Effect of Metallic Iron Concentration on End-Product Distribution during Metallic Iron-Assisted Autotrophic Denitrification

The main objective of this study was to determine the optimum composition of a reactive porous medium containing sand and metallic iron, to be used for Fe(0)-assisted hydrogenotrophic denitrification. This determination is important to ensure that the end-product distribution after such treatment is acceptable, i.e., ammonia formation due to abiotic nitrate reduction by metallic iron in such media is minimized, while a reasonable rate of biological denitrification is maintained. Based on a previous study it was established that steel wool, with its relatively low specific surface area, exhibited the least propensity to abiotically reduce nitrate. It was also established that to achieve acceptable end-product distribution, the steel wool concentration in the reactive porous media has to be lowered even below the lowest value, i.e., 4.0?g steel wool/m3 of sand, used during that study. It was further hypothesized that to counter any detrimental effect of lower steel wool concentration on biological nitrate removal rate, increase of the retention time in porous media to values higher than 13 days, the maximum value investigated in that study, may be necessary. In the present study, experiments were conducted in batch reactors containing denitrifying microorganisms and various concentrations of steel wool and in semibatch reactors containing sand seeded with denitrifying microorganisms and various concentrations of steel wool. Based on the results of the semibatch experiments, it appears that to achieve acceptable end-product distribution, the steel wool concentration in the reactive porous media has to be maintained around 2.0?g steel wool/m3 sand and the corresponding retention time in the reactive media must be around 26 days.     

Enhanced Sand Filtration for Storm Water Phosphorus Removal

Batch studies with an initial phosphorus concentration typical of storm water were conducted at the University of Minnesota on C 33 sand, calcareous sand, limestone, three blast oxygen furnace (BOF) by-products, aluminum oxide, and chopped granular steel wool for the removal of dissolved phosphorus from synthetic storm water runoff. Based on the findings of these batch studies, sand filtration enhanced with steel wool, calcareous sand, or limestone has the potential to be a practical and cost-effective method of removing dissolved phosphorus from storm water runoff. Column studies are then performed on four enhancements with C 33 sand filtration: calcareous sand, limestone, chopped granular steel wool, and steel wool fabric. Synthetic storm water runoff with a variable dissolved phosphorus concentration passed through the columns while the flow rate was measured and effluent samples were taken and analyzed for total and dissolved phosphorus concentration and pH. As found in the batch studies, C 33 sand retained dissolved phosphorus but the capacity was quickly exhausted. Combinations of C 33 sand with limestone or calcareous sand clogged the columns and prevented them from draining completely. Steel wool, however, significantly increased the duration and level of phosphorus retention as compared to C 33 sand alone and did not clog the columns. Between 34 and 81% of the dissolved phosphorus was retained by the six steel-enhanced columns. Fine oxidized iron particles observed in the effluent are too small to be completely captured by typical geotextile fabric and may compromise phosphorus removal performance, but phosphorus adsorbed to iron oxide will be of limited bioavailability. Steel-enhanced sand filtration is modeled with contact time, total mass of phosphorus retained, and influent concentration as variables. Enhancing sand filtration systems with steel wool fabric would minimally increase installation costs and would increase the material cost by 3–5%. Based on these findings, steel-enhanced sand filtration is a potentially cost-effective treatment for removing dissolved phosphorus from storm water runoff.     

Treatment of High Nitrate-Containing Wastewaters by Sequential Heterotrophic and Autotrophic Denitrification

The treatment performance of sequential heterotrophic and autotrophic denitrification process was evaluated using synthetic wastewaters containing high nitrate concentrations. The effluents from two sequentially connected reactors, for heterotrophic denitrification and sulfur-based autotrophic denitrification, were analyzed for more than 200 days. Experimental results indicated that higher than 95% of the nitrate removal could be achieved with volumetric nitrate loading rates of 2.16, 3.24, and 4.32 kg/m3?d. The maximum denitrification rates, with 1,000 mgN/l influent nitrate concentrations, for the heterotrophic and sulfur-packed autotrophic reactors, were found to be 2.47 and 3.61 kg/m3?d, respectively. A sequential heterotrophic and autotrophic denitrification process is considered a good alternative for the sole autotrophic denitrification process, providing excellent nitrate removal, especially for nitrate-rich wastewaters with very low organic contents.     

