Feasibility of CO₂/SO₂ uptake enhancement of calcined limestone modified with rice husk ash during pressurized carbonation

The calcination/carbonation cycle using calcium-based sorbents appears to be a viable method for carbon dioxide (CO?) capture from combustion gases. Recent attempts to improve the CO?/SO? uptake of a calcium-based sorbent modified by using rice husk ash (RHA) in the hydration process have succeeded in enhancing its effectiveness. The optimal mole ratio of RHA to calcined limestone (M(Si/Ca)) was adjusted to 0.2. The cyclic CO? capture characteristics and the SO? uptake activity of the modified sorbent were evaluated in a calcination/pressurized carbonation reactor system. Scanning electron microscope (SEM) images and X-ray diffraction (XRD) spectrum of the sorbent were also taken to supplement the study. The results showed that the carbonation conversion was greatly increased for the sorbent with M(Si/Ca) ratio of 0.2. For this sorbent formulation the optimal operating conditions were 700-750 °C and 0.5-0.7 MPa. CO? absorption was not proportional to CO? concentration in the carbonation atmosphere, but was directly related to reaction time. The CO? uptake decreased in the presence of SO?. SO? uptake increased, and the total calcium utilization was maintained over multiple cycles. Analysis has shown that the silicate component is evenly or well distributed, and this serves as a framework to prevent sintering, thus preserving the available microstructure for reaction. The sorbent also displayed high activity to SO? absorption and could be used to capture CO? and SO? simultaneously.     

Photocatalytic Production of Methane and Hydrogen Through Reduction of Carbon Dioxide with Water Using Titania Pellets

This paper presents an experimental study on employing a pellet form of catalyst in photo-reduction of carbon dioxide with water. Water was first absorbed into titania pellets. Highly purified carbon dioxide gas was then discharged into a reactor containing the wet pellets, which were then illuminated continuously for 65 hours using UVC lamps. Analysing the products accumulated in the reactor confirmed that methane and hydrogen were produced through photo-reduction of carbon dioxide with water. No other hydrocarbons were detected. Increasing the temperature in the reactor has showed little change on the amount of methane produced.     

Assessment of spent mushroom substrate as sorbent of fungicides: influence of sorbent and sorbate properties

The capacity of spent mushroom substrate (SMS) as a sorbent of fungicides was evaluated for its possible use in regulating pesticide mobility in the environment. The sorption studies involved four different SMS types in terms of nature and treatment and eight fungicides selected as representative compounds from different chemical groups. Nonlinear sorption isotherms were observed for all SMS-fungicide combinations. The highest sorption was obtained by composted SMS from Agaricus bisporus cultivation. A significant negative and positive correlation was obtained between the K(OC) sorption constants and the polarity index values of sorbents and the K(OW) of fungicides, respectively. The statistic revealed that more than 77% of the variability in the K(OW) could be explained considering these properties jointly. The other properties of both the sorbent (total carbon, dissolved organic carbon, or pH) and the sorbate (water solubility) were nonsignificant. The hysteresis values for cyprodinil (log K(OW)= 4) were for all the sorbents much higher (>3) than for other fungicides. This was consistent with the remaining sorption after desorption considered as an indicator of the sorption efficiency of SMS for fungicides. Changes in the absorption bands of fungicides sorbed by SMS observed by FTIR permitted establishing the interaction mechanism of fungicides with SMS. The findings of this work provide evidence for the potential capacity of SMS as a sorbent of fungicides and the low desorption observed especially for some fungicides, although they suggest that more stabilized or humified organic substrates should be produced to enhance their efficiency in environmental applications.     

Carbon dioxide capture from combustion flue gases with a calcium oxide chemical loop. Experimental results and process development

Post-combustion carbonate looping processes are based on the capture of carbon dioxide from the flue gases of an existing power plant in a circulating fluidized bed reactor (CFB) of calcium oxide (the carbonator) particles. The calcination of calcium carbonate in a new oxy-fired CFBC power plant regenerates the sorbent (calcium oxide particles) and obtains high purity carbon dioxide. This communication presents experimental results from a small test facility (30 kWt) operated in continuous mode using two interconnected CFB reactors as carbonator and calciner. Capture efficiencies between 70 and 97% have been obtained under realistic flue gas conditions in the carbonator reactor (temperatures around 650 °C). The similarity between process conditions and those existing in CFBC power plants should allow a rapid scaling up of this technology. The next steps for this process development are also outlined.     

