硫酸铅在柠檬酸钠-酸体系中的浸出转化

硫酸铅可以在柠檬酸钠-乙酸体系中脱硫转化生成柠檬酸铅。考察了柠檬酸钠投加量、反应时间、固液比以及反应温度对PbSO4浸出转化的影响。实验结果表明,PbSO4的转化率随着柠檬酸钠投加量和反应时间的增加而增大,固液比和反应温度对浸出过程影响不大。溶液中溶解的铅含量随着柠檬酸钠投加量的增大而增大,其他条件对其影响不明显。最佳浸出工艺条件是：柠檬酸钠与PbSO。的物质的量之比为2：1,固液比为1／5～1／3,反应温度为25℃,反应时间为2h,此时PbSO4的转化率可达到99％左右,溶液中的铅含量为总铅的3．8％左右。PbSO4浸出得到[Pb,（C。H,O,）,]·3H2O,它在350℃左右可完全分解,得到PbO／Pb粉末。     

Refinement of the density-modified displacement method for efficient treatment of tetrachloroethene source zones

A novel method to remediate dense nonaqueous phase liquid (DNAPL) source zones that incorporates in situ density conversion of DNAPL via alcohol partitioning followed by displacement with a low interfacial tension (IFT) surfactant flood has been developed. Previous studies demonstrated the ability of the density-modified displacement (DMD) method to recover chlorobenzene (CB) and trichloroethene (TCE) from heterogeneous porous media without downward migration of the dissolved plume or free product. However, the extent of alcohol (n-butanol) partitioning required for in situ density conversion of high-density NAPLs, such as tetrachloroethene (PCE), could limit the utility of the DMD method. Hence, the objective of this study was to compare the efficacy of two n-butanol delivery approaches: an aqueous solution of 6% (wt) n-butanol and a surfactant-stabilized macroemulsion containing 15% (vol) n-butanol in water, to achieve density reduction of PCE-NAPL in two-dimensional (2-D) aquifer cells. Results of liquid-liquid equilibrium studies indicated that density conversion of PCE relative to water occurred at an n-butanol mole fraction of 0.56, equivalent to approximately 5 ml n-butanol per 1 ml of PCE when in equilibrium with an aqueous solution. In 2-D aquifer cell studies, density conversion of PCE was realized using both n-butanol preflood solutions, with effluent NAPL samples exhibiting density reductions ranging from 0.51 to 0.70 g/ml. Although the overall PCE mass recoveries were similar (91% and 93%) regardless of the n-butanol delivery method, the surfactant-stabilized macroemulsion preflood removed approximately 50% of the PCE mass. In addition, only 1.2 pore volumes of the macroemulsion solution were required to achieve in situ density conversion of PCE, compared to 6.4 pore volumes of the 6% (wt) n-butanol solution. These findings demonstrate that use of the DMD method with a surfactant-stabilized macroemulsion containing n-butanol holds promise as an effective source zone remediation technology, allowing for efficient recovery of PCE-DNAPL while mitigating downward migration of the dissolved plume and free product.     

Selective separation of copper(II) and nickel(II) from aqueous media using the complexation-ultrafiltration process

The polyethylenimine (PEI) as complexing agent was used to study the complexation-ultrafiltration (CP-UF) process in the selective removal of Cu(II) from Ni(II) contained in aqueous media. Preliminary tests showed that optimal chemical conditions for Cu(II) and Ni(II) complexation by the PEI polymer were pH>6.0 and 8.0, respectively, and polymer/metal weight ratio of 3.0 and 6.0, respectively. The effect of some important operating parameters on process selectivity was studied by performing UF tests at different parameters: pH, polymer/metal weight ratio, transmembrane pressure (TMP), and membrane cut-off in a batch experimental set-up. It was observed that process selectivity was achieved by choosing the pH value for obtaining a preferential copper complexation (pH 6.0), and the polymer/metal ratio needed to bound only the copper ion (3.0). The selective separation by UF tests was performed by using both a laboratory aqueous solution and a real aqueous effluent (water from Emoli torrent, Rende (CS)). The Iris 30 membrane at TMP of 200 kPa (2 bar) for both aqueous media gave the best results. A complete nickel recovery was reached, and copper recovery was the highest for this membrane (94% and 92%). Besides at this pressure, a lower water amount was needed to obtain total nickel recovery by diafiltration. A little higher membrane fouling was obtained by using the river effluent due to the presence of dissolved organic and inorganic matter.     

