Pt nanoparticles entrapped in ordered mesoporous carbons:An efficient catalyst for the liquid-phase hydrogenation of nitrobenzene and its derivatives

Pt nanoparticles entrapped in ordered mesoporous CMK-3 carbons with p6mm symmetry were prepared using a facile impregnation method, and the resulting materials were characterized using X-ray diffraction spectroscopy, N2 adsorption-desorption, scanning electron microscopy, transmission electron microscopy, energy dispersive X-ray spectroscopy, and X-ray photoelectron spectroscopy. The Pt nanoparticles were highly dispersed in the CMK-3 with 43.7% dispersion. The Pt/CMK-3 catalyst was an effective catalyst for the liquid-phase hydrogenation of nitrobenzene and its derivatives under the experimental conditions studied here. The Pt/CMK-3 catalyst was more active than commercial Pt/C catalyst in most cases. A highest turnover frequency of 43.8 s-1 was measured when the Pt/CMK-3 catalyst was applied for the hydrogenation of 2-methyl-nitrobenzene in ethanol under optimal conditions. It is worthy of note that the Pt/CMK-3 catalyst could be recycled easily, and could be reused at least fourteen times without any loss in activity or selectivity for the hydrogenation of nitrobenzene in ethanol.

Prediction of the environmental fate and aquatic ecological impact of nitrobenzene in the Songhua River using the modified AQUATOX model

An accidental discharge of nitrobenzene happened in November 2005 in the Songhua River,China.The AQUATOX model was modified and adapted to simulate the time-dependent nitrobenzene distribution in this multimedia aquatic system and its potential ecological impacts.Nitrobenzene concentrations in flowing water,sediment,and biota were predicted.Based on the initial concentrations of nitrobenzene observed in the field during the accidental discharge,that is,0.167-1.47 mg/L at different river segments, the predic...

Nitrobenzene biodegradation ability of microbial communities in water and sediments along the Songhua River after a nitrobenzene pollution event

More than 100 t of nitrobenzene (NB) and related compounds were discharged into the Songhua River,the fourth longest river in China,because of the world-shaking explosion of an aniline production factory located in Jilin City on November 13,2005.As one of the efforts to predict the fate of residual NB in the river,NB biodegradation abilities by microbes in the water and sediments from different river sections were evaluated systematically.The results indicated that microbial communities from any section of ...

Characterization of the Songhua River sediments and evaluation of their adsorption behavior for nitrobenzene

The explosion at a plant of the Jilin Petrochemical Corporation on 13 November,2005,and the spill of an estimated 100 t of toxic substances (nitrobenzene as the main component) into the Songhua River received worldwide attention.This study has focused on the adsorption behavior of nitrobenzene that spilled onto sediments along the Songhua River,which was one of the efforts to evaluate the fate of nitrobenzene after the spillage event.The organic carbon contents of these sediments along the Songhua River var...

Degradation of nitrobenzene in aqueous solution by ozone-ceramic honeycomb

The degradation of nitrobenzene by ceramic-honeycomb catalyzed ozonation was investigated. The results showed that the presence of ceramic honeycombs significantly increased the oxidation rate of nitrobenzene by ozone compared to the case of ozone oxidation alone. In this paper, the effects of various factors on the catalytic oxidation were investigated, such as the amount of catalysts, the ozone dosage, the temperature, the pH value and the presence of tert-butanol. With the addition of tert-butanol the removal of nitrobenzene decreased sharply, which appeared to support that, the degradation of nitrobenzene by ozonation followed a radical type mechanism. The EPR experiments verified that higher nitrobenzene removal rate was attributed to more OH radicals generated in the catalyzed ozonation than ozonation alone.

Location and PCR analysis of catabolic genes in a novel Streptomyces sp. DUT_AHX capable of degrading nitrobenzene

A novel strain of Streptomyces sp.DUT_AHX was isolated from sludge contaminated with nitrobenzene and identified on the basis of physiological and biochemical tests and 16S ribosomal DNA (rDNA) sequence analysis.The optimal degradation conditions were as follows:temperature 30℃,pH 7.0-8.0,shaking speed 150-180 r/min,and inocula 10%(V/V).The strain,which possessed a partial reductive pathway with the release of ammonia,was also able to grow on mineral salts basal (MSB) medium plates with 2-aminophenol, pheno...