Optimization of carbon dioxide absorption in a continuous bubble column reactor using response surface methodology

Carbon dioxide absorption using amine based solvents is a well-known approach for carbon dioxide removal. Especially with the increasing concerns about greenhouse gas emissions, there is a need for an optimization approach capable of multifactor calibration and prediction of interactions. Since conventional methods based on empirical relations are not efficiently applicable, this study investigates use of Response Surface Methodology as a strong optimization tool. A bubble column reactor was used and the effect of solvent concentration (10.0, 20.0 and 30.0 vol%), flow rate (4.0, 5.0 and 6.0 L min⁻¹), diffuser pore size (0.5, 1.0 and 1.5 mm) and temperature (20.0, 25.0 and 30.0°C) on the absorption capacity and also overall mass transfer coefficient was evaluated. The optimization results for maintaining maximum capacity and overall mass transfer coefficient revealed that different optimization targets led to different tuned operational factors. Overall mass transfer coefficient decreased to 34.7 min⁻¹ when the maximum capacity was the desired target. High reaction rate along with the highest absorption capacity was set as desirable two factor target in this application. As a result, a third scenario was designed to maximize both mass transfer coefficient and absorption capacity simultaneously. The optimized condition was achieved when a gas flow rate of 5.9 L min⁻¹, MEA solution of 29.6 vol%, diffuser pore size of 0.5 mm and temperature of 20.6°C was adjusted. At this condition, mass transfer coefficient reached a maximum of 38.4 min⁻¹, with a forecasted achievable absorption capacity of 120.5 g CO₂ per kg MEA.     

Calcium oxide for CO2 capture: Operational window and efficiency penalty in sorption-enhanced steam methane reforming

Calcium oxide (CaO) is a material that is being widely investigated in the context of CO₂ capture. One such application is as a CO₂ sorbent in the sorption-enhanced steam methane reforming processes (SERP). CO₂ is captured in an adsorption mode, where the conversion of CH₄ to H₂ is also enhanced, and released later in a separate desorption mode. This work presents an analysis of the relation between different process conditions and parameters during both adsorption and desorption modes. The interrelation between these conditions and the sorbent properties as well as the targeted carbon capture ratio is analysed. Conditions relevant for capturing 85% of carbon in the feed on CaO are determined and interlinked. A steam-to-carbon ratio of 4.2 has been determined to be relevant under 600 °C and 17 bar adsorption conditions. Similarly, process conditions relevant for regenerating the sorbent are determined and interlinked. For purge steam-to-CO₂ ratio of 1.8 at a desorption pressure of 1 bar, relevant desorption temperature has been calculated to be 820 °C. System simulations under these adsorption and desorption conditions resulted in a system efficiency of 50.8%. Effect of tuning process operating conditions on system efficiency as well as the efficiency penalty associated with the regeneration of the sorbent are investigated by process simulations using Aspen Plus^®. Possible system heat integration routes to reduce the efficiency penalty are proposed and the results of the process simulations are presented.     

Forest-based biomass supply potential and economics for the pellet production in Nepal

In the current study, the potential of forest-based biomass supply for the pellet production in Nepal is investigated. This study showed that about 2.76 million tonnes (Mt) biomass in the form of pellets are potentially available from forest-based biomass. Considering a processing capacity of 6 tonnes (t)/hr of a pellet plant, the production cost of the pellets was calculated to be $43.53/t. Pellets are generally used as fuel to produce thermal energy in industries, which helps to save the economy and the environment of the country.     

