Dynamics of ammonia volatilization from simulated urine patches and aqueous urea applied to pasture. III. Field verification of a simplified model

Published field experimental data [11, 15, 19] were used to compare measured NH_3(g) losses following applications of urine or aqueous urea to pasture soils with values predicted by a simplified ammonia volatilization model [16]. Total measured losses were generally in close agreement with predictions. For example, predicted losses following applications of urine to a ryegrass-white clover pasture in Canterbury, New Zealand were 20.7% in summer and 22.4% in autumn and were highly correlated with measured losses of 21.5% and 24.4% respectively (r = 0.998).The model was also tested for instantaneous rate of ammonia gas loss at 33 discrete sampling times for the summer experiment. Correlations were again highly significant (r = 0.951 for urine and r = 0.885 for urea).The interception of urine solution by herbage and litter on the pasture surface is discussed and was shown to account for some of the discrepancies between measurements and predictions. Soil surface pH was confirmed as an important factor in determining the extent of ammonia gas loss, and the practicalities of measuring this parameter under field conditions are presented. It was concluded that the model offers the potential for predicting ammonia volatilization losses following urine or aqueous urea applications to short pasture in non-leaching, non-nitrifying environments.     

Experimental model validation of an integrated process for the removal of carbon dioxide from aqueous ammonia solutions

In this work modelling and experimental validation of an integrated process for the removal of carbon dioxide from ammonia solutions - the so called decarbonisation - is presented. In this process, carbon dioxide and small amount of ammonia is stripped out from the solution at ambient pressure in a packed column. Recovery of the stripped ammonia can be reached by combining absorption of ammonia and condensation of stripping steam. The integration of stripping, absorption and direct-contact condensation (DCC) can be achieved in one compact unit in which stripping takes place in the lower part of the packed column, and the DCC and ammonia absorption in its upper part. This unit has been modelled in a rigorous way considering heat and mass transfer as well as reaction rates in multicomponent reactive stripping, absorption and direct-contact condensation in packed columns (Ma?kowiak et al., 2009). Extensive experimental investigations in a pilot scale packed column with diameters of 0.15 and 0.32 m have been performed for both, the stripping and for DCC. Relevant operation parameters as well as column dimensions were varied during the experiments in order to investigate their influence on the selectivity of the decarbonisation and to achieve a broad data base for the validation. Experimental validation of the two sub-processes and the entire decarbonisation shows good agreement between calculated and experimental values. Based on the validated model a successful optimisation of the decarbonisation process in industrial scale has been performed, leading to increased carbon dioxide removal and reduction of ammonia losses.     

Ruthenium supported on zeolite A: preparation and characterisation of a stable catalyst for ammonia synthesis

Reaction of Ru(NH₃)₆Cl₃ with Na-A and K-A zeolites yielded oligomeric amino-oxo-complexes supported on the zeolite. Controlled thermal activation under hydrogen converted the precursor in a two-step reaction into an active catalyst with good long-term stability and resistance against small doses of oxygen poison. Several nanometers sized Ru metal particles are chemically bonded to the zeolite surface which provides in the K form an alkali promoter at the metal-zeolite interface. Extensive oxidation breaks the metal-support anchoring and re-reduction produces Ru metal particles sintering rapidly into large metal crystals with only small residual catalytic activity.     

Predicting the effect of soil-water-air dynamics on ammonia volatilization from applied urea with a mechanistic model

To assess the influence of varying soil water and soil air contents on ammonia volatilization from surface applied urea, a mechanistic model is used to simulate the system. The results are discussed in terms of the effects of soil-water-air dynamics on the movement of urea, ammoniacal-nitrogen and soil base, and on the rate of urea hydrolysis, and their influence on ammonia volatilization. Changing the soil moisture between 90% and 125% of field capacity did not have a marked influence on ammonia volatilization. The predicted losses were at their minimum with a moisture content slightly above field capacity, and increased sharply as the soil moisture fell below 90% of the field capacity. Ammonia volatilization losses measured by experiment at differentf values agreed very well with those predicted by the model. The relative contribution of the liquid pathway over the gaseous pathway of movement of NH₃ through soil increased with increase inf, and, at a givenf, decreased with increase in the pH.     

