A Method for Predicting the Performance of Packed Columns Operating with a Reactive Scrubbing Liquid That Control Gaseous Air Pollutants

Abstract

A method for predicting the performance of packed columns that control gaseous air pollutants has been developed that exploits the advances in both computer software and hardware commonly used by practicing engineers. The solution of the simultaneous partial differential equations that describe the absorption process in packed columns that occurs in the presence of chemical reaction is obtained by converting the partial differential equations to systems of ordinary differential equations. These systems of ordinary differential equations are then solved using the method of lines along with a variable step, variable order numerical method. The method is applicable to systems in which there are multiple reactions within the liquid phase. The reactions can be of any order and can be reversible. The programming is simple and the machine running time is minimal. The method is illustrated here with an example.     

A reaction-based paradigm to model reactive chemical transport in groundwater with general kinetic and equilibrium reactions

This paper presents a reaction-based water quality transport model in subsurface flow systems. Transport of chemical species with a variety of chemical and physical processes is mathematically described by M partial differential equations (PDEs). Decomposition via Gauss-Jordan column reduction of the reaction network transforms M species reactive transport equations into two sets of equations: a set of thermodynamic equilibrium equations representing N(E) equilibrium reactions and a set of reactive transport equations of M-N(E) kinetic-variables involving no equilibrium reactions (a kinetic-variable is a linear combination of species). The elimination of equilibrium reactions from reactive transport equations allows robust and efficient numerical integration. The model solves the PDEs of kinetic-variables rather than individual chemical species, which reduces the number of reactive transport equations and simplifies the reaction terms in the equations. A variety of numerical methods are investigated for solving the coupled transport and reaction equations. Simulation comparisons with exact solutions were performed to verify numerical accuracy and assess the effectiveness of various numerical strategies to deal with different application circumstances. Two validation examples involving simulations of uranium transport in soil columns are presented to evaluate the ability of the model to simulate reactive transport with complex reaction networks involving both kinetic and equilibrium reactions.     

Contaminant transport in groundwater in the presence of colloids and bacteria: Model development and verification

Colloids and bacteria (microorganisms) naturally exist in groundwater aquifers and can significantly impact contaminant migration rates. A conceptual model is first developed to account for the different physiochemical and biological processes, reaction kinetics, and different transport mechanisms of the combined system (contaminant–colloids–bacteria). All three constituents are assumed to be reactive with the reactions taking place between each constituent and the porous medium and also among the different constituents. A general linear kinetic reaction model is assumed for all reactive processes considered. The mathematical model is represented by fourteen coupled partial differential equations describing mass balance and reaction processes. Two of these equations describe colloid movement and reactions with the porous medium, four equations describe bacterial movement and reactions with colloids and the porous medium, and the remaining eight equations describe contaminant movement and its reactions with bacteria, colloids, and the porous medium. The mass balance equations are numerically solved for two-dimensional groundwater systems using a third-order, total variance-diminishing scheme (TVD) for the advection terms. Due to the complex coupling of the equations, they are solved iteratively each time step until a convergence criterion is met. The model is tested against experimental data and the results are favorable.     

Analytical solutions for multiple species reactive transport in multiple dimensions

Many numerical computer codes used to simulate multi-species reactive transport and biodegradation have been developed in recent years. Such numerical codes must be validated by comparison of the numerical solutions with an analytical solution. In this paper, a method for deriving analytical solutions of the partial differential equations describing multiple species multi-dimensional transport with first-order sequential reactions is presented. Although others have developed specific solutions of multi-species transport equations, here a more general analytical approach, capable of describing any number of reactive species in multiple dimensions is derived. A substitution method is used to transform the multi-species reactive transport problem to one that can be solved using previously published single-species solutions for various initial and boundary conditions. One- and three-dimensional examples are presented to illustrate the steps involved in extending single-species solutions to a four-species system with sequential first-order reactions.     