Hydrogen production from biomass

The ‘hydrogen economy’ has received considerable attention in academic, industrial and political contexts. There are opportunities for vast reductions in greenhouse gas emissions, increased energy security and greater overall efficiency. However, if hydrogen is to become a fundamental energy source for electrical power generation, as well as a transportation fuel, novel generation pathways will be necessary to meet the increase in demand. A promising means for generating hydrogen is the thermochemical conversion of biomass to a synthesis gas, composed of a mixture of hydrogen, carbon monoxide, carbon dioxide and methane. In order to manipulate the composition and maximise the hydrogen output, a calcium-based carbon dioxide sorbent can be utilised in situ. The removal of carbon dioxide alters the reaction chemistry to preferentially produce hydrogen. In this work we report on the characterisation of a likely Ca-based carbon dioxide sorbent and demonstrate the merits of hydrogen production from biomass, with in situ carbon dioxide capture, on the basis of a thermodynamic study. Using this model we show that hydrogen output from biomass gasification can be increased from 40%-vol to 80%-vol (dry basis) when a carbon dioxide sorbent is used.     

Removal of Se(IV) from aqueous solution using sulphuric acid-treated peanut shell

A carbonaceous sorbent was prepared from peanut shell via sulphuric acid treatment. Se(IV) removal from aqueous solution on the sorbent was studied varying time, pH, Se(IV) concentration, temperature and sorbent status (wet and dry). Se(IV) removal was faster using the wet sorbent than the dry sorbent following a pseudo-first-order model. Se(IV) removal increases at low pH values, and decreases as pH increases until pH 7. Sorption was found to fit the Langmuir equation and sorption capacity for the wet sorbent was higher than that for the dry one. Both sorbents showed an increased selenium sorption by rising the temperature. Redox processes between Se(IV) and the carbon sorbent are involved. Analysis by scanning electron microscope and X-ray powder diffraction for the sorbent after the reaction with acidified Se(IV) confirmed the availability of elemental selenium as particles on the sorbent surface as a result of Se(IV) reduction. Physicochemical tests showed an increase in sorbent acidity, cation exchange capacity (CEC) and surface functionality after the reaction with acidified Se(IV), indicating the oxidation processes occurring on the sorbent surface. Due to its reduction properties, the sorbent seems efficient for Se(IV) removal from aqueous solution.     

Carbon dioxide capture and recovery by means of TSA and/or VSA

Experimental work is performed with a 5A zeolite on a small laboratory column with heating from the wall. Carbon dioxide adsorption occurs at atmospheric pressure and different CO₂ concentrations in nitrogen. Comparisons of different methods of desorption by heating, purge and/or vacuum are studied. Desorption by heating only leads to almost pure CO₂ (around 99% purity) and a recovery nearly linear to the heating temperature, ranging from 45% at 130 °C to 79% at 210 °C. Recovery can be subsequently increased with a nitrogen purge to more than 98% but the recovered carbon dioxide is diluted due to the dispersive character of the desorption wave and the operation time is long. Increasing the flow rate decreases the desorption time but has no effect on the purity because the total purge volume remains about the same. Substitution of the purge step with a vacuum step leads to pure CO₂ and almost total recovery. Desorption under vacuum only without heating leads to pure CO₂ (around 99% purity) but limited recovery (85% in the present work).Desorption under vacuum seems to be more simple for large-scale applications. When using a water liquid ring pump, the temperature of the ring must be kept as low as possible to provide a high operating capacity.     

Recycling of an industrial sludge and marine clay as light-weight aggregates

The geographical limitations of Singapore, its restricted natural resources and voluminous municipal and industrial waste streams, make environmental management a major challenge for the island state. In an attempt to find ways to reduce importation of raw materials and the waste sent to landfill, light weight aggregates were produced from marine clay and a CaF(2)-rich semiconductor industry sludge. Aggregates were produced in a bench-scale rotary kiln with three clay/sludge loadings (90/10, 70/30 and 50/50%). All three mixtures showed good bloating behavior during firing and the ceramic pellets (1-1.5cm diameter) had densities well below that required for light-weight aggregates. In the initial tests, the pore sizes of the aggregates were in general too large resulting in high water absorption. Comparisons between the composition of the two waste products and the aggregates showed a significant loss of fluorine (40-60%) during processing; a problem which may require flue gas treatment. Leach testing showed that the formed aggregates would not pose a human or environmental hazard in terms of fluorine mobilization.     

