Degradation of chlorobenzene by non-thermal plasma coupled with catalyst:influence of catalyst,interaction between plasma and catalyst

Non-thermal plasma(NTP)is considered to be a promising technology for the removal of volatile organic compounds;however,its application is limited by low CO_(2) selectivity and undesirable by-products.To overcome these issues,this paper discusses the degradation of chlorobenzene(CB)in systems of NTP coupled with catalysts,and the influence of catalyst locations in the NTP was investigated.In addition,the interaction between plasma and catalyst was also explored.The results indicated that the degradability of CB was remarkably improved through the combination of NTP with catalysts,and the formation of ozone was effectively inhibited.The degradation efficiency increased from 33.9%to 79.6%at 14 kV in the NTPcatalytic system,while the ozone concentration decreased from 437 to 237 mg m^(-3),and the degradation efficiency of in plasma catalysis(IPC)systems was superior to that of the post plasma catalysis system,while the inhibition ability of ozone exhibited an opposing trend.In the IPC system,the degradation efficiency was 87.7%at 14 k V,while the ozone concentration was151 mg m^(-3).Besides,the plasma did not destroy the pore structure and crystal structure of the catalyst,but affected the surface morphology and redox performance of the catalyst.Thus,NTP coupled catalytic system could improve the degradation performance of CB.Furthermore,the plasma discharge characteristics played a major role in the NTP synergistic catalytic degradation of CB.Finally,based on the experiment analysis results,the general reaction mechanism of CB degradation in an IPC reaction system was proposed.

A Study on Side Reactions of Hydroxyethylation of 3-Nitro-4- chlorobenzenesulfinic Acid with Ethylene Oxide

The reaction of 3-nitro-4-chlorobenzenesulfinic acid and ethylene oxide to obtain 2-nitro-4-（β-hydroxyethylsulfonyl）chlorobenzene had been studied. Except hydroxyethylation on the sulfur atom of 3-nitro-4-chlorobenzenesulfinic acid to form the target product, 2-nitro-4-（β- hydroxyethylsulfonyl）chlorobenzene, there presented three kinds of side reactions： 1. Condensation and elimination of HCI to form biphenyl sulfone derivatives; 2. Addition to give bisulfonyl ethane derivative via vinyl sulfone; and 3. Hydroxylethylation on O-atom to produce hydroxylethylsulfinate due to the tautomerism of sulfinic acid.

Chlorobenzene degradation by electro-heterogeneous catalysis in aqueous solution:intermediates and reaction mechanism

This study was performed to investigate the variables that influence chlorobenzene (CB) degradation in aqueous solution by electro-heterogeneous catalysis.The effects of current density,pH,and electrolyte concentration on CB degradation were determined.The degradation effciency of CB was almost 100% with an initial CB concentration of 50 mg/L,current density 15 mA/cm2,initial pH 10,electrolyte concentration 0.1 mol/L,and temperature 25°C after 90 min of reaction.Under the same conditions,the degradation eff...

Biodegradation of Gaseous Chlorobenzene by White-rot Fungus Phanerochaete chrysosporium

Objective To evaluate the effect of white rot fungus Phanerochaete chrysosporium on removal of gaseous chlorobenzene. Methods Fungal mycelium mixed with a liquid medium was placed into airtight bottles. A certain amount of chlorobenzene was injected into the headspace of the bottles under different conditions. At a certain interval, the concentrations in the headspace were analyzed to evaluate the degradation of chlorobenzene by P. chrysosporium. Results The degradation effects of P. chrysosporium on chlorobenzene under different conditions were investigated. The difference in the optimum temperature for the growth of the fungi and chlorobenzene degradation was observed. The data indicated that a lower temperature （28℃） would promote the degradation of chlorobenzene than the optimum temperature for the growth of the fungi （37℃）. A low nitrogen source concentration （30 mg N/L） had a better effect on degrading chlorobenzene than a high nitrogen source concentration （higher than 100 mg N/L）. A high initial concentration （over 1100 mg/m3） of chlorobenzene showed an inhibiting effect on degradation by P chrysosporium. A maximum removal efficiency of 95% was achieved at the initial concentration of 550 mg/m3. Conclusion P. chrysosporium has a rather good ability to remove gaseous chlorobeuzene. A low nitrogen source concentration and a low temperature promote the removal of chlorobenzene by P. chrysosporium. However, a high initial chlorobenzene concentration can inhibit chlorobenzene degradation.