Modeling of Nitrate Adsorption and Reduction in Fe0-Packed Columns through Impulse Loading Tests

A conventional tracer study using Li+ and Cl? was conducted on four Fe0-packed column reactors for nitrate removal. Both Li+ and Cl? showed strong adsorption onto iron media and thus were not ideal tracers for the study. Tests using an impulse loading of nitrate were then innovated to investigate the transport and reduction of nitrate in the reactors. The impulse loading was superposed on a continuous constant feeding of nitrate which generated a steady effluent baseline. A multivariable model incorporating hydraulic dispersion, adsorption/desorption, and reduction of nitrate was developed and numerically solved. Both Langmuir adsorption and linear adsorption isotherms were separately applied to describe nitrate adsorption on the reactive surface. The parameters of the model were estimated by fitting the model with the response curves from the impulse loading tests. These estimated parameters were consistent with previous studies. Specifically, the modeling results suggest a significant adsorption of nitrate by the iron media, causing an evident retardation effect. The research may lead to new methods for studying the fate of contaminants in porous reactive environments.     

Nitrate Removal with Sulfur-Limestone Autotrophic Denitrification Processes

Nitrate removal using sulfur and limestone autotrophic denitrification (SLAD) processes was evaluated with four laboratory-scale fixed-bed column reactors. The research objectives were (1) to determine the optimum design criteria of the fixed-bed SLAD columns; and (2) to evaluate the effects of biofouling on the SLAD column performance. A maximum denitrification rate of 384 g NO3?-N/(m3?day) was achieved at a loading rate between 600 and 700 g NO3?-N/(m3?day). The effluent nitrite concentration started to rise gradually once the loading rate was above 600 g NO3?-N/(m3?day). A loading rate between 175 and 225 g NO3?-N/(m3?day) achieved the maximum nitrate-N removal efficiency (～95%). Biofouling was evaluated based on tracer studies, the measured biofilm thickness, and modeling. The porosities of the columns fluctuated with time, and the elongation of the filter media was observed. Biofouling caused short-circuiting and decreased nitrate removal efficiency. A SLAD column will require backwashing after 6 months of operation when the influent is synthetic ground water but will foul and require backwashing within 1–2 months when the influent is real ground water.     

Nitrogen Transformations during Soil–Aquifer Treatment of Wastewater Effluent—Oxygen Effects in Field Studies

Depth-dependent oxygen concentrations and aqueous-phase total ammonia and nitrate/nitrite ion concentrations were measured in the field during the infiltration of wastewater effluent. Measurements illustrated the dependence of nitrogen fate and transport on oxygen availability. Infiltration basins were operated by alternating wet (infiltration) and dry periods. During infiltration periods, ammonia was removed within the top few feet of sediments via adsorption. Biochemical activity rapidly eliminated residual molecular oxygen in the infiltrate, making the soil profile anoxic. During dry periods, oxygen reentered the basin profile and sorbed ammonia was converted to nitrate via nitrification. Oxygen penetrated to a depth of about 0.6?m?(2?ft) within the first few days of dry periods. At greater depths, oxygen levels increased more slowly due to a combination of slow transport kinetics and biochemical (nitrogenous) oxygen demand. During normal wet/dry basin cycles consisting of about 4 wet and 4 dry days, the local vadose zone remained anoxic at depths greater than about 1.5?m?(5?ft) below land surface. As a consequence, conditions for denitrification were satisfied in the deeper sediments. That is, the nitrate nitrogen produced in near surface sediments moved freely downward with infiltrating water where it encountered an extensive anoxic zone before reaching local monitoring or extraction wells. The relative importance of dissolved organics and sorbed ammonia as electron donors for denitrification reactions remains to be established.     