A phosphorus budget of a poultry farm and a dairy farm in the southeastern U.S., and the potential impacts of diet alterations

Current and potential environmental problems associated with P transport from lands receiving high application rates of animal waste are a major concern. Phosphorus management strategies are needed to reduce P loading on land. This study was conducted to compare on-farm P budgets for a modern broiler farm and a dairy farm under traditional diets and management practices. Phosphorus inputs, recycling and outputs were assessed for both farms. A typical broiler and a dairy farmer from North Carolina were interviewed and pertinent information for the study was obtained, in cooperation with extension agents, and other professionals associated with the farms. The annual on-farm P surplus for the broiler farm was 6,380 kg, while that for the dairy farm was 1,141 kg. This corresponds to an annual application of 65 kg P ha^–1 for the broiler farm and 20 kg P ha^–1 for the dairy farm in excess of removal. The potential for reducing P surpluses by the addition of phytase enzymes and/or the use of low phytic acid corn (Zea mays L.) feed in the broiler farm diet was also assessed. Estimates by animal nutritionists indicate that feed supplementation with phytase enzyme can reduce the broiler farm's P surplus by 33%. The use of low phytic acid corn can reduce the surplus by 49% and a combination of the two can reduce the surplus by 58%. In this study, the incorporation of soybean (Glycine max (L.) Merr.) and alfalfa (Medicago sativa) land into the waste utilization plan of the dairy farm decreases the annual P surplus from 20 to 9 kg P ha^–1. The use of new feed technology and expanding waste application to a larger land base can significantly alter the P budgets of broiler and dairy farms and reduce P surpluses, minimizing the risk of environmental problems.     

Ammonia/hydrogen mixtures in an SI-engine: Engine performance and analysis of a proposed fuel system

In recent years there has been increasing focus on using metal ammine complexes for ammonia storage. In this paper a fuel system for ammonia fuelled internal combustion engines using metal ammine complexes as ammonia storage is analyzed. The use of ammonia/hydrogen mixtures as an SI-engine fuel is investigated in the same context. Ammonia and hydrogen were introduced into the intake manifold of a CFR-engine. Series of experiments with varying excess air ratio and different ammonia to hydrogen ratios was conducted. This showed that a fuel mixture with 10 vol.% hydrogen performs best with respect to efficiency and power. A comparison with gasoline was made, which showed efficiencies and power increased due to the possibility of a higher compression ratio. The system analysis showed that it is possible to cover a major part of the necessary heat using the exhaust heat. It is proposed to reduce the high NO_x emissions using SCR as exhaust after treatment.     

Transferring the color imagery from an image: A color network model for assisting color combination

In order to transfer the color imagery from an image to another object to generate color schemes, a color network model is proposed. It consists of two subnets: source net for describing the color information of the reference image; target net for demonstrating the target object to be colored. Thus, the problem of reusing features of color patterns is translated into the mapping process from the source net to target net. Four indicators are designed to measure the conformity between the two nets: color sequence, adjacency, concentration, and the subspace size. In the meantime, a comprehensive aesthetic evaluation given by the designer is introduced to search the optimum combination of the four indicators to help generate imagery matching schemes. A prototype system is developed based on CorelDraw as a design tool. The feasibility of the color network model is then verified through a color combination of graphic design task.     

Modelling of non-stationary ammonia synthesis kinetics over an iron catalyst: I. Deriving a model and estimating parameters from transient response data

The transient reaction kinetic models of ammonia synthesis in a Berty reactor are identified and the parameters in the models are estimated from their transient responses. The basic model is founded on widely held views concerning the mechanism of ammonia formation on iron catalyst. The results obtained in this study show that a two-site, dissociative adsorption model is acceptable while a competitive adsorption model is not.     