Fe (III) supported on resin as effective catalyst for the heterogeneous oxidation of phenol in aqueous solution

FeIII supported on resin as an effective catalyst for oxidation was prepared and applied for the degradation of aqueous phenol. Phenol was selected as a model pollutant and the catalytic oxidation was carried out in a batch reactor using hydrogen peroxide as the oxidant. The influent factors on oxidation, such as catalyst dosage, H2O2 concentration, pH, and phenol concentration were examined by considering both phenol conversion and chemical oxygen demand (COD) removal. The FeIII-resin catalyst possesses a high oxidation activity for phenol degradation in aqueous solution. The experimental results of this study show that almost 100% phenol conversion and over 80% COD removal can be achieved with the FeIII-resin catalyst catalytic oxidation system. A series of prepared resin were investigated for improving the oxidation efficiency. It was found that the reaction temperature and initial pH in solution significantly affected both of phenol conversion and COD removal efficiency. The activity of the catalyst significantly decreased at high pH, which was similar to the Fenton-like reaction mechanism. Results in this study indicate that the FeIII-resin catalytic oxidation process is an efficient method for the treatment of phenolic wastewater.     

Seizure modeling of Pb(II) and Cd(II) from aqueous solution by chemically modified sugarcane bagasse fly ash: isotherms, kinetics, and column study

Heavy metal pollution is a common environmental problem all over the world. The purpose of the research is to examine the applicability of bagasse fly ash (BFA)—an agricultural waste of sugar industry used for the synthesis of zeolitic material. The zeolitic material are used for the uptake of Pb(II) and Cd(II) heavy metal. Bagasse fly ash is used as a native material for the synthesis of zeolitic materials by conventional hydrothermal treatment without (conventional zeolitic bagasse fly ash (CZBFA)) and with electrolyte (conventional zeolitic bagasse fly ash in electrolyte media (ECZBFA)) media. Heavy metal ions Pb(II) and Cd(II) were successfully seized from aqueous media using these synthesized zeolitic materials. In this study, the zeolitic materials were well characterized by different instrumental methods such as Brunauer–Emmett–Teller, XRF, Fourier transform infrared spectroscopy, powder X-ray diffraction, and scanning electron microscopic microphotographs. The presence of analcime, phillipsite, and zeolite P in adsorbents confirms successful conversion of native BFA into zeolitic materials. Seizure modeling of Pb(II) and Cd(II) was achieved by batch sorption experiments, isotherms, and kinetic studies. These data were used to compare and evaluate the zeolitic materials as potential sorbents for the uptake of heavy metal ions from an aqueous media. The Langmuir isotherm correlation coefficient parameters best fit the equilibrium data which indicate the physical sorption. Pseudo-second-order and intra-particle diffusion model matches best which indicates that the rate of sorption was controlled by film diffusion. The column studies were performed for the practical function of sorbents, and breakthrough curves were obtained, which revealed higher sorption capacity as compared to batch method. Synthesized zeolitic material (CZBFA and ECZBFA), a low-cost sorbent, was proven as potential sorbent for the uptake of Pb(II) and Cd(II) heavy metal ions.     

