all the species in both the radial and axial directions of the laminar jet, thereby enabling an understanding of the correct sequence in which the reaction steps involved in the reactive absorption of CO₂ in aqueous mixed amines occur.     

Effect of feeding strategy and COD/sulfate ratio on the removal of sulfate in an AnSBBR with recirculation of the liquid phase

The objective of this work was to analyze the effect of the interaction between feeding strategy and COD/sulfate ratio on the removal efficiency of sulfate and organic matter from a synthetic wastewater. An anaerobic sequencing batch reactor with recirculation of the liquid phase and containing immobilized biomass on polyurethane foam (AnSBBR) was used. The AnSBBR with a total volume of 3.7 L, treated 2.0 L synthetic wastewater in 8-h cycles at 30 ± 1 °C and was inoculated with anaerobic biomass from a UASB. Two feeding strategies were assessed: (a) batch and (b) batch followed by fed-batch. In strategy (a) the reactor was fed in 10 min with 2 L wastewater containing sulfate and carbon sources. In strategy (b) 1.2 L wastewater (containing only the sulfate source) was fed during the first 10 min of the cycle and the remaining 0.8 L (containing only the carbon source) in 240 min. The COD/sulfate ratios assessed were 1 and 3. Based on these values and on the concentrations of organic matter (0.5–11.25 gCOD/L) and sulfate (0.5 and 2.5 gSO₄^2?/L), the sulfate and organic matter loading rates applied equaled 1.5 and 4.5 gSO₄^2?/L d for sulfate and 1.5, 4.5 and 13.5 gCOD/L d for organic matter. After stabilization of the system time profiles were run of monitored parameters (COD, sulfate, sulfide and sulfite). In general, the reactor showed to be robust for use in the anaerobic treatment of wastewaters containing sulfate. Gradual feeding (strategy b) of the carbon source favored sulfate reduction, resulting in sulfate removal efficiencies of 84–98% and organic matter removal efficiencies of 48–95%. The best results were observed under COD/sulfate ratio equal to 1 (loading rates of 1.5 and 4.5 gSO₄^2?/L d for sulfate, and 1.5 and 4.5 gCOD/L d for organic matter). When COD/sulfate ratio was 3 (loading rates of 1.5 and 4.5 gSO₄^2?/L d for sulfate, and 4.5 and 13.5 gCOD/L d for organic matter) the effect of feed mode became less significant. These results show that the strategy batch followed by fed-batch is more advantageous for COD/sulfate ratios near the stoichiometric value (0.67) and higher organic matter and sulfate concentrations.