A method for predicting the performance of packed columns operating with a reactive scrubbing liquid that control gaseous air pollutants

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.     

A Novel Design for Anaerobic Chemical Oxygen Demand and Nitrogen Removal from Leachate in a Semiaerobic Landfill

Abstract

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 ·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·day and 20 g COD/m³ ·day, while those of crushed column under anaerobic condition (column E) for COD and NO₃ ^?-N at about 400 and 150 g COD/m³ ·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.     

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.     

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.     

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.     

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.     

Deep bed filtration of anaerobic cattle manure effluents with natural zeolite

Abstract

This study was carried out in a pilot plant for the treatment of anaerobic cattle manure waste. The pilot plant consisted of a semicontinous anaerobic reactor, a settling tank, a filtration process and an ionic exchange column. The study was focused on the filtration process, with natural zeolite as filtering material. In the filtration process different media sizes of natural zeolites packed in columns were tested. The ranges of media size were 0.4 ‐ 1.0, 1.0 ‐ 3.0 and 3.0 ‐ 5.0 mm. Filtration systems operated by gravity flow from 2 to 10 m³m^‐2h^‐1. The process control was done by assays of solids, turbidity, total and soluble COD, ammonium and orthophosphate. The results showed a better behaviour in the filters packed with a media size range between 1.0 and 3.0 mm, operating at 7 m³m^‐2h^‐1, principally when effluent gross particles were previously retained in an Heterogeneous Media Filter, operating at 4 m³m^‐2h^‐1. The head losses diagrams in the filter runs were obtained, at each operational conditions. The hydraulic behaviour of traditional silica sand and natural zeolite beds were compared at the same operational conditions.     

Hydration Properties of Eco-Cement Pastes from Waste Sludge Ash Clinkers

Abstract

Three types of hydraulic cements have been developed by incorporating sludge ash from a primary sewage treatment plant and a water purification plant, as well as slag from steelworks (ferrate), as a partial replacement for clay, silica, alumina, and iron oxide in raw cement meal. The raw meal for the pre-determined recipes was prepared by heating it to 1400 °C for 6 hr in a clinkerization process, using a simulated incinerator and smelter. The major components of ordinary Portland cement, C₃S, C₂S, C₃A, and C₄AF, were all found in the clinkers. Of the three types of eco-cements, the eco-cement A paste was most similar to ordinary Portland cement in terms of composition and compressive strength development, while the eco-cement B paste showed early strength development. The differential thermal analysis species analyses indicated that the hydrates in the eco-cement pastes were mainly calcium hydroxide and CSH gels, like those found in ordinary Portland cement paste. Moreover, the degree of hydration, as determined by nuclear magnetic resonance, increased in all eco-cement pastes with an increasing curing age. The results indicate that it indeed is feasible to use sludge ash and ferrate to replace up to 20% of the mineral components of raw materials for cement.     

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.     

Removal of sulfamethoxazole and sulfapyridine by carbon nanotubes in fixed-bed columns

Sulfamethoxazole (SMX) and sulfapyridine (SPY), two representative sulfonamide antibiotics, have gained increasing attention because of the ecological risks these substances pose to plants, animals, and humans. This work systematically investigated the removal of SMX and SPY by carbon nanotubes (CNTs) in fixed-bed columns under a broad range of conditions including: CNT incorporation method, solution pH, bed depth, adsorbent dosage, adsorbate initial concentration, and flow rate. Fixed-bed experiments showed that pH is a key factor that affects the adsorption capacity of antibiotics to CNTs. The Bed Depth Service Time model describes well the relationship between service time and bed depth and can be used to design appropriate column parameters. During fixed-bed regeneration, small amounts of SMX (3%) and SPY (9%) were irreversibly bonded to the CNT/sand porous media, thus reducing the column capacity for subsequent reuse from 67.9 to 50.4 mg g^?1 for SMX and from 91.9 to 72.9 mg g^?1 for SPY. The reduced column capacity resulted from the decrease in available adsorption sites and resulting repulsion (i.e., blocking) of incoming antibiotics from those previously adsorbed. Findings from this study demonstrate that fixed-bed columns packed with CNTs can be efficiently used and regenerated to remove antibiotics from water.     

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.     

A comparative evaluation of the performance of full-scale high-rate methane biofilter (HMBF) systems and flow-through laboratory columns

Methane biofilter (MBF) technology, a cost effective method to control atmospheric emission of CH₄, is usually developed as a passively aerated system to control low-volume point-source emissions such as those from landfills with gas collection systems. Actively aerated high-rate methane biofilter (HMBF) systems are designed to overcome the shortcomings of passively aerated systems by ensuring the entire filter bed is utilized for CH₄ oxidation. Flow-through column experiments point to the fact that CH₄ oxidation rates of actively aerated systems could be several times higher than that of passively aerated systems. However, reports of the performance of field HMBF systems are not available in literature. Furthermore, there are no studies that demonstrate the possibility of using laboratory data in the design and operation of field systems. The current study was conducted to fill this research gap and involve a comparative study of the performance of laboratory columns to field performance of a HMBF system using solution gas produced at an oil battery site as the CH₄ source. The actively aerated column studies confirmed past results with high CH₄ oxidation rates; one column received air at two injection points and achieved an oxidation rate of 1417 g/m³/d, which is the highest reported value to date for compost-filled columns. Subsequent studies at a specially designed field HMBF filled with compost showed a higher oxidation rate of 1919 g/m³/d, indicating the possibility of exceeding the high CH₄ oxidation rates observed in the laboratory. The achievement of observed field oxidation rates being higher than those in the laboratory is attributed to the capability of maintaining higher temperatures in field HMBFs. Furthermore, results show that field HMBFs could operate at lower than stoichiometric air to CH₄ ratios, and lower retention times than that of laboratory columns. Results indicated that laboratory columns may not truly represent field behavior, and said results could only be used in the preliminary design of field HMBFs.     

