The challenge in understanding the corrosion mechanisms under oxyfuel combustion conditions

Basic research on the corrosive effect of flue gases has been performed at the BAM Federal Institute for Materials Research and Testing (Germany). Conditions at both high and low temperatures were simulated in specially designed experiments. Carburization occured in flue gases with high CO₂ content and temperatures higher than 500 °C. In SO₂ containing flue gases sulphur was detected in the oxide scale. At lower temperatures no corrosion was observed when gases with low humidity were investigated. Humidity higher than 1500 ppm was corrosive and all steels with Cr contents lower than 12% revealed corroded surfaces. At low temperatures below 10 °C a mixture of sulphuric and nitric acid condensed on metal surfaces. Acid condensation caused severe corrosion. Humidity, CO₂, O₂, and SO₂ contents are the important factors determining corrosion. Below 300 °C acid condensation is the primary reason for corrosion. Low humidity and low temperatures are conditions which can be expected in the CO₂ separation and treatment process. This work includes major conditions of the flue gas and CO₂ stream in CCS plants and CCS technology.     

Storage and characterization of cotton gin waste for ethanol production

In 2002, about 17.1 million bales of cotton were ginned in the United States and the estimated cotton gin waste was 2.25 × 10⁹ kg. The disposal of cotton gin waste (CGW) is a significant problem in the cotton ginning industry, but CGW could be potentially used as feedstock for bioethanol. Freshly discharged CGW and stored CGW were characterized for storage stability and potential for ethanol production by determining their summative compositions. The bulk densities of the fresh wet and dry CGW were 210.2 ± 59.9 kg m⁻³ and 183.3 ± 52.2 kg m⁻³, respectively. After six months of storage the volume of piles A, B, and C decreased by 38.7%, 41.5%, and 33.3%, respectively, relative to the volume of the pile at the start of the storage. The ash content of the CGW was very high ranging from 10% to 21% and the acid-insoluble fraction was high (21–24%). The total carbohydrate content was very low and ranged from 34% to 49%. After three months storage, chemical compositional analysis showed the loss of total carbohydrates was minimal but after six months, the losses were as high as 25%. This loss of carbohydrates suggests that under open storage conditions, the feedstock must be processed within three months to reduce ethanol yield losses.     

Study of inexpensive oxygen carriers for chemical looping combustion

Norwegian industrial tailings and by-products, as well as naturally occurring minerals and ores have been surveyed with the purpose of identifying candidate oxygen carrier materials for use in a chemical looping combustion process. Nine materials, based on manganese and/or iron oxide, were selected for an initial screening test; six were deemed promising and were hence investigated further. Thermogravimetric experiments were performed to investigate the oxygen capacity, the reaction kinetics and reversibility of the oxygen absorption reaction. A manganese ore with a reversible capacity of 4.9 wt% oxygen at 1000 °C was selected as the most promising for chemical looping combustion applications. This material was modified by addition of calcia to explore the possibility of enhancing the kinetic, catalytic and mechanical properties. The addition of excess calcium relative to manganese resulted in formation of calcium manganite and related phases. The oxygen capacity of the modified material was 4.5 wt% at 1000 °C, but it has potential advantages in terms of kinetics and chemical and mechanical stability relative to the pure ore.     

The use of digital photos to assess visual cover for wildlife in rangelands

Grassland vegetation can provide visual cover for terrestrial vertebrates. The most commonly used method to assess visual cover is the Robel pole. We test the use of digital photography as a more accurate and repeatable method. We assessed the digital photography method on four forage grassland species (Pseudoroegneria spicata, Festuca campestris, Poa pratensis, Achnatherum richardsonii). Digital photos of 2-dimensional cutout silhouettes of three bird species sharp-tailed grouse, western meadowlark and savannah sparrow were used to model the impact of clipping (i.e., grazing) on visual cover. In addition, photos of artificial voles were used to model litter on cover available to small mammals. Nine sites were sampled and data were analyzed by the dominant grass species in each study plot. Regression analysis showed that digital photos (r² = 0.62) were a better predictor than the Robel pole (r² = 0.26) for assessment of cover. Clipping heights showed that clipping at less than 15 cm left the silhouettes 50% exposed. Digital photo analysis revealed that visual cover was affected by the type of grass species, with F. campestris > P. pratensis > A. richardsonii > P. spicata. Biomass and litter were both positively related to cover for small mammals.     