Non-isothermal flow of carbon dioxide in injection wells during geological storage

During sequestration, carbon dioxide within injection wells is likely to be in a dense state and therefore its weight within the wellbore will play an important role in determining the bottomhole pressure and thus the injection rate. However, the density could vary significantly along the well in response to the variation in pressure and temperature. A numerical procedure is formulated in this paper to evaluate the flow of carbon dioxide and its mixtures in non-isothermal wells. This procedure solves the coupled heat, mass and momentum equations with the various fluid and thermodynamic properties, including the saturation pressure, of the gas mixture calculated using a real gas equation of state. This treatment is particularly useful when dealing with gas mixtures where experimental data on mixture properties are not available and these must be predicted. To test the developed procedure two wellbore flow problems from the literature, involving geothermal gradients and wellbore phase transitions are considered; production of 97% carbon dioxide and injection of superheated steam. While these are not typical carbon dioxide injection problems they provide field observations of wellbore flow processes which encompass the mechanisms of interest for carbon dioxide injection, such as phase transition, temperature and density variations with depth. These two examples show that the developed procedure can offer accurate predictions. In a third application the role of wellbore hydraulics during a hypothetical carbon dioxide injection application is considered. The results obtained illustrate the potential complexity of carbon dioxide wellbore hydraulics for sequestration applications and the significant role it can play in determining the well bottomhole pressure and thus injection rate.     

Interactions of carbamazepine in soil: effects of dissolved organic matter

Pharmaceutical compounds (PCs) and dissolved organic matter (DOM) are co-introduced into soils by irrigation with reclaimed wastewater. We targeted carbamazepine (CBZ) as a model compound to study the tertiary interactions between relatively polar PCs, DOM, and soil. Sorption-desorption behavior of CBZ was studied with bulk clay soil and the corresponding clay size fraction in the following systems: (i) without DOM, (ii) co-introduced with DOM, and (iii) pre-adsorption of DOM before CBZ introduction. Sorption of the DOM to both sorbents was irreversible and exhibited pronounced sorption-desorption hysteresis. Carbamazepine exhibited higher sorption affinity and nonlinearity, and a higher degree of desorption hysteresis with the bulk soil than the corresponding clay size fraction. This was probably due to specific interactions with polar soil organic matter fractions that are more common in the bulk soil. Co-introduction of CBZ and DOM to the soil did not significantly affect the sorption behavior of CBZ; however, following pre-adsorption of DOM by the bulk soil, an increase in sorption affinity and decrease in sorption linearity were observed. In this latter treatment, desorption hysteresis of CBZ was significantly increased for both sorbents. We hypothesize that this was due to either strong chemical interactions of CBZ with the adsorbed DOM or physical encapsulation of CBZ in DOM-clay complexes. Based on this study, we suggest that DOM facilitates stronger interactions of polar PCs with the solid surface. This mechanism can reduce PC desorption ability in soils.     

Investigation of amine amino acid salts for carbon dioxide absorption

The carbon dioxide capture potential of amine amino acid salts (AAAS), formed by mixing equinormal amounts of amino acids; e.g. glycine, β-alanine and sarcosine, with an organic base; 3-(methylamino)propylamine (MAPA), was assessed by comparison with monoethanolamine (MEA), and with amino acid salt (AAS) from amino acid neutralized with an inorganic base; potassium hydroxide (KOH). Carbon dioxide absorption and desorption experiments were carried out on the solvent systems at 40 °C and 80 °C respectively. Experimental results showed that amine amino acid salts have similar CO₂ absorption properties to MEA of the same concentration. They also showed good signs of stability during the experiments. Amino acid salt from an inorganic base, KOH, showed lower performance in CO₂ absorption than the amine amino acid salts (AAAS) mainly due to a lower equilibrium temperature sensitivity. AAAS showed better performance than MEA of same concentration. AAAS from neutralization of sarcosine with MAPA showed the best performance and the performance could be further enhanced when promoted with excess MAPA. The solvent comparison is semi-quantitative since the bubble structure, and thus gas–liquid interfacial area may not be the same for all experiments, however superficial gas velocities were kept constant.     