Chlorobenzenes in waterweeds from the Xijiang River (Guangdong section) of the Pearl River

The Xijiang River is the major source of water for about 4.5 millions of urban population and 28.7 millions of rural population. The water quality is very important for the health of the rural population. The concentration and distribution of chlorobenzenes （CBs） in both water and waterweeds collected from 4 stations in the Xijiang River （Gangdong section） of the Pearl River in April and November were determined. The result showed that nearly every congener of CBs was detected. The total contents of CBs （ZCBs） in the river water ranged from 111.1 to 360.0 ng/L in April and from 151.9 to 481.7 ng/L in November, respectively. The pollution level of CBs in the water in April was higher than that in November. The contents of ZCBs in waterweeds ranged from 13.53×10^2μg/g to 38.27×10^2μg/g dry weight （dw）. There was no significant difference between April and November in waterweeds. The distribution of CBs in roots, caulis, and leaves of Vallisneria spiralis L. showed different patterns. The leaves mainly contained low-molecular-weight CBs （DCBs）, whereas the roots accumulated more PCBs and HCBs. The average lgBCFlip （bioconcentration factor） of CBs ranged from 0.64 to 3.57 in the waterweeds. The spatial distribution character of CBs in the Xijiang River was： Fengkai County 〈 Yunan County 〈 Yun＇an County 〈 Gaoyao County according to the ZCBs, and the pollution deteriorated from the upstream to the downstream of the Xijiang River. Further analysis demonstrated that the discharge of waste containing CBs may be the main source of CBs pollution in the Xijiang River .

Catalytic Dechlorination of Chlorobenzene in Water by Pd/Fe System

Chlorobenzene was dechlorinated by Pd/Fe bimetallic system in water through catalytic reduction. The dechlorination rate increases with increase of bulk loading of Pd due to the increase of both the surface loading of the Pd and the total surface area. For conditions with 0.005% Pd/Fe, 45% dechlorination efficiency was achieved within 5 h. The dechlorinated reaction is believed to take place on the bimetal surface in a pseudo-first-order reaction, with the rate constant being 0.0043 min-1.

Catalytic dechlorination of chlorobenzene in water by Pd/Fe bimetallic system

Catalytic reductive dechlorination of monochlorobenzene(MCB) was carried out in the palladium/iron system. With low Pd loading(0 005%), 45% dechlorination efficiency was achieved within 5 h. Pd as catalyst accelerated the reductive dechlorination reaction. Dechlorination mechanism and kinetics were discussed. The reaction took place on the bimetal surface in a pseudo first order reaction, with the rate constant being 0 0071 min -1 ( K SA =8 0×10 -3 L/(m 2·h). The reduction product for MCB was benzene.

Electrokinetic movement of multiple chlorobenzenes in contaminated soils in the presence of β-cyclodextrin

This study investigated the electrokinetic （EK） behavior of multiple chlorobenzenes, including 1,2,3,4-tetrachlorobenzene （TeCB）, 1,2,4,5-tetrachlorobenzene （i-TeCB）, and 1,2,3-trichlorobenzene （TCB） in contaminated clayed soils. The effect of β-cyclodextrin （β- CD） on the EK removal of the chlorobenzenes was studied. The largest removal was obtained when Na2CO3/NaHCO3 buffer was used as anodic purging solution without β-CD. The removal efficiencies were related to the aqueous solubilities of chlorobenzenes. With the same cumulative electroosmotic flow, greater solubility led to higher removal efficiency. The addition of β-CD inhibited the EK removal efficiency of all chlorobenzenes. The inhibition increased with the increase of β-CD concentration. With the same β-CD concentration, the inhibition increased with the rise of electric potential. It was found that the inclusion compounds between β-CD and chlorobenzenzes were less soluble than chlorobenzenes. The formation of the less soluble inclusion compounds reduced the aqueous solubility of chlorobenzenes and led to the partial immobilization of the chlorobenzenes that desorbed from soil. It was feasible to use the EK technology to remove chlorobenzenes in contaminated soils using water as the anodic flushing solution. The addition of β-CD was not recommended for the EK removal of chlorobenzenes.