An analytically solved kinetic model for pesticide degradation in single compartment systems

An analytical kinetic model was developed to simulate the degradation of pesticides in systems such as soil or water. Based on a single compartment system, a set of simultaneous first-order differential equations was analytically solved by the eigenvalue and eigenvector method. The developed model is capable of simulating the concentrations of parent compound and any net of degradation products connected by irreversible reactions.     

Modeling microbial-mediated reduction in batch reactors

The governing equations that depict microbially-mediated reduction of heavy metals in the subsurface include a system of coupled nonlinear partial differential equations (PDE's) that describe physical (transport), chemical (sorption), and microbial (reduction/oxidation) processes. The existence of nonlinear reaction terms makes numerical simulations more challenging; however, with the advent of time-splitting solution algorithms, nonlinear reaction terms can be isolated from the convective-dispersive components of the governing transport equations and then solved as a coupled system of nonlinear ordinary differential equations (ODE's). In this paper, four methods are evaluated for solving coupled systems of nonlinear ODE's that describe microbially-mediated reduction/oxidation processes. The evaluation involves a series of comparisons of transient simulations of electron donor oxidation, electron acceptor reduction, and microbial biomass accumulation. The methods evaluation is initiated with a comparison of simulation results obtained with the four methods to those generated with an analytical model. Next, laboratory observations, of nitrite consumption by Nitrobacter winogradski in batch reactors are used in a comparison of batch system simulations generated using each of the four methods and BIOKEMOD (biogeochemical kinetic/equilibrium reaction model). The evaluation finds one of the four methods, the quasi-steady-state approximation (QSSA), to be among the most accurate and easiest to implement. Final validation of the QSSA is performed simulating experimental results of microbially-mediated chromium reductions in batch cultures.     

Leaching of the organophosphorus nematicide fosthiazate

Fosthiazate is an organophosphorus nematicide which was recently included in Annex I of the Directive 91/414/EEC under the clause that it should be used with special care in soils vulnerable to leaching. Thus, the leaching of fosthiazate was investigated in columns packed with three different soils which represented situations of high (site 2), intermediate (site 1) and low (site 3) leaching potential. The recommended dose of fosthiazate was applied at the surface of the soil columns and fosthiazate fate and transport was investigated for the next two months. Fosthiazate concentrations in the leachate collected from the bottom of the columns packed with soil from site 2 exceeded 0.1 microgl(-1) in most cases. This soil was characterized as acidic, indicating longer fosthiazate persistence, with low organic matter content, indicating weak adsorption, thus representing a situation vulnerable to leaching. In contrast, the lowest concentrations of fosthiazate in the leachate were evident in the columns packed with soil from site 3. This soil was characterized as alkaline, indicating faster degradation, with higher organic matter content, indicating stronger adsorption, thus representing a situation not favoring leaching of fosthiazate. The highest concentration of fosthiazate in the leachate from the columns packed with soil from site 2 was 3.44 microgl(-1) compared to 1.17 and 0.16 microgl(-1), which were the corresponding maximum values measured in columns packed with soil from sites 1 and 3, respectively. The results of the current study further suggest that fosthiazate is mobile in soil and can leach under conducive soil conditions like acidic soils with low organic matter content.     

Metal mobility during in situ chemical oxidation of TCE by KMnO4

The potential for trace-metal contamination of aquifers as a side effect of In Situ Chemical Oxidation (ISCO) of chlorinated solvent contamination by KMnO(4) is investigated with column experiments. The experiments investigate metal mobility during in situ chemical oxidation of TCE by KMnO(4) under conditions where pH, flow rate, KMnO(4), TCE, and trace-metal concentrations were controlled. During ISCO, the injection of MnO(4) creates oxidizing conditions, and acidity released by the reactions causes a tendency toward low pH in aquifers. In order to evaluate the role of pH buffering on metal mobility, duplicate columns were constructed, one packed with pure silica sand, and one with a mixture of silica sand and calcite. Aqueous solutions of TCE and KMnO(4) (with 1 mg/L Cu, Pb, Zn, Mo, Ni, and Cr(VI)) were allowed to mix at the inlet to the columns. After the completion of the experiments, samples of Mn oxide were removed from the columns and analyzed by analytical scanning and transmission electron microscopy. In order to relate the results of the laboratory experiments to field settings, the analyses of Mn-oxide samples from the lab experiments were compared to samples of Mn oxide collected from a field-scale chemical-oxidation experiment that were also analyzed by analytical electron microscopy as well as time-of-flight secondary-ion mass spectroscopy. The pH ranged from 2.40 in the silica sand column to 6.25 in the calcite-containing column. The data indicate that aqueous Mo, Pb, Cu and Ni concentrations are attenuated almost completely within the columns. In contrast, Zn concentrations are not significantly attenuated and Cr(VI) is transported conservatively. The results indicate that within the range 2.40 to 6.25, metal mobility is not affected by pH. Comparison of analyses of Mn-oxide from the lab and field demonstrate that a variety of metals are sequestered from solution by Mn oxide.     