Degradation of Nitrobenzene-Containing Wastewater with O_3 and H_2O_2 by High Gravity Technology

Nitrobenzene-containing industrial wastewater was degraded in the presence of ozone coupled with H2O2 by high gravity technology. The effect of high gravity factor, H2O2 concentration, pH value, liquid flow-rate, and reaction time on the efficiency for removal of nitrobenzene was investigated. The experimental results show that the high gravity technology enhances the ozone utilization efficiency with O3/H202 showing synergistic effect. The degradation efficiency in terms of the COD removal rate and nitrobenzene removal rate reached 45.8% and 50.4%, respectively, under the following reaction conditions, viz.： a high gravity factor of 66.54, a pH value of 9, a H2O2/O3 molar ratio of 1：1, a liquid flow rate of 140 L/h, an ozone concentration of 40 rag/L, a H2O2 multiple dosing mode of 6 mL/h, and a reaction time of 4 h. Compared with the performance of conventional stirred aeration mixers, the high gravity technology could increase the COD and nitrobenzene removal rate related with the nitrobenzene-containing wastewater by 22.9% and 23.3%, respectively.

QSAR Study of Nitrobenzenes’ Toxicity to Tetrahymena Pyriformis Using Semi-empirical Quantum Chemical Methods

The molecular geometries and electronic structures of 30 nitrobenzenes have been calculated by using semi-empirical MO AM1 and PM3 methods. EHOMO, ELUMO, ENHOMO, ENLUMO, AE, QNO2, Qc and V were selected as the structural descriptors. The acute toxicity （-log/C50） of nitrobenzenes to tetrahymena pyriformis along with the above eight structural parameters was used to establish the quantitative structure-activity relationships （QSARs）. The results indicate that the established model based on AM I method is superior to that on PM3 method not only for the stability but also for the predictive powers of the model. Based on AM1 parameters, a further classifying discussion was presented for the study of nitrobenzene toxic mechanism. The results show that the substituents, nitro group and halogen substituents on the aromatic ring are crucial to the chemicals＇ toxicity. For nitrobenzenes without halogen or other substituent, the reduction of nitro group is the main route. However, for those with halogen substituents, their next lowest unoccupied molecular orbital may take part in the toxic action betweeen the chemicals and macromolecules, and ENLUMO has the most important effect on these chemicals＇ toxicity.

Concentration level and geographical distribution of nitrobenzene in Chinese surface waters

Nitrobenzene was reported to occur at relatively high concentrations in some Chinese surface water and to cause an environmental pollution event in 2005.To map the distribution of nitrobenzene in the Chinese surface water throughout China,surface water samples were collected from over 600 sites in the 7 major watersheds and three drainage areas.The samples were analyzed for concentration of nitrobenzene.Overall,nitrobenzene was more frequently detected at higher concentrations in the rivers of North China,i...

QSAR Studies on the Toxicity of Nitrobenzenes to Population Growth of Tetrahymena Pyriformis

The IGC 50 (50% inhibitory growth concentration) values of 27 nitrobenzenes were determined for the population growth endpoint of Tetrahymena pyriformis . The toxicity order of the observed compounds was found to be as follows: dinitro compounds>mononitro compounds, dichloronitrobenzenes>monochloronitrobenzenes, meta substituted nitrobenzenes>ortho /para substituted nitrobenzenes(NT, NPh, NAnis) except for the dinitrobenzenes and nitroanilines(DNB, NAn). Quantitative structure activity relationships(QSARs) were developed with the logarithm of the reciprocal of IGC 50 [lg(IGC 50 ) -1 ] in mole liter as dependent variable and six molecular descriptors lg P , 1 X Ⅴ, I, 1K a, ∑σ - and E LUMO as independent variables. Via multiple regression analysis, one best equation was obtained: lg(IGC 50 ) -1 =3.029+0.860∑ σ -+0.341I n=27, r=0.924, r 2=0.854, s=0.265, f=70.44 , Pr> f =0.000 1 The equation was used to estimate IGC 50 for five analogues.

Reduction of nitrobenzene by the catalyzed Fe/Cu process

The polarization behavior of the couple Fe/Cu in 100 mg/L nitrobenzene aqueous solution was studied using Evans coupling diagrams.The results indicated that the iron corrosion was limited by both anodic and cathodic half-cell reactions under the neutral conditions,and cathodically controlled under the alkaline conditions.Batch experiments were performed to study the effect of solution pH,reaction duration,concentration,type of electrolyte,and dissolved oxygen(DO)on the reduction of nitrobenzene by the catal...

Phototransformation of nitrobenzene in the Songhua River:Kinetics and photoproduct analysis

Nitrobenzene (NB) pollution of the Songhua River caused by an explosion at a petrochemical plant in Jilin City,Jilin Province, China,attracted public concern over the fate of NB in the river.As one of the efforts to predict the fate of residual NB in the river,the kinetics and mechanism of phototransformation of NB in natural water from four sections of the Songhua River were investigated.It was found that photodegradation of NB in water proceeded via pseudo-first-order reaction kinetics under simulated sol...