Heterogeneous Photocatalytic Mineralization of Chlorobenzene by Paratungstate-loaded Titania Catalysts in an Aqueous Medium

Paratungstate-loaded titania catalysts were prepared %via% the addition of a series of aqueous solutions of paratungstate(denoted as W_ 7) into an isopropanol solution of Ti[OCH(CH_ 3)_ 2]_ 4 by means of the sol-gel method. The catalysts were characterized by EDX, BET, FTIR, UV-Vis DRS, XRD and the results indicate that such paratungstate-loaded catalysts maintained their heptatungstate structure in the anatase titania matrix up to 400 ℃. The catalysts were tested for the heterogeneous photodegradation of chlorobenzene in aqueous media and showed a better catalytic activity than P-25 TiO_ 2 because paratungstate can prevent the recombination of the holes and electrons produced during irradiation. Moreover, the paratungstate-loaded titania catalysts can resist the disaggregation during the photoirradiation and can be easily recycled from the aqueous suspensions after reactions.

Measurement and Correlation of Isobaric Vapor-Liquid Equilibrium of Three Binary Systems Containing Chlorobenzene at 50.00 and 101.33 kPa

Isobaric vapor-liquid equilibrium(VLE) data for three binary systems, chlorobenzene + N,N-dimethylformamide, chlorobenzene + furfural, and chlorobenzene + benzaldehyde, were measured at 50.00 and 101.33 kPa using a modified Rose-Williams still. Gas chromatography was used to analyze the compositions of the samples and no azeotropic behavior was found. All of the measured VLE values were checked by the semi-empirical method proposed by Herington and the point-to-point Van Ness test method modified by Fredenslund. The experimental data were correlated by using the Wilson, the non-random two-liquid and universal quasi-chemical activity coefficient models. The corresponding parameters for the three models were obtained.

Study on the Effect of Underground Temperature on the Adsorption Behavior of Chlorobenzene under Artificial Recharge Condition

[ Objective] The research aimed to study the effect of underground temperature on the adsorption behavior of chlorobenzene under artifi- cial recharge condition. [ Method] Based on the prior researches, combining actual condition of the artificial recharge test site, the adsorption be- havior of chlorobenzene under the background of artificial recharge was discussed. [ Reset ] The adsorption reaction of chlorobenzene correspon- ded with quasi-first-order and quasi-second-order kinetics equations at certain concentration. When temperature rose, reaction rate accelerated, and adsorption balance time shortened to 12 （0 ℃）, 10 （10 ℃） and 8 （20 ℃） h. The adsorption of chlorobenzene corresponded with isothermal adsorption model very well at different concentrations. When temperature ranged from 0 to 20 ℃, the adsorption amount of medium on chloroben- zene increased at equilibrium time. The maximal adsorption amounts calculated by Langmuir model were 20.747, 21. 505, 23.364 μg/g at 0, 10 and 20 ℃, respectively. [ Conclusion] The adsorption of chlorobenzene in aquifer medium was endothermic reaction, and the best season of artifi- cial recharne was in summer.

Carbon Dioxide Fixation Method for Electrosynthesis of Benzoic Acid from Chlorobenzene

Carbon dioxide fixation technique was developed as an alternative dechlorination method of chlorobenzenes. Electrolysis of chlorobenzene was carried out in a one-compartment cell fitted with an aluminium anode and a platinum cathode. Electrolysis in N, N-dimethylformamide （DMF） solution containing 0.1 M of tetrapropylammonium bromide （TPAB） at 0 ℃, 100 ml/min of CO2 flow rate and 120 mA/cm^2 of current density was found to be the optimum conditions of this electrocarboxylation, which gave 72% yield of benzoic acid from chlorobenzene. These conditions were then applied to 1,2-dichlorobenzene and 1,3-dichlorobenzene in order to convert them to their corrcsponding benzoic acids.