Assessment of interfacial mass transfer in water-unsaturated soils during vapor extraction

This paper presents results of a numerical investigation of soil vapor extraction (SVE) systems at the laboratory scale. The SVE technique is used to remove volatile chlorinated hydrocarbons (VCHC) from the water-unsaturated soil zone. The developed numerical model solves equations of flow, transport and interfacial mass transfer regarding an isothermal n-component and three-phase system. The mathematical model is based on a simple pore network and phase distribution model and designed to be scaled by a characteristic length. All mathematical expressions are structured into VCHC specific and VCHC non-specific parameters. Furthermore, indicators are introduced that help to separate thermodynamic equilibrium from thermodynamic non-equilibrium domains and to determine the controlling physical parameters. For numerical solution, the system of partial differential equations is discretized by a finite volume method and an implicit Euler time stepping scheme. Computational effort is reduced notably through techniques that enable spatial and temporal adaptivity, through a standard multigrid method as well as through a problem-oriented sparse-matrix storage concept. Computations are carried out in two dimensions regarding the laboratory experiment of Fischer et al. [Water Resour. Res. 32 (12) 1996 3413]. By varying the characteristic length scale of the pore network and phase distribution model, it is shown that the experimental gas phase concentrations cannot be explained only by the volatility and diffusivity of the VCHC. The computational results suggest a sorption process whose significance grows with the aqueous activity of the less or non-polar organic compounds.     

堆肥 + 零价铁可渗透反应墙修复黄土高原地下水中铬铅复合污染简

为了研究堆肥+零价铁混合可渗透反应墙（PRB）修复黄土高原地下水中铬铅复合污染的可行性,分别用堆肥、零价铁、堆肥+ 零价铁、堆肥+ 零价铁+活性炭为反应介质,通过模拟柱实验考察PRB修复铬铅复合污染黄土高原地下水的效果。结果表明,在实验进行30 d后当反应柱1和2对六价铬的去除率接近于零,而且对二价铅的去除率迅速下降时,反应柱3对2种污染物仍保持较高的去除率;反应介质质量比为10：2：1的反应柱4和质量比为10：1：2的反应柱5对污染物的去除效果均优于质量比为10：1：1的反应柱3;反应50 d后,添加活性炭的反应柱6对2种污染物的去除率仍在90%。这说明使用堆肥+零价铁混合可渗透反应墙修复黄土高原地下水中铬铅复合污染是可行的;且以堆肥+零价铁作为介质的反应柱去除效果优于单独以堆肥或铁粉为介质的反应柱;增加铁粉或堆肥的用量有利于铬铅复合污染的去除;且同时添加活性炭更有助于污染物的去除。     