Growth management of vetiver (Vetiveria zizanioides) under Mediterranean conditions

In spite of the advantages of Vetiver grass in light of environmental aspects, this plant is not used in the Mediterranean region. The objectives of the present study were: (i) to elucidate growth parameters and establishment of Vetiver under Mediterranean conditions suitable for its various environmental applications; and (ii) to develop management practices for growing vetiver under Mediterranean conditions. In greenhouse experiments conducted under controlled conditions it was found that, in general, increasing the minimum/maximum temperatures to 21-29 degrees C significantly increased plant height. In the Mediterranean region, this range of air temperatures is obtained mainly during the summer, from June to September. For air temperatures up to 15-23 degrees C the effect of day length on plant height was insignificant, whereas in air temperature >15-23 degrees C, the plant heights under long day conditions were significantly higher than under short day. The number of sprouts per plant increased exponentially with increasing air temperature, and was not significantly affected by the day length at any air temperature range. In open fields, the heights of irrigated vetiver plants were significantly higher than those of rain-fed plants. It was concluded that, once they were established, vetiver plants could survive the dry summer of the Mediterranean region under rain-fed conditions, but they would be shorter than under irrigation. Cutting or burning of the plant foliage during the spring did not improve the survival of vetiver during the dry summer. In order to obtain fast growth of vetiver and to increase the possibility of its using the rainwater, the plants should be planted in the winter, during February and March. However, under this regime, the vetiver plant cannot be used as a soil stabilizer during the first winter, because the plant is still small. In contrast, under irrigation it is advantageous to plant vetiver at the beginning of the summer; the plant then has sufficient time to grow and develop before the beginning of the winter, so that its effect as a soil stabilizer in the following wet winter could be maximal. It was found that vetiver could grow in a wide range of substrates, such as: sandy soil, loamy sand, clay soil, crushed limestone, sandy clay loam, and tuff/peat mixture.     

Enhanced desorption of herbicides sorbed on soils by addition of Triton X-100

A study of the desorption of atrazine (1-chloro-3-ethylamino-5-isopropylamino-2,4,6-triazine) and linuron [1-methoxy-1-methyl-3-(3,4-dichlorophenyl)urea] adsorbed on soils with different organic matter (OM) and clay contents was conducted in water and in the presence of the non-ionic surfactant Triton X-100 at different concentrations. The aim was to gain insight into soil characteristics in surfactant-enhanced desorption of herbicides from soils. Adsorption and desorption isotherms in water, in all Triton X-100 solutions for atrazine, and in solutions of 0.75 times the critical micelle concentration (cmc) and 1.50cmc for linuron fit the Freundlich equation. All desorption isotherms showed hysteresis. Hysteresis coefficients decreased for linuron and increased or decreased for atrazine in Triton X-100 solutions. These variations were dependent on surfactant concentration and soil OM and clay contents. In the soil-water-surfactant system desorption of linuron from all soils was always greater than in the soil-water system but for atrazine this only occurred at concentrations higher than 50cmc. For the highest Triton X-100 concentration (100cmc), the desorption of the most hydrophobic herbicide (linuron) was increased more than 18-fold with respect to water in soil with an OM content of 10.3% while the atrazine desorption was increased 3-fold. The effect of Triton X-100 on the desorption of both herbicides was very low in soil with a high clay content. The results indicate the potential use of Triton X-100 to facilitate the desorption of these herbicides from soil to the water-surfactant system. They also contribute to better understanding of the interactions of different molecules and surfaces in the complex soil-herbicide-water surfactant system.     

The effect of flow path and mixing layer on phosphorus release: physical mechanisms and temperature effects

Soil phosphorus (P) concentrations typically are greater in surface soils compared with subsurface soils. Surface soils have a greater chance to interact with runoff leading to P transport to streams. The thin surface layer where P concentrates is referred to as the mixing layer denoting where water and chemicals mix during transport. The objective of this study was to evaluate the effect of hydrologic flow paths on soluble reactive phosphorus (SRP) loss at two temperatures. Laboratory flumes were built to simulate infiltration, return flow, saturation excess, and interflow, and subsequent interaction with the mixing layer. The sandy loam soil in the flumes was kept at saturation throughout all experiments, so that biochemical effects were normalized. Flow through the flumes was maintained at 3.6 mm/h for 24 to 99 h (at 6 and 25 degrees C) with water entering and exiting the flumes at different ports (to simulate different flow paths) or as low intensity rainfall. Experiments were performed with and without an artificially created P-enriched surface layer (5 mm thick, total P increased from 1010 mg/kg in the original soil to 2310 mg/kg by addition of dissolved phosphate). Results indicated that (i) SRP release was greater in soil with a mixing layer than in soil without a mixing layer; (ii) SRP release was greater during experiments at 25 degrees C than at 6 degrees C; (iii) at 25 degrees C, SRP release was greatest when water traversed the mixing layer in the upward direction (i.e., in return flow), and by flow parallel to the mixing layer (i.e., surface runoff); and (iv) at 6 degrees C, SRP release in subsurface flow following rainfall was slightly greater than in return flow and infiltration. Our results confirmed the presence of a variable, temperature-dependent desorption process when runoff water interacted with the mixing layer. Our findings have important implications for how different water flow paths in and over the soil interact with P in the soil, and what the ultimate concentration will be in runoff and interflow.     