Treatment of municipal wastewater using a contact oxidation filtration separation integrated bioreactor

A new contact oxidation filtration separation integrated bioreactor (CFBR) was used to treat municipal wastewater. The CFBR was made up of a biofilm reactor (the upper part of the CFBR) and a gravitational filtration bed (the lower part of the CFBR). Polyacrylonitrile balls (50 mm diameter, 237 m²/m³ specific surface, 90% porosity, and 50.2% packing rate) were filled into the biofilm reactor as biofilm attaching materials and anthracite coal (particle size 1–2 mm, packing density 0.947 g/cm³, non-uniform coefficient (K₈₀ = d₈₀/d₁₀) < 2.0) was placed into the gravitational filtration bed as filter media. At an organic volumetric loading rate of 2.4 kg COD/(m³ d) and an initial filtration velocity of 5 m/h in the CFBR, the average removal efficiencies of COD, ammonia nitrogen, total nitrogen and turbidity were 90.6%, 81.4%, 64.6% and 96.7% respectively, but the treatment process seemed not to be effective in phosphorus removal. The average removal efficiency of total phosphorus was 60.1%. Additionally, the power consumption of the CFBR was less than 0.15 kWh/m³ of wastewater treated, and less than 1.5 kWh/kg BOD₅ removal.     

A preliminary investigation of the efficacy of riparian fencing schemes for reducing contributions from eroding channel banks to the siltation of salmonid spawning gravels across the south west UK

The low productivity of salmonids in many river systems across the UK is testament to their intolerance of water quality perturbations including those associated with excessive sedimentation. Catchment and fishery managers concerned with combating such issues require reliable information on the key sources of the sediment problem to target management and on the efficacy of the mitigation options being implemented. In recognition of the latter requirement, a pre- and post-remediation sediment sourcing survey was used to examine the potential for using sediment tracing to assemble preliminary information on the efficacy of riparian fencing schemes for reducing sediment contributions from eroding channel banks to salmonid spawning gravels in the Rivers Camel, Fal, Lynher, Plym, Tamar and Tavy in the south west of the UK. Respective estimates of the overall mean proportion (±95% confidence limits) of the interstitial sediment input to salmonid spawning gravels originating from eroding channel banks during the pre- (1999–2000) and post-remediation (2008–2009) study periods were computed at 97 ± 1% vs. 69 ± 1%, 94 ± 1% vs. 91 ± 1%, 12 ± 1% vs. 10 ± 1%, 92 ± 1% vs. 34 ± 1%, 31 ± 1% vs. 16 ± 1% and 90 ± 1% vs. 66 ± 1%. Whilst the study demonstrates the potential utility of the fingerprinting approach for helping to assemble important information on the efficacy of bank fencing as a sediment source control measure at catchment scale, a number of limitations of the work and some suggestions for improving experimental design are discussed. Equivalent data are urgently required for many sediment mitigation options to help inform the development of water quality policy packages designed to protect aquatic ecosystems.     

Artificial aggregate made from waste stone sludge and waste silt

In this research, waste stone sludge obtained from slab stone processing and waste silt from aggregate washing plants were recycled to manufacture artificial aggregate. Fine-powdered stone sludge was mixed with waste silt of larger particle size; vibratory compaction was applied for good water permeability, resulting in a smaller amount of solidifying agent being used. For the densified packing used in this study, the mix proportion of waste stone sludge to waste silt was 35:50, which produced artificial aggregate of more compact structure with water absorption rate below 0.1%. In addition, applying vibratory compaction of 33.3 Hz to the artificial aggregate and curing for 28 days doubled the compressive strength to above 29.4 MPa. Hence, recycling of waste stone sludge and waste silt for the production of artificial aggregate not only offers a feasible substitute for sand and stone, but also an ecological alternative to waste management of sludge and silt.     