Dynamics of ammonia volatilization from simulated urine patches and aqueous urea applied to pasture. II. Theoretical derivation of a simplified model

Theoretical considerations for the development of a simplified model for predicting volatilization losses of ammonia gas (NH_3(g)) from the urine patches of grazing herbivores in a pasture ecosystem are presented. The volatilization of NH_3(g) is treated as a physico-chemical phenomenon based on the soil solution chemistry of urine patches to develop a general equation to describe the rate of volatilization from a pasture surface. A semi-empirical approach was then used in which published data define typical limits for the parameters appearing in the volatilization equation. This led to the simplification of the general volatilization equation into a more useable and more readily verifiable form.The dominant factor in determining the rate of volatilization of NH_3(g) was shown to be the soil surface pH. To better understand the dynamics of pH changes within urine patches, the more extensive literature dealing with volatilization losses from flooded soils was reviewed. From the apparent similarities between the two systems a procedure was described by which a careful monitoring of soil surface pH as a function of time could be used to solve the simplified equation.To calculate NH_3(g) fluxes this model requires the following as input data: a knowledge of the disposition of the applied-N within the soil profile; the rate of urea hydrolysis in the topsoil; and soil surface pH and temperature measurements throughout the duration of a volatilization event.     

Simulation of swirling coal combustion using a full two-fluid model and an AUSM turbulence-chemistry model

A full two-fluid model of reacting gas-particle flows with an algebraic unified second-order moment turbulence-chemistry model for the turbulent reaction rate of NO formation are used to simulate swirling coal combustion. The sub-models are the k-ε-k_p two-phase turbulence model, the EBU-Arrhenius volatile and CO combustion model, the six-flux radiation model, coal devolatilization model and char combustion model. The prediction results are in good agreement with the experimental results taken from references.     

Alternative fuel and gasoline in an SI engine: A comparative study of performance and emissions characteristics

The strict regulation of environmental laws, the price of oil and its restricted resources, has made engine manufacturers use other energy resources instead of oil and its products. Despite the fact that nowadays alternative fuels are not currently widely used in vehicular applications, using these kinds of fuels will be definitely inevitable in the future. In this paper, a computer code is developed in Matlab environment and then its results are validated with experimental data. This simulated engine model could be used as an powerful tool to investigate the performance and emission of a given SI engine fueled by alternative fuels including hydrogen, propane, methane, ethanol and methanol. Also, the superior of alternative fuels is shown by comparing the performance and emissions of alternative fueled engines to those in conventional fueled engines. Eventually, it is concluded that volumetric efficiency of the engine working on hydrogen is the lowest (28% less that gasoline fueled engine), gasoline produce more power than the all being tested alternative fuels and BSFC of methanol is 91% higher than that of gasoline while BSFC of hydrogen is 63% less than gasoline.     

Heterogeneous modeling of an autothermal membrane reactor coupling dehydrogenation of ethylbenzene to styrene with hydrogenation of nitrobenzene to aniline: Fickian diffusion model

Coupling of reactions in catalytic membrane reactors provides a route to process intensification. Dehydrogenation of ethylbenzene and hydrogenation of nitrobenzene form a promising pair of processes to be coupled in a membrane reactor. The heat released from the hydrogenation side is utilized to break the endothermality on the dehydrogenation side, while hydrogen produced on the dehydrogenation side permeates through the hydrogen-selective membranes, enhances the equilibrium conversion of ethylbenzene and reacts with nitrobenzene on the permeate side to produce aniline. Mathematical reactor models are excellent tools to evaluate the extent of improvement before experiments are set up. However, a careful selection of phenomena considered by the reactor model is needed in order to obtain accurate model predictions.To investigate the effect of the intraparticle resistances on the performance of the cocurrent configuration of the coupling reactor, a heterogeneous fixed bed reactor model is developed with Fickian diffusion inside the catalyst pellets. For the condition of interest, the styrene yield is found to be 82% by the homogenous model, 73% by the heterogeneous model for isothermal pellets, and 69% by the heterogeneous model with non-isothermal pellets. Hence, the homogeneous model overestimates the yield by 5–15% of their actual values.     