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.     

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.     

The opposing effects of bacterial activity and gas production on anaerobic TCE degradation in soil columns

This laboratory study explores the effect of growth substrate concentration on the anaerobic degradation of trichloroethylene (TCE) in sand packed columns. In all columns the growth substrate rapidly degraded to gas, that formed a separate phase. Biomass accumulated in the 0–4.8 cm section of the columns in proportion to the influent growth substrate concentration and biomass concentrations in the remaining sections of all columns were similar to the column receiving the lowest substrate concentration. Increases in growth substrate concentration up to 3030 mg-COD l⁻¹ promoted TCE degradation, but a further increase to 14 300 mg-COD l⁻¹ reduced the amount of TCE completely dechlorinated but did not affect the production of chlorinated TCE intermediates. The mathematical model developed here satisfactorily described the enhancement in TCE dehalogenation for substrate concentration up to 3030 mg-COD l⁻¹; reproducing TCE dehalogenation for 14 300 mg-COD l⁻¹ required that the moisture content used in simulation be lowered to 0.1. The study shows that volatilization of TCE can be significant and volatilization losses should be taken into account when anaerobic activity in in-situ bioremediation applications is stimulated via addition of growth substrates. An implication of the modeling simulations is that maintaining a lower, but uniform, substrate concentration over the contaminated region may lead to faster contaminant degradation.     

Kinetics of endosulfan sorption on to wood charcoal

Abstract

A part of the research work conducted to evaluate the efficiency of a locally available low cost wood charcoal in removing endosulfan, an organochlorine insecticide, has been presented here in this paper. In the batch experiments conducted at 1 mg/I initial concentration of endosulfan, it was found that wood charcoal could remove endosulfan from water up to 95%. Kinetic profiles were developed for various conditions and they followed second order kinetic reactions. Adsorption equilibrium time was determined by two different approaches namely rough estimate and 2% slope criteria. The equilibrium time was found to be 5 hrs. Forward, reverse, and overall reaction rate constants were determined by approximating the kinetic data to the first order reversible kinetic model. Rate constants increased with increasing initial concentration of endosulfan. Rate limiting process was determined by using kinetics data and further confirmed by the multiple interruption test. Pore and film diffusion coefficients were determined from the half time equations. Film diffusion appeared to be the rate limiting which was further supported by the multiple interruption test.     

The use of nanovermiculite catalyst in the study of removal of the organic load and degradation of atrazine via ozone process in RPB reactor

Abstract

The main objective of this study is the degradation of a synthetic solution of atrazine by a modified vermiculite catalyzed ozonation, in a rotating packed bed (RPB) reactor. A 0.5?L RPB reactor was used to perform the experiments, using a Central Composite Design (CCD) response surface to construct the quadratic model based on the factors: pH, catalyst concentration and reactor rotation frequency. The response variable was the removal of the organic load measured in terms of Chemical Oxygen Demand (COD). After the complete quadratic model was constructed through the response surface, the COD degradation process had an optimal removal of 41% under the following conditions: pH 8.0, rotation of 1150?rpm and catalyst concentration 0.66?g L^?1.     

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.     

Backfitting Electrostatic Precipitators: Gas Velocity and Reliability Considerations

Abstract

The kinetic behavior of the toluene biofiltration process was investigated in this research. Toluene was used as a model compound for less water-soluble gas pollutants. The limiting factor in the overall toluene biofiltration process was determined by analyzing the effectiveness factor of the biofilm along the biofilter. Experiments were conducted in three laboratory-scale biofilters packed with mixtures of chaff/compost, D.E. (diatomaceous earth)/compost and GAC (granular activated carbon)/compost, respectively. A mathematical model previously proposed was verified in this study as being applicable to these biofilters packed with different filter materials. Both the experimental and theoretical results confirmed that the biodegradation rate along the biofilter followed the zero order, fractional order to first order kinetics as toluene concentration decreased. Moreover, at higher toluene concentration, biodegradation rate and mass flux of toluene were lower near the bottom of the biofilter due to substrate inhibition. Analysis of the effectiveness factor indicated that biofiltration of a less soluble compound such as toluene should not be operated at high gas flow rates (low gas residence times) due to the mass transfer limitation of such a system. At an approximate constant inlet toluene concentration of 0.9 g/m³, the toluene removal efficiency in these three biofilters would drop below 90% when the gas residence time decreased to 2.5, 2.5, and 2.0 min, respectively.