Optimization of Fenton oxidation pre-treatment for B. thuringiensis – Based production of value added products from wastewater sludge

Fenton oxidation pretreatment was investigated for enhancement of biodegradability of wastewater sludge (WWS) which was subsequently used as substrate for the production of value- added products. The Response surface method with fractional factorial and central composite designs was applied to determine the effects of Fenton parameters on solubilization and biodegradability of sludge and the optimization of the Fenton process. Maximum solubilization and biodegradability were obtained as 70% and 74%, respectively at the optimal conditions: 0.01 ml H₂O₂/g SS, 150 [H₂O₂]₀/[Fe²⁺]₀, 25 g/L TS, at 25 °C and 60 min duration. Further, these optimal conditions were tested for the production of a value added product, Bacillus thuringiensis (Bt) which is being used as a biopesticide in the agriculture and forestry sector. It was observed that Bt growth using Fenton oxidized sludge as a substrate was improved with a maximum total cell count of 1.63 × 10⁹ CFU ml^?1 and 96% sporulation after 48 h of fermentation. The results were also tested against ultrasonication treatment and the total cell count was found to be 4.08 × 10⁸ CFU ml^?1 with a sporulation of 90%. Hence, classic Fenton oxidation was demonstrated to be a rather more promising chemical pre-treatment for Bt - based biopesticide production using WWS when compared to ultrasonication as a physical pre-treatment.     

Determination of effects of turbulence flow in a cathode environment on electricity generation using a tidal mud-based cylindrical-type sediment microbial fuel cell

We examined the possibility of harvesting electricity from the surface of a tidal mud flat using a cylindrical-type sediment microbial fuel cell (SMFC), a marine mud battery (MMB), which can be applied in a sea environment where the ebb and flow occur due to tidal difference. In addition, we indirectly investigated the influence of ebb and flow in a lab, using aeration, argon gassing, and by agitating the cathodic solution. The MMBs consisted of cylindrical acrylic compartments containing a nylon membrane, an anode, and a cathode in a single body. The MMBs were stuck vertically into an artificial tidal mud flat such that the anode electrode was in direct contact with the tidal mud surface. As a result, the maximum current and power density generated were 35 mA/m² and 9 mW/m², respectively, thus verifying that it is possible to harvest electricity from the surface of a tidal mud flat using an MMB without burying the anode electrode in the tidal mud. Furthermore, the results of tests using an artificial turbulence flow showed the flow induced by the tidal ebb and flow could allow the performance of MMBs to be enhanced.     

Application of polyacrylamide to reduce phosphorus losses from a Chinese purple soil: A laboratory and field investigation

Use of anionic polyacrylamide (PAM) to control phosphorus (P) losses from a Chinese purple soil was studied in both a laboratory soil column experiment and a field plot experiment on a steep slope (27%). Treatments in the column study were a control, and PAM mixed uniformly into the soil at rates of 0.02, 0.05, 0.08, 0.10, and 0.20%. We found that PAM had an important inhibitory effect on vertical P transport in the soil columns, with the 0.20% PAM treatment having the greatest significant reduction in leachate soluble P concentrations and losses resulting from nine leaching periods. Field experiments were conducted on 5 m wide by 21 m long natural rainfall plots, that allowed collection of both surface runoff and subsurface drainage water. Wheat was planted and grown on all plots with typical fertilizer applied. Treatments included a control, dry PAM at 3.9 kg ha^?1, dry PAM at 3.9 kg ha^?1 applied together with lime (CaCO₃ at 4.9 t ha^?1), and dry PAM at 3.9 kg ha^?1 applied together with gypsum (CaSO₄·2H₂O at 4 t ha^?1). Results from the field plot experiment in which 5 rainfall events resulted in measurable runoff and leachate showed that all PAM treatments significantly reduced runoff volume and total P losses in surface runoff compared to the control. The PAM treatments also all significantly reduced water volume leached to the tile drain. However, total P losses in the leachate water were not significantly different due to the treatments, perhaps due to the low PAM soil surface application rate and/or high experimental variability. The PAM alone treatment resulted in the greatest wheat growth as indicated by the plant growth indexes of wheat plant height, leaf length, leaf width, grain number per head, and dried grain mass. Growth indexes of the PAM with Calcium treatments were significantly lesser. These results indicate that the selection and use of soil amendments need to be carefully determined based upon the most important management goal at a particular site (runoff/nutrient loss control, enhanced plant growth, or a combination).     