A Study of Removing Chlorobenzene by the Synergistic Effect of Catalysts and Dielectric-Barrier Discharge Driven by Bipolar Pulse-Power

In this study, the improvement in the removal of chlorobenzene （C6H5Cl） in the air was investigated by combining dielectric barrier discharge （DBD） driven by bipolar pulse-power with catalysts. Molecular sieve 4A （MS-4A） and MnO2/γ-Al2O3 （MnO2/ALP） as two kinds of catalysts were tested at different positions in a DBD reactor. Catalysts were located either in the discharging area between two electrodes, or just behind the discharging area （in the afterglow area） closed to the outlet. The results indicated that DBD reactor with a bipolar pulse power-supply produced strong instant discharge and energetic particles, which can effectively activate catalysts of MS-4A and MnO2/ALP located in the afterglow area to achieve the synergistic effects on effective fission of chemical bonds of chlorobenzene. It was considered that the gas-chlorobenzene and the chlorobenzene adsorbed on the catalysts were decomposed simultaneously.

Thermal Decomposition of Diphenyl Tetroxane in Chlorobenzene Solution

The thermal decomposition of Cyclic Diperoxide of Benzaldehyde 3,6-diphenyl-1,2,4,5-tetroxane, (DFT) in chlorobenzene solution in the studied temperature range (130°C - 166°C) satisfactorily satisfies a first order law up to 60% conversions of diperoxide. DFT would decompose through a mechanism in stages and initiated by the homolytic breakdown of one of the peroxidic bonds of the molecule, with the formation of the corresponding intermediate biradical. The concentration studied was very low, so that the effects of secondary reactions of decomposition induced by free radicals originated in the reaction medium can be considered minimal or negligible. The activation parameters for the unimolecular thermal decomposition reaction of the DFT are ΔH# = 30.52 ± 0.3 kcal·mol-1 and ΔS# = -6.38 ± 0.6 cal·mol-1 K-1. The support for a step-by-step mechanism instead of a process concerted is made by comparison with the theoretically calculated activation energy for the thermal decomposition of 1,2,4,5-tetroxane.

Heterobimetallic CoCeO_(x) derived from cobalt partially-substituted Ce-UiO-66 for chlorobenzene efficient catalytic destruction

Here,a metal-organic framework(MOF)-templated strategy was applied to synthesize the CoCeO_(x) bimetallic catalysts by calcining Co partially-substituted Ce-UiO-66.It is indicated that the substituted Co limited Ce cations in Ce-UiO-66 framework,which affects its growth and structure crystallinity to some extent.After pyrolysis treatment,the derived bimetallic oxide(CoCeO_(x)-M)can basically keep the octahedral structure and the surface area is much higher than the bulk metal composite oxide(CoCeO_(x)-B)prepared by traditional coprecipitation.Results reveal that CoCeO_(x)-M performs the best chlorobenzene degradation capacity,superior stability and vapor tolerance compared with those of CeO_(2)-M(derived from Ce-UiO-66)and CoCeO_(x)-B.At the same time,it is favorable to inhibit the formation of CO during the oxidation reaction.The superior catalytic performance of CoCeO_(x)-M is attributed to a good dispersion of metal cations,high surface area and active oxygen concentration,and good redox property.Moreover,the formation of organic byproducts especially chlorinated organics can be obviously prohibited over CoCeO_(x)-M compared with that of CeO_(2)-M.Mechanism study reveals that chlorobenzene dissociates on the surface of CoCeO_(x)-M to form carboxylates such as acetate species,maleate and phenolate before finally oxidized into CO_(2),H_(2)O,and HCl.The present work poses new insights into the fabrication of efficient catalysts for industrial CVOC purification.

Atmospheric heterogeneous reaction of chlorobenzene on mineralα-Fe_(2)O_(3)particulates:a chamber experiment study

Despite the large emission of chlorinated volatile organic compounds(CVOCs)into the atmosphere,the ultimate fate of these compounds remains largely unknown.Herein,we explore the photochemical conversion of an important class of CVOCs,namely chlorobenzene(CB),on mineralα-Fe_(2)O_(3)particulates under atmospheric relevant conditions.A series of chamber reactions composed of the CB with/without SO_(2)or NO_(2)are performed,followed by in situ diffuse reflectance infrared Fourier transform spectroscopy measurements and density functional theory calculations.We show that CB can be considerably degraded byα-Fe_(2)O_(3)under light irradiation,whereas the reaction is markedly suppressed by adding SO_(2)or NO_(2)owing to their competitive adsorption and surface acidification.In particular,we discover that CB can be ultimately converted into polychlorinated dibenzo-p-dioxins and dibenzofurans(PCDD/Fs)under dark state or light irradiation,suggesting a possible origin of atmospheric PCDD/Fs from this overlooked photochemical source.