Transport of Escherichia coli in 25 m quartz sand columns

To help improve the prediction of bacteria travel distances in aquifers laboratory experiments were conducted to measure the distant dependent sticking efficiencies of two low attaching Escherichia coli strains (UCFL-94 and UCFL-131). The experimental set up consisted of a 25 m long helical column with a diameter of 3.2 cm packed with 99.1% pure-quartz sand saturated with a solution of magnesium sulfate and calcium chloride. Bacteria mass breakthrough at sampling distances ranging from 6 to 25.65 m were observed to quantify bacteria attachment over total transport distances (α(L)) and sticking efficiencies at large intra-column segments (α(i)) (>5m). Fractions of cells retained (F(i)) in a column segment as a function of α(i) were fitted with a power-law distribution from which the minimum sticking efficiency defined as the sticking efficiency of 0.001% bacteria fraction of the total input mass retained that results in a 5 log removal were extrapolated. Low values of α(L) in the order 10(-4) and 10(-3) were obtained for UCFL-94 and UCFL-131 respectively, while α(i)-values ranged between 10(-6) to 10(-3) for UCFL-94 and 10(-5) to 10(-4) for UCFL-131. In addition, both α(L) and α(i) reduced with increasing transport distance, and high coefficients of determination (0.99) were obtained for power-law distributions ofα(i) for the two strains. Minimum sticking efficiencies extrapolated were 10(-7) and 10(-8) for UCFL-94 and UCFL-131, respectively. Fractions of cells exiting the column were 0.19 and 0.87 for UCFL-94 and UCL-131, respectively. We concluded that environmentally realistic sticking efficiency values in the order of 10(-4) and 10(-3) and much lower sticking efficiencies in the order 10(-5) are measurable in the laboratory, Also power-law distributions in sticking efficiencies commonly observed for limited intra-column distances (<2m) are applicable at large transport distances(>6m) in columns packed with quartz grains. High fractions of bacteria populations may possess the so-called minimum sticking efficiency, thus expressing their ability to be transported over distances longer than what might be predicted using measured sticking efficiencies from experiments with both short (<1m) and long columns (>25 m). Also variable values of sticking efficiencies within and among the strains show heterogeneities possibly due to variations in cell surface characteristics of the strains. The low sticking efficiency values measured express the importance of the long columns used in the experiments and the lower values of extrapolated minimum sticking efficiencies makes the method a valuable tool in delineating protection areas in real-world scenarios.     

Multicomponent simulation of wastewater-derived nitrogen and carbon in shallow unconfined aquifers. I. Model formulation and performance

One of the most common methods to dispose of domestic wastewater involves the release of septic effluent from drains located in the unsaturated zone. Nitrogen from such systems is currently of concern because of nitrate contamination of drinking water supplies and eutrophication of coastal waters. The objectives of this study are to develop and assess the performance of a mechanistic flow and reactive transport model which couples the most relevant physical, geochemical and biochemical processes involved in wastewater plume evolution in sandy aquifers. The numerical model solves for variably saturated groundwater flow and reactive transport of multiple carbon- and nitrogen-containing species in a three-dimensional porous medium. The reactive transport equations are solved using the Strang splitting method which is shown to be accurate for Monod and first- and second-order kinetic reactions, and two to four times more efficient than sequential iterative splitting. The reaction system is formulated as a fully kinetic chemistry problem, which allows for the use of several special-purpose ordinary differential equation (ODE) solvers. For reaction systems containing both fast and slow kinetic reactions, such as the combined nitrogen-carbon system, it is found that a specialized stiff explicit solver fails to obtain a solution. An implicit solver is more robust and its computational performance is improved by scaling of the fastest reaction rates. The model is used to simulate wastewater migration in a 1-m-long unsaturated column and the results show significant oxidation of dissolved organic carbon (DOC), the generation of nitrate by nitrification, and a slight decrease in pH.     

A novel design for anaerobic chemical oxygen demand and nitrogen removal from leachate in a semiaerobic landfill