Carbon dioxide storage capacity in uneconomic coal beds in Alberta,Canada: Methodology,potential and site identification

Methodology is presented for a first-order regional-scale estimation of CO₂ storage capacity in coals under sub-critical conditions, which is subsequently applied to Cretaceous-Tertiary coal beds in Alberta, Canada. Regions suitable for CO₂ storage have been defined on the basis of groundwater depth and CO₂ phase at in situ conditions. The theoretical CO₂ storage capacity was estimated on the basis of CO₂ adsorption isotherms measured on coal samples, and it varies between ∼20 kt CO₂/km² and 1260 kt CO₂/km², for a total of approximately 20 Gt CO₂. This represents the theoretical storage capacity limit that would be attained if there would be no other gases present in the coals or they would be 100% replaced by CO₂, and if all the coals will be accessed by CO₂. A recovery factor of less than 100% and a completion factor less than 50% reduce the theoretical storage capacity to an effective storage capacity of only 6.4 Gt CO₂. Not all the effective CO₂ storage capacity will be utilized because it is uneconomic to build the necessary infrastructure for areas with low storage capacity per unit surface. Assuming that the economic threshold to develop the necessary infrastructure is 200 kt CO₂/km², then the CO₂ storage capacity in coal beds in Alberta is greatly reduced further to a practical capacity of only ∼800 Mt CO₂.     

Mineralization of integrated gasification combined-cycle power-station wastewater effluent by a photo-fenton process

The aim of this work was to study the mineralization of wastewater effluent from an integrated-gasification combined-cycle (IGCC) power station sited in Spain to meet the requirements of future environmental legislation. This study was done in a pilot plant using a homogeneous photo-Fenton oxidation process with continuous addition of H₂O₂ and air to the system.The mineralization process was found to follow pseudo-first-order kinetics. Experimental kinetic constants were fitted using neural networks (NNs). The NNs model reproduced the experimental data to within a 90% confidence level and allowed the simulation of the process for any values of the parameters within the experimental range studied. At the optimum conditions (H₂O₂ flow rate = 120 mL/h, [Fe(II)] = 7.6 mg/L, pH = 3.75 and air flow rate = 1 m³/h), a 90% mineralization was achieved in 150 min.Determination of the hydrogen peroxide consumed and remaining in the water revealed that 1.2 mol of H₂O₂ was consumed per each mol of total organic carbon removed from solution. This result confirmed that an excess of dissolved H₂O₂ was needed to achieve high mineralization rates, so continuous addition of peroxide is recommended for industrial application of this process.Air flow slightly improved the mineralization rate due to the formation of peroxo-organic radicals which enhanced the oxidation process.     

Watershed-scale assessment of arsenic and metal contamination in the surface soils surrounding Miyun Reservoir,Beijing, China

Concentrations of As and selected metals were determined in surface soils of the Miyun Reservoir watershed of Beijing, China. The degree to which concentrations of As and metals exceeded the corresponding background concentration of soils was: Cr > Cu > Zn > As > Ni with no apparent anthropogenic contamination with Cd and Pb. Based on the results of a combination of multivariate statistics and geostatistical analysis, greater concentrations of Cr and Ni in soils were determined to be primarily from iron ore mining near where the Chaohe River enters the northeast portion of the reservoir. Agricultural activities were responsible for the observed elevated concentrations of Cu and Zn in soils. Relatively great concentrations of As were found in soils near the upstream regions of the Baihe River in Chicheng County where small gold mining activities have taken place. The greatest potential for adverse effects of Cr and Cu occurred along the eastern shore of Miyun Reservoir.     