Oxidation of methane over palladium catalysts: effect of the support

This work is focused on the deep catalytic oxidation of methane over supported palladium catalysts. The influences of the metal loading, oxidation state of palladium, nature of supports, presence of promoters in the supports (for zirconia-based supports), and thermal stability have been studied experimentally. Catalysts were prepared by incipient wetness of commercially available supports with aqueous solutions of palladium nitrate. For gamma-alumina support, it was observed that the optimal amount of palladium is between 0.5% and 2%, with higher amounts leading to a loss in specific activity. Concerning the oxidation state of the catalyst, it is concluded that for all the supports tested in the present work, a reduction of the catalyst is not needed, yielding the same conversion at steady state catalysts reduced and oxidised. The thermal stability of various supported catalysts were also studied, zirconia supports being the most active. These supports, specially Y-modified zirconia support, do not suffer appreciable deactivation below 500 degrees C.     

Catalytic wet air oxidation of bisphenol A solution in a batch-recycle trickle-bed reactor over titanate nanotube-based catalysts

Catalytic wet air oxidation (CWAO) is classified as an advanced oxidation process, which proved to be highly efficient for the removal of emerging organic pollutant bisphenol A (BPA) from water. In this study, BPA was successfully removed in a batch-recycle trickle-bed reactor over bare titanate nanotube-based catalysts at very short space time of 0.6 min g_CAT?g^?1. The as-prepared titanate nanotubes, which underwent heat treatment at 600 °C, showed high activity for the removal of aqueous BPA. Liquid-phase recycling (5- or 10-fold recycle) enabled complete BPA conversion already at 200 °C, together with high conversion of total organic carbon (TOC), i.e., 73 and 98 %, respectively. The catalyst was chemically stable in the given range of operating conditions for 189 h on stream.     

Wet peroxide degradation of atrazine

The high temperature (150-200 degrees C), high pressure (3.0-6.0 MPa) degradation of atrazine in aqueous solution has been studied. Under these extreme conditions atrazine steadily hydrolyses in the absence of oxidising agents. Additionally, oxygen partial pressure has been shown not to affect atrazine degradation rates. In no case mineralisation of the parent compound was observed. The addition of the free radical generator hydrogen peroxide to the reaction media significantly enhanced the depletion rate of atrazine. Moreover, partial mineralisation of the organics was observed when hydrogen peroxide was used. Again, oxygen presence did not influence the efficiency of the promoted reaction. Consecutive injections of hydrogen peroxide throughout the reaction period brought the total carbon content conversion to a maximum of 65-70% after 40 min of treatment (suggesting the total conversion of atrazine to cyanuric acid). Toxicity of the effluent measured in a luminometer decreased from 93% up to 23% of inhibition percentage. The process has been simulated by means of a semi-empirical model.     

Oxidative degradation of 2,4-xylidine by photosensitization with 2,4,6-triphenylpyrylium: homogeneous and heterogeneous catalysis

The possibility of using zeolites containing the 2,4,6-triphenylpyrylium cation as photocatalysts for the degradation of pollutants has been tested on aqueous xylidine (2,4-dimethylaniline) solutions as models for contaminated wastewaters. The influence of the photocatalyst and substrate concentrations on xylidine oxidation has been investigated in homogeneous solution, by performing a series of experiments chosen according to the experimental design methodology (Doehlert uniform array). The empirical models and the corresponding response surfaces obtained from data analysis have been used for simulating and predicting degradation efficiency. The results have shown that conversion increases with increasing amounts of photocatalyst and decreasing concentration of the model pollutant. The fluorescence of 2,4,6-triphenylpyrylium was quenched by xylidine with a rate constant k(q) of 3.1x10(9)M(-1)s(-1). This result suggests a direct electron transfer between the excited pyrylium salt and xylidine. Because of the limited stability of the photocatalyst in homogeneous media, a pyrylium containing Y-zeolite has been tested for the photocatalytic oxidation of xylidine under heterogeneous conditions. The results suggest that the supported catalyst has a much improved stability and that xylidine oxidation rates remain nearly constant during the whole reaction time. An additional advantage of the pyrylium containing zeolite photocatalyst is that it can be recycled and used for further experiments.     