Enhancement of Denitrification in Upflow Sludge Bed Reactors with Sludge Wasting

From the performance data of the upflow sludge bed (USB) reactors (with sufficient carbon), the rate-limiting step in denitrification is nitrate reduction. Biological denitrification in the USB reactors (superficial velocity=0.5, 1.0, 2.0, and 4.0 m/h) can be greatly enhanced with sludge wasting from the bioreactor [i.e., maintain granular sludge retention time (GSRT) at 20 days], including high volumetric loading rates of up to 6.61 g NO3?–N/L day, high specific denitrification rates [arithmetic mean=0.31–0.42 g NO3?–N/g volatile suspended solids (VSS) day], high denitrification efficiencies (97.6–97.8%), and relatively low washout rates of biomass granules (arithmetic mean ω?=0.13–0.31 g VSS/L day). The biomass concentration, average granule size (dp), and microbial density of the USB reactors with sludge wasting were greater than those of the USB reactors without sludge wasting (i.e., the former grew more compact granules than the latter). From the granulation experiment, the granule size distribution and dp of the broken-up granules in the sludge-bed zone can restore to those of the original granules in one GSRT, implying that spontaneous flocculation of extra-cellular polymer of denitrifying-bacteria cells occurred in the USB reactor, which may also be accelerated by a rigorous backing-mixing effect of continuous production of biogas. Accordingly, the USB reactor with sludge wasting can be regarded as a promising alternative to treat high-strength nitrate wastewater.     

Enhancement of Nitrate Reduction in Fe0-Packed Columns by Selected Cations

Tests were conducted in Fe0-packed columns to investigate the effects of adding selected cations on nitrate removal by Fe0. Due to a rapid passivation of Fe0, only negligible nitrate was reduced in the columns without adding the selected cation. However, adding certain selected cations (Fe2+, Fe3+, or Al3+) in feed solution can significantly enhance nitrate reduction. Extending hydraulic retention time (HRT) increased nitrate removal by the columns, but the increase was not linearly proportional to HRT. Decreases in columns’ hydraulic conductivity (K) were monitored in an 8?month operating period. A modest decrease in K was recorded in the upper and the middle section of the media bed, whereas a significant decrease in K occurred in the inlet section. X-ray diffraction analyses indicate that magnetite (Fe3O4) was the dominant species of the iron corrosion products in the entire height of the column media under anoxic and other test conditions. In the inlet section, however, lepidocrocite and goethite were also identified. Cementation was found to occur only in the inlet section, suggesting that lepidocrocite and goethite, rather than magnetite, might be responsible for the cementation and thereby cause the hydraulic clogging. The magnetite coating would not necessarily cause clogging of the media.     

Reaction Kinetics of Immobilized-Cell Denitrification. II: Experimental Study

Laboratory experiments were conducted to characterize the performance of an immobilized-cell denitrification process treating nitrate-contaminated groundwater and to provide supporting data for the validation of a quasi-steady state model based on half-order reaction kinetics. The treatment process consists of laboratory-scale, plug-flow reactors packed with biocatalyst particles. Pseudomonas denitrificans (American Type Culture Collection 13867), a heterotrophic denitrifier, was cultured and immobilized in calcium alginate particles. Ethanol was used as the source of organic carbon. Thirty concentration profiles were obtained at four levels of nitrate concentration and at three ranges of flow rate. An analysis of the nitrate and nitrite concentration profiles suggested that a half-order reaction rate model could be used to describe the reduction of both nitrate and nitrite. The half-order reaction rate constants for nitrate and nitrite reduction were dependent on the age of the biocatalyst particles and the nitrate loading history. The validity of the half-order denitrification model was satisfactorily tested with experimental data. As illustrated by preliminary calculations, the immobilized-cell denitrification process is feasible for practical applications, particularly for small drinking water systems.     