Amine volatility in CO2 capture

Amine volatility is a key screening criterion for amines to be used in CO₂ capture. Excessive volatility may result in significant economic losses and environmental impact. It also dictates the capital cost of the water wash. This paper reports measured amine volatility in 7 m MEA (monoethanolamine), 8 m PZ (piperazine), 7 m MDEA (n-methyldiethanolamine)/2 m PZ (piperazine), 12 m EDA (ethylenediamine), and 5 m AMP (2-amino-2-methyl-1-propanol) at 40–60 °C with lean and rich loadings giving CO₂ partial pressures of 0.5 and 5 kPa at 40 °C. The amine concentrations were chosen to maximize CO₂ capture capacity at acceptable viscosity. At the lean loading condition (where volatility is of greatest interest), the amines are ranked in order of increasing volatility: 7 m MDEA/2 m PZ (6/2 ppm), 8 m PZ (8 ppm), 12 m EDA (9 ppm), 7 m MEA (31 ppm), and 5 m AMP (112 ppm). The apparent amine partial molar excess enthalpies in these systems were estimated to range from ～10 to 87 kJ/mol of amine.     

In-depth analysis of aluminum flows in Austria as a basis to increase resource efficiency

Based on the method of material flow analysis (MFA), a static model of Austrian aluminum (Al) flows in 2010 was developed. Extensive data research on Al production, consumption, trade and waste management was conducted and resulted in a detailed model of national Al resources. Data uncertainty was considered in the model based on the application of a rigorous concept for data quality assessment. The model results indicated that the growth of the Austrian “in-use” Al stock amounts to 11 ± 3.1 kg yr⁻¹ cap⁻¹. The total “in-use” Al stock was determined using a bottom-up approach, which produced an estimate of 260 kg Al cap⁻¹. Approximately 7 ± 1 kg of Al yr⁻¹ cap⁻¹ of old scrap was generated in 2010, of which 20% was not recovered because of losses in waste management processes. Quantitatively, approximately 40% of the total scrap input to secondary Al production originated from net imports, highlighting the import dependency of Austrian Al refiners and remelters. Uncertainties in the calculation of recycling indicators for the Austrian Al system with high shares of foreign scrap trade were exemplarily illustrated for the old scrap ratio (OSR) in secondary Al production, resulting in a possible range of OSRs between 0 and 66%. Overall, the detailed MFA in this study provides a basis to identify resource potentials as well as resource losses in the national Al system, and it will serve as a starting point for a dynamic Al model to be developed in the future.     

Coupled reservoir-geomechanical analysis of CO2 injection and ground deformations at In Salah,Algeria

In Salah Gas Project in Algeria has been injecting 0.5–1 million tonnes CO₂ per year over the past 5 years into a water-filled strata at a depth of about 1800–1900 m. Unlike most CO₂ storage sites, the permeability of the storage formation is relatively low and comparatively thin with a thickness of about 20 m. To ensure adequate CO₂ flow-rates across the low-permeability sand-face, the In Salah Gas Project decided to use long-reach (about 1–1.5 km) horizontal injection wells. In an ongoing research project we use field data and coupled reservoir-geomechanical numerical modeling to assess the effectiveness of this approach and to investigate monitoring techniques to evaluate the performance of a CO₂ injection operation in relatively low-permeability formations. Among the field data used are ground surface deformations evaluated from recently acquired satellite-based inferrometry (InSAR). The InSAR data shows a surface uplift on the order of 5 mm per year above active CO₂ injection wells and the uplift pattern extends several km from the injection wells. In this paper we use the observed surface uplift to constrain our coupled reservoir-geomechanical model and conduct sensitivity studies to investigate potential causes and mechanisms of the observed uplift. The results of our analysis indicate that most of the observed uplift magnitude can be explained by pressure-induced, poro-elastic expansion of the 20-m-thick injection zone, but there could also be a significant contribution from pressure-induced deformations within a 100-m-thick zone of shaly sands immediately above the injection zone.     