Study on the fluorescence characteristics of bromadiolone in aqueous and organized media and application in analysis

The fluorescence spectroscopic behavior of bromadiolone (anticoagulant rodenticide), a substituted 4-hydroxycoumarin derivative, was investigated in water and in organized media like micelles and cyclodextrins. A detailed study on various photophysical parameters like fluorescence intensity (I_F), quantum yield (), lifetime (τ) and steady state fluorescence anisotropy (r) of bromadiolone in aqueous and in organized media was carried out. Bromadiolone in aqueous solution was observed to be in an aggregated state, thereby showing weak emission due to self-quenching. Marked enhancement of fluorescence intensity was observed in organized media like micelles and β-cyclodextrin. A preliminary investigation has been done to find out whether this enhancement of fluorescence can be used to develop a sensitive analytical method for determination of bromadialone in aqueous media. A linear relationship between the fluorescence intensity and concentration of bromadiolone was observed in the range of 0.15–7.9 μg ml⁻¹ in cetyltrimethylammonium bromide (CTAB) and 0.5–26.4 μg ml⁻¹ in β-cyclodextrin medium. The lower detection limit was found to be 37 ng ml⁻¹ in presence of CTAB and 23 ng ml⁻¹ in β-cyclodextrin. Comparison with 4-hydroxycoumarin, an unsubstituted analogue, was made.     

Specific detection of p-chlorobenzoic acid by Escherichia coli bearing a plasmid-borne fcbA'::lux fusion

In this communication we report on a genetically engineered bacterium that reacts by light emission to the presence of 4-chlorobenzoic acid. To construct this strain, DNA fragment (1.7 kb) upstream from the 4-chlorobenzoic acid dehalogenase (fcb) operon of Arthrobacter SU was fused to Vibriofischeri luxCDABE genes. An Escherichia coli strain transformed with a multi-copy plasmid (pASU) bearing this fusion responded to the presence of 4-chlorobenzoic acid and a few closely related compounds by increased luminescence, exhibiting a high specificity but a relatively low sensitivity. While it could be somewhat, improved by manipulating the experimental pH, sensitivity remained too low for real time applicability. Nevertheless, the principle of using dehalogenase promoters as environmental pollution sensor was demonstrated.     

Leaching study of polycyclic aromatic hydrocarbon bioavailability from a coal-derived solid product

The leaching behavior of selected four- to six-ring polycyclic aromatic hydrocarbons (PAH) from a tumorigenic coal-derived solid product was determined using three media to evaluate their potential bioavailabilities. Equilibrium PAH concentrations generally exceeded the aqueous solubilities after less than five days of leaching. PAH selectively accumulated in phospholipid vesicles at individual concentrations greater than 1 μg/g, which is ca. 100-fold over that in the bulk aqueous leachate. The results suggest that the PAH are quite bioavailable from the solid product, and that cell membranes can be exposed to considerable quantities of these PAH over an extended bioassay.     

Microbial degradation of arsenobetaine, the major water soluble organoarsenic compound occurring in marine animals

The conversion of arsenobetaine into other arsenic compounds by microorganisms occurring in the bottom sediments from coastal waters was demonstrated for the first time. Three arsenic metabolites were observed on high performance liquid chromatogram during incubation at 25 °C for 80 days in 2 kinds of media, 1/5 ZoBell 2216E and a medium composed of inorganic salts. The time course pattern of arsenic metabolites during incubation was fairly different between these 2 media.     

Total arsenic and selenium analysis in Marcellus shale,high-salinity water,and hydrofracture flowback wastewater

Trace levels of arsenic and selenium can be toxic to living organisms yet their quantitation in high ionic strength or high salinity aqueous media is difficult due to the matrix interferences which can either suppress or enhance the analyte signal. A modified thiol cotton fiber (TCF) method employing lower flow rates and centrifugation has been used to remove the analyte from complex aqueous media and minimize the matrix interferences. This method has been tested using a USGS (SGR-1b) certified reference shale. It has been used to analyze Marcellus shale samples following microwave digestion as well as spiked samples of high salinity water (HSW) and flow back wastewater (WRF6) obtained from an actual gas well drilling operation. Quantitation of arsenic and selenium is carried out by graphite furnace atomic spectroscopy (GFAAS). Extraction of arsenic and selenium from Marcellus shale exposed to HSW and WRF6 for varying lengths of time is also reported.     