Sorption of cadmium and zinc from aqueous solutions by zeolite 4A, zeolite 13X and bentonite

The sorption and desorption of cadmium and zinc on zeolite 4A, zeolite 13X and bentonite has been studied using batch sorption studies. Parameters such as equilibrium time, effect of pH and sorbent dose were studied. The sorbents exhibited good sorption potential for cadmium and zinc with a peak value at pH 6.0 and 6.5, respectively. The sorption followed the Freundlich sorption model. More than 70% sorption occurred within 20 min and equilibrium was attained at around 90 min for the three sorbents. The metals sorption by zeolite 4A was higher than that by zeolite 13X and bentonite. The desorption studies were carried out using NaCl solution and the effect of NaCl concentration on desorption was also studied. Maximum desorption of 76% for cadmium and 80% for zinc occurred with 10% NaCl.     

Size distribution of organic matter and associated propiconazole in agricultural runoff material

Sorption and desorption characteristics of propiconazole (1-[[2-(2,4-dichlorophenyl)-4-propyl-1,3-dioxolan-2-yl]methyl]-1H-1,2,4-triazole) to different particle/aggregate-size fractions of agricultural runoff material were investigated. Emphasis was put on clay and colloidal size fractions to evaluate their role as potential sorbents and carriers for this pesticide. The runoff material was separated into size fractions ranging from 2 mm to ca. 15 nm by wet sieving, sedimentation, centrifugation, and membrane ultrafiltration. Each fraction was characterized by its organic C content and C/N ratio. Distinctive sorption properties of clay-sized particles and colloids were investigated. The obtained size fractions differed significantly in their organic C concentration, C/N ratio, and sorption properties to propiconazole. Organic matter was mainly associated in aggregates >2 microm. Binding of propiconazole to this coarse fraction made up 80% of the sorbed propiconazole. The distribution coefficient between solid and aqueous phases increased with decreasing particle size. The colloidal fraction (<0.16 microm) exhibited the highest sorbtivity, with a distribution coefficient of 113 L kg(-1), which was more than four times higher than that in the bulk sample (27 L kg(-1)). The fraction <2 microm represented 8% of the total sample weight, but contributed to 20% of the sorbed propiconazole. Strong hysteresis was observed for the sorption-desorption of propiconazole on the runoff material. Under dilution very little sorbed propiconazole will be released into the water phase. Due to its high sorbtivity and mobility and the strong sorption-desorption hysteresis, particles in the fraction <2 microm can be important carriers of propiconazole in runoff suspensions with high sediment load.     

Optimal Absorbent Evaluation for the CO2 Separating Process by Absorption Loading,Desorption Efficiency,Cost, and Environmental Tolerance

The CO₂ absorption capacities of potassium glycinate, potassium sarcosinate (choline, proline), mono-ethanolamine (MEA), and tri-ethanolamine were evaluated to find the optimal absorbent for separating CO₂ from gaseous products by a CO₂ purification process. The absorption loading, desorption efficiency, cost, and environmental tolerance were assessed to select the optimal absorbent. MEA was found to be the optimum absorbent for separating the CO₂ and H₂ mixture in gaseous product. The maximum absorption loading rate was 0.77 mol CO₂ per mol MEA at temperature of 20°C and absorbent concentration of 2.5 mol/L, whereas desorption efficiency was 90% by heating for 3 h at 130°C. MEA was found to be an optimal absorbent for the purification process of CO₂ during gaseous production.