Degradation of Wastewater Containing Nitrobenzene by High Gravity-Ultrasonic/Ozonation/Electrolysis Technology

The integrated high gravity-ultrasonic/ozonation/electrolysis technology was applied in the pretreatment of wastewater containing nitrobenzene. The effect ofpH value, high gravity factor, liquid flow-rate and electric current density on removal of COD and nitrobenzene compounds was investigated. Experimental results have determined the optimal pro- cess regime involving a high gravity factor of 100, an electric current density of 20 mA/cm2, a liquid flow-rate of 100 L/h, and an initial liquid pH value of 11. After the wastewater had been treated for 180 rain, the degradation of nitrobenzene and COD reached 99% and 80%, respectively, with the biochemical coefficient （BOD/COD） equating to 0.64, and the subse- quent treatment of wastewater could be carried out by conventional biochemical means. Compared with traditional aeration- ozone contactors, a rotating packed bed with high mass transfer characteristics could be used to increase the ozonation treat- ment efficiency.

Effects of Nitrobenzene on Liver Antioxidant Defense System of Carassius auratus

With superoxidedismutase（SOD）, catalase（CAT）, glutathione S-transferase（GST） and malondialdehyde （MDA） as characteristic indexes, the effects of nitrobenzene（NB） on the liver antioxidant defense system of Carassius auratus were studied under the indoors stimulant conditions, and the toxic mechanisms were discussed. The exposure concentrations of NB were 0.5, 1.0, 5.0 and 10.0 mg/L, and the exposure time was 5, 10 and 15 days, respectively. The results show that the stress responses of four antioxidant indexes in the fish liver to nitrobenzene were different. The SOD activity was firstly inhibited and then induced. The CAT and GST activities were mainly induced. The MDA content in the high concentration group showed a significant time-effect relationship. In addition, the changes of CAT and SOD activities were not synchronous, and GST played an important part in the detoxification process of nitrobenzene.

A DFT-based Quantum Theoretic QSAR Study of Nitrobenzenes' Toxicity to Tetrahymena Pyriformis

In this study,DFT-B3LYP level of theory with the 6-311G basis set was used to calculate a set of molecular descriptors of 36 nitrobenzenes.Quantitative structure-activity relationship（QSAR） models of the toxicity（pIGC50） of 36 nitrobenzenes were established using some of the following calculated descriptors：HOMO energy（EHOMO）,LUMO energy（ELUMO）,the difference between LUMO and HOMO energy values（ΔE=ELUMO–EHOMO）,average polarizability（P）,dipole moment（μ）,molecular volume（V） and the charge of nitro group（Q-NO2）.The QSAR models obtained by employing stepwise multiple regression techniques are aimed at correlating the structures with their reported experimental toxicity values. Among the models presented in this study, statistically the most significant one is a two-parameter linear equation with the correlation coefficient （R2） of 0.896 and cross-validated correlation coefficient （R2cv） of 0.878. To further validate the predictive ability of the resulting model, external validation was carried out with R2~xt and Q^2,ext values of 0.894, 0.900, 0.909, 0.874, 0.885 and 0.903, respectively. This study also reconstructed the obtained models using AMl-based calculated descriptors to demonstrate the superiority of DFT over AM1 for quantum calculations of mechanical descriptors. The results were discussed in the light of the main factors that influence the toxicity of nitrobenznenes.

Recovery of Aniline from Wastewater by Nitrobenzene Extraction Enhanced with Salting-Out Effect

Objective Nitrobenzene extraction enhanced by salting-out effect was employed to recover aniline from wastewater at 25 ℃. Method Batchwise experiments were conducted to elucidate the influence of various operating variables on the extracting performance, including acidity of wastewater, initial aniline concentration, ratios of solvent to wastewater, extraction stages, concentrations and different types of inorganic salts, such as NaCl, KCI, Na2SO4, CaCl2 and K29O4. Results Nitrobenzene with a concentration of 20% and a pH value of 9.1 at the temperature of 25 ℃ together with NaCl of a concentration of 14 wt.% realized nearly 100% aniline recovery at the fifth stage of wastewater treatment. Conclusions High pH values and volume ratios of nitrobenzene/wastewater are more suitable for recovery of aniline. In addition, recovery of aniline is significantly elevated with increase of the concentration of salts, whose promoting effects are in the following order: NaCI〉Na2SO4〉K2SO4〉CaC12〉KCI on the weight basis of wastewater. Furthermore, aniline in wastewater can be almost completely recovered by five-stage sequential nitrobenzene extraction, which is promoted continuously by the salting-out effect.