The removal capacity of carbon and nitrogen from an artificial leachate was evaluated by using laboratory-scale columns, and a design was proposed to remove nitrogen more efficiently from a semiaerobic landfill. Five columns (i.e., two artificial municipal waste columns under anaerobic and semiaerobic conditions, an artificial construction waste column under semiaerobic conditions, and two crushed stone columns under anaerobic and semiaerobic conditions) were used. The influent load rates of organics [g chemical oxygen demand (COD)/m3 x day], NH4+, NO3- and aeration conditions for the columns were varied, and the removal capacities of the columns for COD, NH4+-N, and NO3--N were measured. Among the packed column materials, crushed stone was shown to be most effective in removing COD, NH4+ N, and NO3--N from artificial leachate. Average removal rates of crushed column under the semiaerobic condition (column D) for COD and NH4+-N were estimated at about 150 g COD/m3 x day and 20 g COD/m3 x day, while those of crushed column under anaerobic condition (column E) for COD and NO3--N at about 400 and 150 g COD/m3 x day, respectively. It also was found that denitrification and nitrification reactions in column D occurred at the same time, and the ratio of denitrification to nitrification was estimated to be about 80%. Therefore, an anaerobic structure, which could be attached to the bottom of a main pipe in a semiaerobic landfill, is suggested to remove nitrogen and organic substances more effectively.     

Modelling soot and SOF emissions from a diesel engine

Modelling of soot and SOF emissions from a typical European turbocharged diesel engine has been made. The model consists of a detailed kinetic mechanism with 472 reactions (120 chemical species) and data from the thermodynamic diagnostic procedure of the combustion process of the engine. The forward kinetic constants were obtained from literature and the background constants from a self-developed non-linear fitting routine based on the Marquardt algorithm. The dilution and mixing processes inside the engine are represented by a simple Wiebe function. The system of ordinary differential equations is solved with the Rosenbrock method for rigid systems and using the interpolating Lagrange polynomials to calculate the heat capacity of each species at the corresponding temperature. The kinetic model has been implemented in Digital Visual Fortran 6.0. The model has been executed for five different fuels and three mixtures of biodiesel and reference diesel operating under three diverse conditions from the European transient urban/extraurban Certification Cycle and the results of soot and SOF predicted are compared with experimental data.     

Laboratory study on leachability of five herbicides in South Australian soils

Norflurazon, oxadiazon, oxyfluorfen, trifluralin and simazine are herbicides widely used in the vineyards of the Barossa Valley, South Australia. The leaching behaviour of norflurazon, oxadiazon, oxyfluorfen and trifluralin was investigated on four key soils in the Barossa Valley. Leaching potential on packed soil columns and actual mobility using intact soil columns were investigated. On the packed soil columns, norflurazon was the most leachable herbicide. More of the herbicides were detected in the leachates from the sandy soils (Mountadam and Nuriootpa) than from the clayey soils (Lyndoch and Tanunda). Organic matter is generally low in soils in the Barossa region. Porosity and saturated conductivity significantly affect herbicide movement and in the sandy Mountadam and Nuriootpa soils, the water flux is greater than for the higher clay content Lyndoch and Tanunda soils. Increasing the time interval between herbicide application and the incidence of "rainfall" reduced the amounts of herbicides found in the leachates. The use of intact soil columns and including simazine for comparison showed that both norflurazon and simazine were present in the leachates. Simazine was the first herbicide to appear in leachates. Sectioning of the intact soil columns after leaching clearly demonstrated that norflurazon and simazine reached the bottom of the soil columns for all soils studied. Greater amounts of norflurazon were retained in the soil columns compared with simazine. The other herbicides were mostly retained in the initial sections of the soil columns.     

Transport and reduction of nitrate in clayey till underneath forest and arable land

Transport and reduction of nitrate in a typically macroporous clayey till were examined at variable flow rate and nitrate flux. The experiments were carried out using saturated, large diameter (0.5 m), undisturbed soil columns (LUC), from a forest and nearby agricultural sites. Transport of nitrate was controlled by flow along the macropores (fractures and biopores) in the columns. Nitrate reduction (denitrification) determined under active flow mainly followed first order reactions with half-lives (t(1/2)) increasing with depth (1.5-3.5 m) from 7 to 35 days at the forest site and 1-7 h at the agricultural site. Nitrate reduction was likely due to microbial degradation of accumulated organic matter coupled with successive consumption of O2 and NO3- in the macropore water followed by reductive dissolution of Fe and Mn from minerals along the macropores. Concentrations of total organic carbon measured in soil samples were near identical at the two study sites and consequently not useful as indicator for the observed differences in nitrate reduction. Instead the high reduction rates at the agricultural site were positively correlated with elevated concentration of water-soluble organic carbon and nitrate-removing bacteria relative to the forest site. After high concentrations of water-soluble organic carbon in the columns from the agricultural site were leached they lost their elevated reduction rates, which, however, was successfully re-established by infiltration of new reactive organics represented by pesticides. Simulations using a calibrated discrete fracture matrix diffusion (DFMD) model could reasonably reproduce the denitrification and resulting flux of nitrate observed during variable flow rate from the columns.     