Total arsenic and selenium analysis in Marcellus shale, high-salinity water, and hydrofracture flowback wastewater

Trace levels of arsenic and selenium can be toxic to living organisms yet their quantitation in high ionic strength or high salinity aqueous media is difficult due to the matrix interferences which can either suppress or enhance the analyte signal. A modified thiol cotton fiber (TCF) method employing lower flow rates and centrifugation has been used to remove the analyte from complex aqueous media and minimize the matrix interferences. This method has been tested using a USGS (SGR-1b) certified reference shale. It has been used to analyze Marcellus shale samples following microwave digestion as well as spiked samples of high salinity water (HSW) and flow back wastewater (WRF6) obtained from an actual gas well drilling operation. Quantitation of arsenic and selenium is carried out by graphite furnace atomic spectroscopy (GFAAS). Extraction of arsenic and selenium from Marcellus shale exposed to HSW and WRF6 for varying lengths of time is also reported.     

Continuous flow photo-Fenton treatment of ciprofloxacin in aqueous solutions using homogeneous and magnetically recoverable catalysts

The degradation of ciprofloxacin was studied in aqueous solutions by using a continuous flow homogeneous photo-Fenton process under simulated solar light. The effect of different operating conditions on the degradation of ciprofloxacin was investigated by changing the hydrogen peroxide (0–2.50 mM) and iron(II) sulphate (0–10 mg Fe L^?1) concentrations, as well as the pH (2.8–10), irradiance (0–750 W m^?2) and residence time (0.13–3.4 min) of the process. As expected, the highest catalytic activity in steady state conditions was achieved at acidic pH (2.8), namely 85 % of ciprofloxacin conversion, when maintaining the other variables constant (i.e. 2.0 mg L^?1 of iron(II), 2.50 mM of hydrogen peroxide, 1.8 min of residence time and 500 W m^?2 of irradiance). Additionally, magnetite magnetic nanoparticles (ca. 20 nm of average particle size) were synthesized, characterized and tested as a possible catalyst for this reaction. In this case, the highest catalytic activity was achieved at natural pH, namely a 55 % average conversion of ciprofloxacin in 1.8 min of residence time and under 500 W m^?2. Some of the photocatalytic activity was attributed to Fe²⁺ leaching from the magnetic nanoparticles to the solution.     

Removal of propham from water by using electro-Fenton technology: kinetics and mechanism

The removal of a carbamate herbicide, propham, from aqueous solution has been carried out by the electro-Fenton process. Hydroxyl radical, a strong oxidizing agent, was generated catalytically and used for the oxidation of propham aqueous solutions. The degradation kinetics of propham evidenced a pseudo-first order degradation. The absolute rate constant of second order reaction kinetics between propham and ()OH was determined as (2.2+/-0.10)x10(9)m(-1)s(-1). The mineralization of propham was followed by the organic carbon (TOC) removal. The optimal Fe(3+) concentration was found as 0.5mM at 300mA. The 94% of initial TOC of 0.25mM propham solution was removed in 8h at the optimal conditions by using the cathode area to solution volume ratio of 3.33dm(-1). The maximum mineralization current efficiency values were obtained at 60mA in the presence of 0.5mM Fe(3+). During the electro-Fenton treatment, several degradation products were formed. These intermediates were identified by using high performance liquid chromatography, liquid chromatography-mass spectrometry, gas chromatography-mass spectrometry and ion chromatography analysis. The identified by-products allowed proposing a pathway for the propham mineralization.     