Mathematical Modeling of Encapsulated Buffer Performance in Sand Columns

A one-dimensional mathematical model was developed to simulate pH control using an encapsulated phosphate buffer during denitrification in a sand column. The parameters required for the model were obtained from direct physical measurement, from a tracer study to characterize the dispersion coefficient in the column, and from batch experiments designed to obtain an empirical expression describing the variation of the first-order rate constant for the encapsulated buffer core release with pH. First-order kinetic constants describing the rates of denitrification and ethanol biodegradation were obtained by fitting the model to column runs without the encapsulated buffer. With these parameters, the model was subsequently used to predict the performance of column runs containing the encapsulated buffer. Since denitrification was essentially complete in the sand columns, an increase in the effluent pH was observed. This pH increase was counteracted by the controlled release of the acidic core of the encapsulated buffers added in the columns. The model reasonably predicted the release of the encapsulated buffer core and the performance of the encapsulated buffer for controlling pH in the column.     

Development of a Response Surface for Prediction of Nitrate Removal in Sulfur–Limestone Autotrophic Denitrification Fixed-Bed Reactors

Sulfur–limestone autotrophic denitrification (SLAD) processes are very efficient for treatment of ground or surface water contaminated with nitrate. However, detailed information is not available on the interaction among some major variables on the design and performance of the SLAD process. In this study, the response surface method was used by designing a rotatable central composite test scheme with 12 SLAD column tests. A polynomial linear regression model was set up to quantitatively describe the relationship of the effluent and influent nitrate–nitrogen concentration and hydraulic retention time (HRT) in the SLAD column reactors. This model may be used for estimating the effluent nitrate–nitrogen concentration when the influent nitrate–nitrogen concentration ranges between 20 and 110?mg/L and the HRT ranges between 2 and 9?h. Based on our model and the requirement for nitrite control, we recommend that the HRT of the SLAD column reactor be kept ≥ 6?h and the nitrate loading rate less than 200 g NO3?–N/day?m3 media to achieve high nitrate removal efficiency (>99%) and prevent nitrite accumulation from being >1?mg/L NO2?–N.     

Combined System for Biological Removal of Nitrogen and Carbon from a Fish Cannery Wastewater

A combined system composed of three sequentially arranged reactors, anaerobic-anoxic-aerobic reactors, was used to treat the wastewater generated in the tuna cookers of a fish canning factory. These wastewaters are characterized by high chemical oxygen demand (COD) and nitrogen concentrations. The anaerobic process was performed in an upflow anaerobic sludge blanket reactor operated in two steps. During Step I different influent COD concentrations were applied and organic loading rates (OLRs) up to 4 g COD/(L?d) were achieved. During Step II hydraulic retention time (HRT) was varied from 0.5 to 0.8 days while COD concentration in the influent was constant at 6 g COD/L. The OLRs treated were up to 15 g COD/(L?d). When HRTs longer than 0.8 days were used, COD removal percentages of 60% were obtained and these values decreased to 40% for a HRT of 0.5 days. The denitrification process carried out in an upflow anoxic filter was clearly influenced by the amount of carbon source supplied. When available carbon was present, the necessary COD/N ratio for complete denitrification was around 4 and denitrification percentages of 80% were obtained. The nitrification process was successful and was almost unaffected by the presence of organic carbon (0.2–0.8 g TOC/L), with ammonia removal percentages of 100%. Three recycling ratios (R/F) between the denitrification and nitrification reactors were applied at 1, 2, and 2.5. The overall balance of the combined system indicated that COD and N removal percentages of 90% and up to 60%, respectively, were achieved when the R/F ratio was between 2 and 2.5.     

Chloride Interactions with Iron Surfaces: Implications for Perchlorate and Nitrate Remediation Using Permeable Reactive Barriers

Perchlorate (ClO4?) can be reduced by iron surfaces, suggesting that permeable reactive barriers may represent a useful groundwater remediation strategy. However, chloride produced by the reaction inhibits further perchlorate removal. Adsorption of chloride on iron filings was investigated as a potential mechanism of chloride interference. The effect of chloride on the removal of nitrate, another oxyanion reactive at iron surfaces, was also investigated to draw more general conclusions about anion competition when target compounds adsorb electrostatically. A triple layer adsorption model was used to describe chloride sorption isotherms on the iron filings using magnetite as the model surface and defining a single type of surface hydroxyl sorption site. The model considered electrostatic attraction, specific sorption, and the effect of adsorbed Fe2+ on chloride sorption. Experimental and modeling results indicate that chloride competition is probably not of concern for nitrate reduction in permeable reactive barriers. However, perchlorate reduction is significantly inhibited by chloride in both buffered and unbuffered solutions, possibly because the reactive sorbed Fe2+ sites may be preferentially occupied by chloride.     