Emission Factors for Aerial Pyrotechnics and Use in Assessing Environmental Impact of Firework Displays: Case Study from Malta

The measurement of emission factors for PM₁₀ for different aerial (display) firework devices, namely, flash crackers, stars, blast charges, and fuse matches as produced in Malta are reported herein. Additionally, the content in fireworks‐generated PM₁₀ of Al, Ba, Cu, Sr, and Sb is determined. PM₁₀ values were as follows in kg per kg composition: blast charges 0.054; flash crackers 0.43; stars 0.175 (red); 0.176 (blue); 0.254 (green); 0.123 (white); fuse matches 0.204. The metal content in PM₁₀ from fireworks (in kg per kg composition) depends on the type of device burnt, with green stars producing Ba at 0.0553, blue stars Cu at 0.0123, and red stars Sr at 0.0057. White stars and flash crackers containing Sb₂S₃ produce Sb at 0.0395 and 0.1083 kg per kg composition, respectively. We used these emission factors and trade information on chemicals used for the manufacture of pyrotechnics in Malta to estimate the total load of PM₁₀ and associated metalliferous content released to the atmosphere from aerial fireworks displays. In 2007, PM₁₀ emissions amounted to about 37 t and metal loads (in kg) were Al (2193), Ba (1161), Sb (504), Cu (331), and Sr (142). The data and modeling approach presented herein illustrates a general methodology for the assessment of environmental risk from display fireworks especially when more specific information is unavailable.     

A comparison of a pseudo-homogeneous non-equilibrium model and a three-phase non-equilibrium model for catalytic distillation

A comparison of computer simulation results of catalytic distillation (CD) obtained from a three-phase non-equilibrium model and a pseudo-homogeneous non-equilibrium model was performed. Simulations were carried out on the CD processes for the production of ethyl cellosolve (EC) and diacetone alcohol (DAA) using both the pseudo-homogeneous non-equilibrium model and the three-phase non-equilibrium model. Similar results for the synthesis of EC were obtained using these two models. However, only the three-phase non-equilibrium model could adequately describe the CD process for the aldol condensation of acetone (Ac) at low reflux flow rates. Hence our results suggest that for a reaction system that is kinetically controlled, a pseudo-homogeneous non-equilibrium may adequately simulate the temperature profile, yield and selectivity for a CD process. However, for a CD process that is sensitive to solid–liquid mass transfer, the three-phase non-equilibrium model is required.     

Modeling of a bacterial and fungal biofilter applied to toluene abatement: Kinetic parameters estimation and model validation

Biofiltration has been established as a promising alternative to conventional air pollution control technologies. However, gas biofilters modeling has been less developed than experimental research due to the complexity of describing the fundamental processes and the lack of globally accepted physical, chemical and biological parameters. In addition, biofiltration modeling based on degradation activity of fungi has been rarely considered. For this reason, in this work, a dynamic model describing toluene abatement by a bacterial and fungal biofilter is developed, calibrated and validated. The mathematical model is based on detailed mass balances which include the main processes involved in the system: convection, absorption, diffusion and biodegradation. The model was calibrated and validated using experimental data obtained from two equal lab-scale biofilters packed with coconut fiber and pine leaves, respectively. Both reactors were operated under similar conditions during 100 days at an empty bed residence time of 60 s and an average inlet load of 77 g toluene m⁻³ h⁻¹. Biofilters were initially inoculated with a bacterial consortium, even though reactors were mostly colonized by fungi after 60 days of operation according to microscopic observation and reactors pH. Removal efficiency increased notably from 20% for the bacterial period to 80% for the fully developed fungal biofilters. Since kinetic parameters are strongly dependent on the biological population, semi-saturation constants for toluene and maximum growth rates were determined for bacterial and fungal operation periods. Kinetic parameters were fitted by means of an optimization routine using either outlet concentrations or removal efficiency data from the coconut fiber biofilter. A novel procedure in gas biofilters modeling was considered for checking the model calibration, by the assessment of the parameters confidence interval based on the Fisher Information Matrix (FIM). Kinetic parameters estimated in the coconut fiber reactor were validated in the pine leaves biofilter for bacterial and fungal operation. Adequate model fitting to the experimental outlet gas concentration for both bacterial and fungal operation periods was verified by using a standard statistical test.     