Laboratory study on leachability of five herbicides in South Australian soils

Abstract

Norflurazon, oxadiazon, oxyfluorfen, trifluralin and simazine are herbicides widely used in the vineyards of the Barossa Valley, South Australia. The leaching behaviour of norflurazon, oxadiazon, oxyfluorfen and trifluralin was investigated on four key soils in the Barossa Valley. Leaching potential on packed soil columns and actual mobility using intact soil columns were investigated. On the packed soil columns, norflurazon was the most leachable herbicide. More of the herbicides were detected in the leachates from the sandy soils (Mountadam and Nuriootpa) than from the clayey soils (Lyndoch and Tanunda). Organic matter is generally low in soils in the Barossa region. Porosity and saturated conductivity significantly affect herbicide movement and in the sandy Mountadam and Nuriootpa soils, the water flux is greater than for the higher clay content Lyndoch and Tanunda soils. Increasing the time interval between herbicide application and the incidence of “rainfall”; reduced the amounts of herbicides found in the leachates. The use of intact soil columns and including simazine for comparison showed that both norflurazon and simazine were present in the leachates. Simazine was the first herbicide to appear in leachates. Sectioning of the intact soil columns after leaching clearly demonstrated that norflurazon and simazine reached the bottom of the soil columns for all soils studied. Greater amounts of norflurazon were retained in the soil columns compared with simazine. The other herbicides were mostly retained in the initial sections of the soil columns.     

Oxygen Stratification in Industrial Boiler Stacks

The DSS/2 software system was used to numerically simulate oxygen stratification effects in a typical industrial boiler stack. The model developed for the simulation involves turbulent mass transfer in a tube with a constant, high mass flux from the walls of the tube. The concentration profile is considered to be developing, but the velocity profile is assumed to be fully developed. The model is for a gaseous system at constant temperature and pressure; the transport properties are shown to be constant. The universal velocity profile for turbulent flow and von Karman’s expressions for the turbulent eddy diffusivity are incorporated in the model. An expression for a wall concentration profile corresponding to conditions of high mass flux at the wall is developed. The model is then expressed as a system of partial differential equations which are solved using the numerical method of lines together with the DSS/2 numerical integration system. The resulting concentration profiles are presented for various flux rates which might be encountered in a typical stack. These profiles indicate that a potential for oxygen stratification in stacks does exist; they also suggest that careful placement of the oxygen cell probe can help minimize such errors.     

Movement of metolachlor and terbuthylazine in core and packed soil columns

Movement of metolachlor and terbuthylazine including a bromide tracer was studied in core and packed soil columns in PVC pipes (80 mm diameter, 15 mm depth) with two German soil types viz: silt loam and loamy silt. The breakthrough curves (BTCs) for bromide indicated some preferential flow of water both under conventional tillage (CN) and no-till (NT) simulation with silt loam soil. The herbicides leached to a greater extent in NT columns than in CN columns. Leaching was higher in loamy silt soil than in silt loam soil under CN conditions. This result is in agreement with the higher sorption capacity of silt loam having higher organic carbon compared to loamy silt having low organic carbon. Adsorption strength of the herbicides did not affect their breakthrough time, but was reflected in the slope and maximum height of the BTCs. The BTCs showed the expected inverse relationship between leaching and adsorption with greater mobility of the weakly-sorbed metolachlor than the more strongly sorbed terbuthylazine. Maximum amounts of the applied herbicides were recovered from the top soil layer in intact columns. Metolachlor was more mobile in packed columns than in core columns.