完善浓氨水生产工艺流程的几项措施

莱钢焦化厂为解决浓氨水生产工艺流程中的设备腐蚀、泄漏、维修量大、开工率低等问题，采取了以螺旋板换热器代替原列管换热器，以铸铅材质替代铸铁材质，以不锈钢板代替普通钢板，增加吸收塔填料密度等措施，使浓氨水生产工艺开工率达99．5％，泄漏率降至0．1％以下。     

Arsenic Removal by a Colloidal Iron Oxide Coated Sand

A novel treatment process for arsenic removal from contaminated groundwater has been developed for use as a reactive barrier or a small drinking water treatment unit. In this study, modified porous media was made by the deposition of colloidal iron oxide onto sand grains at intermediate pH and ionic strength. Kd values from column experiments were 0.016–0.37?L/kg for As(III) and 0.023–0.85?L/kg for As(V), being lower than those of batch experiments (0.50 and 1.30?L/kg for As(III) and As(V), respectively) due to lower availability of surface adsorption sites in the packed column. Media-independent Kd values reflect the enhancement of arsenic adsorption with an increase of colloidal iron oxide coated sand fraction, apparently due to adsorption equilibration during arsenic transport under the same flow column conditions. The heterogeneous composition of two groundwater samples also reduced arsenic adsorption. Therefore, arsenic elution near the initial breakthrough was regulated by available adsorption surface in a porous coated sand media as well as the effects of competing oxyanions. The exhaustion of adsorption capacity near the critical contamination level is sensitive to geochemical and remedial properties of the contaminants.     

Long-Term Capacity of Plant Mulch to Remediate Trichloroethylene in Groundwater

Passive reactive barriers (PRBs) are commonly used to treat groundwater that is contaminated with chlorinated solvents such as trichloroethylene (TCE). A number of PRBs have been constructed with plant mulch as the reactive medium. The TCE is removed in these barriers through adsorption, biological reductive dechlorination, and abiotic reactions with reduced iron minerals that are formed in the barrier. Generally speaking, adsorption has limited capacity for TCE removal and abiotic dechlorination is dependent on metal sulfides of biogenic origin. Therefore, the long-term performance of these barriers will be controlled by their capacity to support biological activity. Laboratory batch experiments were inoculated with an enrichment culture of dechlorinating microorganisms. Dechlorination of TCE to ethylene was achieved using plant mulch; however, neither water extractable nor organic-solvent extractable components of the mulch could sustain dechlorination of TCE. This indicates that biodegradation of organic wood fibers in the plant cell wall provides electron donors for dechlorination of TCE. Kinetic analysis of the methane production in the batch tests provides supporting evidence that the plant mulch is able to sustain long-term biological activity in a typical barrier constructed with plant tissues. The recognition of the intact plant tissues as a long-term electron donor expands the knowledge about the microbial dechlorination under natural conditions. In addition, the production of dissolved inorganic carbon (DIC) observed in a column study was used to estimate the life cycle of a full-scale biowall installed at Altus AFB, Oklahoma. Based on a consistent downward trend in DIC concentrations in the effluent and a stable concentration in the influent over time, the mulch in the biowall is expected to support microbial activity for 10 years.     