Substance flow analysis of cadmium in Korea

Substance flow analysis (SFA) of cadmium in Korea was carried out to analyze and predict cadmium flows, stocks, and future flows using both static and dynamic models. Cadmium is widely used in industry due to its strong corrosion and chemical resistance at high temperature, excellent electrical conduction, and low melting-point. Cadmium is produced as a by-product from the production processes for zinc and lead ingots. It is used for Ni–Cd batteries, polyvinylchloride (PVC) stabilizers, alloy products, pigments, and others.This examines the current cadmium flows and stocks using static SFA, and aims in predicting the future cadmium flows and stocks in Korea using dynamic SFA. From the static model, 2820 tonnes of cadmium ingots were produced, 0.04 tonnes imported and 2740 tons exported in Korea in 2009. In addition, 81 tonnes of cadmium were used in the manufacture of cadmium products: 80 tonnes for cadmium alloy products and 1 tonne for others. Finally, 175 tonnes of cadmium were imported into Korea for Ni–Cd batteries, 140 tonnes for PVC stabilizers, and 55 tonnes for pigments. Cadmium was used in various industries such as construction (221 tonnes), electrics and electronics (130 tonnes – including cadmium in imported products), transportation (30 tonnes) and others (30 tonnes). In 2009, 430 tonnes of industrial cadmium were discharged, with 10 tonnes being recycled and 420 tonnes discarded.From the dynamic model, cadmium stocks in Korea were estimated to be about 5120 tonnes in 2009. The industrial consumption in 2030 will be reduced to only 110 tonnes, only 27% of the current consumption of 410 tonnes in 2009, due to DIRECTIVE 2002/95/EC OF THE EUROPEAN PARLIAMENT of 27 January 2003 on the restriction of the use of certain hazardous substances in electrical and electronic equipment (RoHS). One possible solution to the Cd oversupply problem is use in cadmium telluride photovoltaic (CdTe PV) systems which have low life cycle Cd emissions (0.02 g Cd/GWh) and high end-of-life semiconductor recycling yields (95%).     

Environmental resource footprinting of drug manufacturing: Effects of scale-up and tablet dosage

The formulation and scale-up of batch processes is one of the major challenges in the development of pharmaceutical dosage forms and at the same time a significant resource demanding process which is generally overlooked in environmental sustainability assessments. First, this paper proposes general trends in the experience curve of cumulative resource consumption of pharmaceutical tablet manufacturing of PREZISTA^® 800 mg through wet granulation (WG) at four consecutive scales in both R&D and manufacturing environments (resp. WG1 = 1 kg/h, WG5 = 5 kg/h, WG30 = 30 kg/h and WG240 = 240 kg/h). Second, the authors aim at evaluating the environmental impact from a life cycle perspective of a daily consumption of PREZISTA^® 2× 400 mg tablets versus the bioequivalent PREZISTA^® 800 mg tablet which was launched to enhance patient compliance. Environmental sustainability assessment was conducted at three different system boundaries, which enables identification, localization and eventually reduction of burdens, in this case natural resource extraction. Exergy Analysis (EA) was used at process level (α) and plant level (β) while a cradle-to-gate Exergetic Life Cycle Assessment (ELCA) was conducted at the overall industrial level (γ) by means of the CEENE method (Cumulative Exergy Extraction from the Natural Environment). Life cycle stages taken into account are Active Pharmaceutical Ingredient (API) production, Drug Product (DP) production and Packaging. At process level (α), the total resource extraction for the manufacturing of one daily dose of PREZISTA^® (800 mg tablet) amounted up to 0.44 MJ_ex at the smallest scale (WG1) while this amount proved to be reduced by 58%, 79% and 83% at WG5, WG30 and WG240 respectively. Expanding the boundaries to the overall industrial level (γ) reveals that the main resource demand is at the production of the Active Pharmaceutical Ingredient (API), excipients, packaging materials and cleaning media used in DP production. At the largest scale (WG240) the use of cleaning media during DP production contributes considerably less to the total resource extraction. Overall, the effect of scale-up and learning on resource consumption during DP production showed to possess a power-law experience curve y = 2.40 * x^−0.57 when shifting from WG1 (smallest lab scale) to WG240 (industrial manufacturing). Tablet dosage (2× 400 mg versus 1× 800 mg) did not significantly affect the absolute environmental burden. However, the relative contribution of resource categories did change due to the different production technology. It could be concluded that in meeting social and economic demands by launching the PREZISTA^® 800 mg tablet, no trade-off in environmental burden occurred. On the long term, future research should strive to take into account R&D processes and all services related to pipeline activities taking place prior to market launch and eventually to allocate impacts to the final product.