Degradation of Nitrobenzene Wastewater via Iron/Carbon Micro-electrolysis Enhanced by Ultrasound Coupled with Hydrogen Peroxide

The zero valent iron/granular active carbon(ZVI/GAC) micro-electrolysis enhanced by ultrasound(US) coupled with hydrogen peroxide(H_2O_2) was investigated for the deep degradation of nitrobenzene-containing wastewater. The results of scanning electron microscopy-energy dispersive X-rays analysis(SEM-EDS) demonstrated that continuously accelerated regeneration of ZVI and GAC in situ by US could improve the process for converting nitrobenzene(NB) to aniline(AN). H_2O_2 was decomposed catalytically by the byproduct Fe^(2+) ions generated in the micro-electrolysis process to hydroxyl radicals and the organic pollutants in the wastewater were finally mineralized to CO2 and H2O. Effects of the ZVI dosage, the ZVI/GAC mass ratio, the initial pH value and the H_2O_2 dosage on the efficiency for degradation of NB were studied in these experiments. The optimal operating conditions covered a ZVI dosage of 15 g/L, a ZVI/GAC mass ratio of 1:2,an initial pH value of 3 and a H_2O_2 dosage of 4 mL. In this case, the NB removal efficiency reached 97.72% and the total organic carbon(TOC) removal efficiency reached 73.42% at a NB concentration of 300 mg/L. The reduction of NB by USZVI/GAC followed the pseudo-first-order kinetics model, and the pseudo-first-order rate constants were given at different initial pH values. The reaction intermediates such as AN, benzoquinonimine, p-benzoquinone, p-nitrophenol and other organic acids were detected and a probable pathway for NB degradation has been proposed.

A novel salt-tolerant Micrococcus sp. DUT_AHX capable of degrading nitrobenzene

A novel strain of Micrococcus sp.DUT_AHX,which was isolated from the sludge of a nitrobenzene(NB)-manufacturing plant and could utilize NB as the sole carbon source,was identified on the basis of physiological and biochemical tests and 16S ribosomal DNA(rDNA)sequence analysis.It can grow at the temperature up to 40℃or in the presence of NaCl concentration up to 12 g/L in Luria-Bertani(LB)medium.The optimal degradation conditions are as follows:temperature 37℃,pH 7.0,and shaking speed 150 r/min.The strain involves a partial reductive pathway due to the release of ammonia and can also utilize 2-aminophenol as the sole carbon source.Furthermore,the enzyme activity tests show that crude extracts of NB-grown strain DUT_AHX mainly contain 2-aminophenol 1,6-dioxygenase activity.The exploitation of salt-tolerant bacteria will be a remarkable improvement in NB bioremediation and wastewater treatment at high salinity and high temperature.

Degradation of nitrobenzene in wastewater by γ-ray irradiation

The degradation of nitrobenzene(NB) by γ ray irradiation was studied. The influences of dose rate and initial NB concentration were investigated in details. At a dose rate of 55 Gy/min, the degradation kinetics was pseudo first order at NB concentrations from 0 2 mmol/L to 4 0 mmol/L. At an initial NB concentration of 0 8 mmol/L, the degradation of NB at various dose rates also followed pseudo first order kinetics. Dissolved oxygen was found to have a positive effect on NB degradation. The degradation products were identified as nitrophenol, nitrosobenzene, and hydroquinone, and so on. Based on the product analysis, possible degradation pathways of nitrobenzene were proposed.

High halogenated nitrobenzene hydrogenation selectivity over nano Ir particles

The selective hydrogenation of halogenated nitrobenzene over noble metal catalysts(Pd, Pt, and Ir) has attracted much attention owing to its high efficiency and environmental friendliness. However, the effect of size on the catalytic performance varies among different metal catalysts. In this study, sub-nano(<3 nm) Ir and Pd particles were prepared, and their catalytic properties for hydrogenation of halogenated nitrobenzene were evaluated.Results show that high selectivity(N 99%) was achieved over small Ir nanoparticles, in which the selectivity over the Pd with same size was much lower than that on Ir nanoparticles. Meanwhile, Ir and Pd have different hydrogen consumption rates and reaction rates. Density functional theory calculations showed that p-chloronitrobenzene(CNB) has different adsorption properties on Ir and Pd. The distance between oxygen(cholorine) and Ir is much shorter(longer) than that between oxygen and Pd. The reaction barriers of dechlorination of p-CNB and p-chloroaniline over different Ir models are much larger than those on Pd. Especially,lower coordination of Ir leads to larger barriers of dechlorination reaction. These theoretical results explain the difference between Ir and Pd on hydrogenation of halogenated nitrobenzene.