Government Sponsored Air Pollution Research Relating to Agriculture

The absorption of hydrogen sulfide and methyl mercaptan by aqueous solutions of chlorine, sodium hydroxide, and chlorine plus sodium hydroxide was studied using a two-inch diameter absorption column packed with ¼ inch Intalox saddles. Absorption rates were noticeably affected by chemical reactions occurring in the aqueous chlorine and hydroxide media. These solutions were studied as a means of controlling sulfur-containing gas emissions from kraft paper mills. The absorption studies indicated that aqueous chlorine solutions at a pH above 12 were effective absorbents for hydrogen sulfide removal in absorption equipment designed to tolerate sulfur in suspension. The absorption of methyl mercaptan in aqueous chlorine solutions appeared to be impractical since dimethyl disulfide was apparently the only product formed and was stripped from the tower by the gas stream. Sodium hydroxide solution was an effective absorbent for both methyl mercaptan and hydrogen sulfide when hydroxide to sulfide or mercaptan feed ratios were greater than 1 or 1.8, respectively. The mercaptan absorption coefficient was approximately twice that for sulfide absorption.     

Characterization of Cr ion exchange with hydrotalcite

Experiments were performed to characterize the removal of chromium from water with uncalcined hydrotalcite, a clay mineral ion exchange media. The process was characterized as a function of pH, temperature, contact time, and both Cr and hydrotalcite concentrations. A Freundlich isotherm, used to describe adsorption equilibria, was used as a model and Freundlich constants were determined. The kinetics of the ion exchange reaction were also modeled using a pseudo-first order reaction rate. Finally, an equilibrium stage process was modeled with sequential batch separations to determine if hydrotalcite ion exchange could reduce aqueous Cr levels to below the EPA limit of 0.1mgl(-1). It was shown that the process is highly pH dependent, only yielding significant removals at pH levels between 2.0 and 2.1. While hydrotalcite concentration, Cr concentration, and time did effect the ion exchange, temperature was not found to be a factor. Under optimal conditions, maximum removals of greater than 95% were achieved. Finally, sequential batch tests performed on initial Cr solutions ranging from 5mgl(-1) to 40mgl(-1), demonstrated that the water could be purified to a level that was not statistically different than the EPA limit, thus demonstrating the applicability of hydrotalcite ion exchange.     

An assessment of the suitable operating conditions for the CeO2/gamma-Al2O3 catalyzed wet air oxidation of phenol

It has been shown that the CeO2/gamma-Al2O3 catalyst is a feasible alternative to CeO2 for the catalytic wet air oxidation (CWAO) of phenol because it remains an effective catalyst and yet is cheaper to prepare. In this study, we found that the optimal cerium content in the CeO2/gamma-Al2O3 catalyst was 20 wt.%, regardless of catalyst loading. Furthermore, at 180 degrees C, with a phenol concentration of 1000 mg l(-1), and an O2 partial pressure of 1.0M Pa or 1.5M Pa, the optimal catalyst loading was 3.0 gl (-1). The efficacy of CWAO of phenol improved with O2 partial pressure, although the effects of O2 pressure were more significant between 0.5 MPa and 1.5 MPa than between 1.5 MPa and 2.0 MPa. After 2 h of reaction, approximately 100% phenol conversion and 80% total organic carbon (TOC) removal was recorded at 180 degrees C, 1000 mg l(-1) of phenol and 3.0 g l(-1) of catalyst. Because these percentages subsequently leveled off, it is suggested that 2 h is a suitable time over which to run the reaction. The efficacy of CWAO of phenol decreased as initial phenol concentration was raised (from 400 to 2500 mg l(-1)), with the exception of phenol conversion after about 2 h, for which 400 mg l(-1) produced the lowest phenol conversion figure. Higher phenol concentrations require both catalyst loading and O2 partial pressure to be increased to maintain high performance. For example, for 2000 mg l(-1) and 2500 mg l(-1) phenol, nearly 100% phenol conversion and 90% TOC removal after 4 h of reaction at 180 degrees C required 4.0 g l(-1) of catalyst and 2.0 MPa.