N2O and NO emission from agricultural fields and soils under natural vegetation: summarizing available measurement data and modeling of global annual emissions

The number of published N₂O and NO emissions measurements is increasing steadily, providing additional information about driving factors of these emissions and allowing an improvement of statistical N-emission models. We summarized information from 1008 N₂O and 189 NO emission measurements for agricultural fields, and 207 N₂O and 210 NO measurements for soils under natural vegetation. The factors that significantly influence agricultural N₂O emissions were N application rate, crop type, fertilizer type, soil organic C content, soil pH and texture, and those for NO emissions include N application rate, soil N content and climate. Compared to an earlier analysis the 20% increase in the number of N₂O measurements for agriculture did not yield more insight or reduced uncertainty, because the representation of environmental and management conditions in agro-ecosystems did not improve, while for NO emissions the additional measurements in agricultural systems did yield a considerable improvement. N₂O emissions from soils under natural vegetation are significantly influenced by vegetation type, soil organic C content, soil pH, bulk density and drainage, while vegetation type and soil C content are major factors for NO emissions. Statistical models of these factors were used to calculate global annual emissions from fertilized cropland (3.3 Tg N₂O-N and 1.4 Tg NO-N) and grassland (0.8 Tg N₂O-N and 0.4 Tg NO-N). Global emissions were not calculated for soils under natural vegetation due to lack of data for many vegetation types.     

A new model for estimation of water uptake of an organic coating by EIS: The tortuosity pore model

In this work, a new and more intricate model of estimate water uptake inside an organic coating by impedance measurements is proposed, the tortuosity pore model (TPM). In this model, the organic coating (film) is considered to be a ternary system, composed of liquid (solution), solid (coating matrix) and gas (air) phases. Moreover, the pores tortuosity inside the coating is taken into consideration. Comparison between this new model and the other models found in the literature will be presented, showing that this new model presents for water uptake better correlation with the values obtained by gravimetry.     

A temperature-dependent model for predicting release rates of pheromone from a polyethylene tubing dispenser

A model was developed to describe release of two formulations of tetradecenyl acetates in Shin Etsu polyethylene tubing pheromone dispensers. Change in pheromone column length in the polyethylene tubing was modeled bydl/dt=l ... (a+bT)/dt (wherel is column length,t is time interval, andT is average temperature for that time interval). Regression of the natural log of relative change in liquid length against time interval and accumulated day degrees in orchards produced the coefficientsa andb. The model was validated by comparing predicted and actual liquid length remaining in field-aged dispensers, as well as measuring release rates by using gas chromatography. Mean daily orchard temperatures and measurement of column length of dispensers on a single date were used to accurately predict column length within 15%, after six months. Predictions of instantaneous release rate were also made from this model, and other possible model uses and limitations are discussed.     

A simplified model of nitric oxide emission from a circulating fluidized bed combustor

A simplified mathematical model leading to a closed form of solution is developed for estimation of nitric oxide emission from a coal fired circulating fluidized bed (CFB) furnace. The furnace is divided into two sections: a lower section below and an upper section above the secondary air injection level. Reactions in the cyclone and the return leg are neglected. Furnace dimensions, coal feed rate, coal composition and furnace temperature are inputs to the model which was validated against several pilot scale and commercial units. Experimental results from two pilot plants and two commercial power plants agree with model predictions. A sensitivity analysis was carried out using the model to examine the effect of different operating parameters and coal properties on the overall NO emission from the furnace. It was found that excess air and furnace temperature are most important factors influencing the NO emission level. The primary to secondary air ratio influences the NO emission level reasonably. Properties of coal are other factors which affect the NO emission to a large extent. The model, though it invovles some simplification, predicts the overall emission of NO with a level of accuracy accepted in commercial operation.