Effects of Surface-Bound Fe2+ on Nitrate Reduction and Transformation of Iron Oxide(s) in Zero-Valent Iron Systems at Near-Neutral pH

Nitrate reduction in an iron/nitrate/water system with or without an organic buffer was investigated using multiple batch reactors under strict anoxic conditions. Nitrate reduction was very limited (<10%) at near-neutral pH in the absence of the organic buffer. However, nitrate reduction was greatly enhanced if the system: (1) had a low initial pH ( ～ 2–3); (2) was primed with adequate aqueous Fe2+; or (3) was in the presence of the organic buffer. In Cases (1) and (3), nitrate reduction usually was involved in three stages. The first stage was quick, and H+ ions directly participated in the corrosion of iron grains. The second stage was very slow due to the formation of amorphous oxides on the surface of iron grains, while the third stage was characterized by a rapid nitrate reduction concurrent with the disappearance of aqueous Fe2+. Results indicate that reduction of nitrate by Fe0 will form magnetite; Fe2+ (aq.) can accelerate reduction of nitrate and will be substoichiometrically consumed. Once nitrate is exhausted in the system, no more Fe2+ will be consumed. In the presence of nitrate, Fe2+ (aq) will be adsorbed onto the surface of iron grains or iron oxides; the surface-complexed Fe(II) (extracted by acetate with pH = 4.1) might be oxidized and become structural Fe(III), resulting in a steadily increasing ratio of Fe(III)/Fe(II) in the oxides formed. The transformation of nonstoichiometric amorphous iron oxides into crystalline magnetite, a nonpassive oxide, triggers the rapid nitrate removal thereafter.     

Modeling of Corroded FRP-Wrapped Reinforced Concrete Columns in Axial Compression

This paper discusses the mechanical behavior of reinforced concrete columns wrapped with fiber-reinforced polymer (FRP) sheets. A numerical routine was developed to predict the behavior of the columns using a step-by-step technique. The routine is based on an existing model and was modified to account for confinement provided by the traditional steel as well as the external FRP wraps. Several empirical equations for the confined concrete were calibrated with results from experimental tests from different published papers. The most accurate equation was incorporated into the routine to predict the stress-strain relation of the column up to failure. A different confinement to the outer concrete cover and the inner core was used to account for the FRP wraps and the transverse steel. The model was calibrated with experimental results from different experiments on FRP-wrapped reinforced concrete columns.The model was taken one step further by using it to predict the behavior of reinforced concrete columns, with a combination of steel corrosion and CFRP wraps. The columns modeled were subjected to harsh corrosive environment over 44 months. The model successfully predicted the load deformation in both axial and circumferential directions in corroded and intact columns, both wrapped and unwrapped, with good accuracy. The analysis forms a solid foundation for accurate evaluation of the effect of corrosion and wrapping on reinforced concrete columns.     

烧结烟气脱硝废弃钒钨钛催化剂资源化利用途径分析

2019年生态环境部等五部联合印发《关于推进实施钢铁行业超低排放的意见》提出,到2025年底前,全国力争80%以上的钢铁产能完成超低排放改造。目前,烧结烟气中NO_x减排成为重中之重。以钒钨钛系催化剂为核心的氨气选择性催化还原法(NH₃-SCR)成为烟气脱硝主流技术之一,并已广泛在钢铁企业投入使用。而随着催化剂使用寿命到期,废弃催化剂产生量逐年增加。据估计,2027年前后中国烧结烟气脱硝废弃催化剂产生量将达到100 000 m³/a。钒钨钛系催化剂含有V₂O₅,具有较强的生物毒性,新版《国家危险废物名录》中,已明确将这类废弃催化剂归为“HW50”危废。随着环保要求日益严厉,加强对钒钨钛系催化剂的有效处置利用已成为钢铁工业急需解决的关键共性难题。围绕废弃催化剂的处理思路和技术手段,总结了国内外废弃催化剂处置现状。主要处理思路分为有价元素提取、废弃催化剂循环利用和无害化处置等。有价元素提取相应的技术手段包括浸出、萃取、沉淀、水热合成、碳热还原等;废弃催化剂循环利用包括掺混制备新催化剂...     

新一代钢铁材料研究的进展

介绍了日本、韩国、欧洲和国内近年来在新一代钢铁材料方面的研究进展情况，并对日本在800MPa超细晶粒钢、1500MPa超高强度钢、耐热钢、耐腐蚀钢等的研究成果和将来的研究项目进行了详细介绍。