Synthesis of hierarchical porous carbon with high surface area by chemical activation of(NH_(4))_(2)C_(2)O_(4) modified hydrochar for chlorobenzene adsorption

In this work,hydrothermal technique combined with KOH activation were employed to develop a series of porous carbons (NPCK-x) using tobacco stem as a low-cost carbon source and (NH_(4))_(2)C_(2)O_(4)as a novel nitrogen-doping agent.Physicochemical properties of NPCK-x were characterized by Brunauer-Emmett-Teller,field emission scanning electron microscopy,X-ray diffraction,Raman microscope,elemental analysis,and X-ray photoelectron spectroscopy.Results showed that the NPCK-x samples possessed large surface areas (maximum:2875 m^(2)/g),hierarchical porous structures,and high degree of disorder.N-containing functional groups decomposed during activation process,which could be the dominant reason for appearance of abundant mesopores and well-developed pore structure.Dynamic chlorobenzene adsorption experiments demonstrated that carbon materials with(NH_(4))_(2)C_(2)O_(4)modification exhibited higher adsorption capacity (maximum:1053 mg/g) than those without modification (maximum:723 mg/g).The reusability studies of chlorobenzene indicated that the desorption efficiency of (NH_(4))_(2)C_(2)O_(4)modified porous carbon reached90.40%after thermal desorption at 100℃ under N2atmosphere.Thomas model fitting results exhibited that the existence of mesopores accelerated the diffusion rate of chlorobenzene in porous carbon.Moreover,Grand Canonical Monte Carlo simulation was conducted to verify that micropores with pore sizes of 1.2–2 nm of the optimized porous carbon were the best adsorption sites for chlorobenzene and mesopores with pore sizes of 2–5 nm were also highly active sites for chlorobenzene adsorption.

Effect of temperature and oxygen on the formation of chlorobenzene as the indicator of PCDD/Fs

Sampling and analysis of polychlorinated dibenzo-p-dioxins and dibenzofurans （PCDD/Fs） are both time-consuming and expensive. In principle, real-time monitoring of chlorobenzene （CBz） as an indicator for PCDD/Fs could be useful to control and optimize incinerator operating conditions. To test this strategy, CBz was analyzed together with PCDD/Fs in flue gas samples collected from a hospital waste incinerator. Moreover, lab experiments were conducted to investigate the effect of temperature and oxygen on CBz formation from fly ash from the same incinerator. The experimental results demonstrate that chlorobenzene （in particular PeCBz） correlate well with PCDD/Fs, in line with previous research. The optimum temperature of CBz formation is in a range of 350 to 400℃ and CBz yield increases significantly with oxygen, in line with PCDD/Fs formation. This study is useful for confirming the de novo mechanism and defining correlations between CBz and PCDD/Fs.

MCM-41 supported nano-sized CuO-CeO2 for catalytic combustion of chlorobenzene

In this paper,MCM-41 was synthesized by a soft template technique and MCM-41 supported CuO-CeO2 nano-sized catalysts with different Cu/Ce molar ratios were prepared by a deposition-precipitation method.N2 adsorption,HRTEM-EDS,H2-TPR,XPS characterization,as well as catalytic activity and durability tests for the catalytic combustion of chlorobenzene(CB)were conducted to explore the relationship between the structure and catalytic performance of the catalysts.It is revealed that cuCe(6:1)/MCM-41 has the highest activity and can completely catalyze the degradation of CB at 260℃.The reasons for the high activity of the catalysts are as follows:MCM-41,a type of mesoporous material which has large pore size and large specific surface area,is suitable as a catalyst carrier.The average diameter of nano-sized CuO and CeO2 particles is about 3-5 nm and adding CeO2 improves the dispersion of active component CuO,which are highly and evenly dispersed on the surface of MCM-41.Characterization results also explain why MCM-41 supported CuO-CeO2 with appropriate proportion can highly enhance the catalytic activity.The reason is that CeO2 acting as an oxygen-rich material can improve the mobility of oxygen species through continuous redox between Ce4^+and Ce3^+,and improve the catalytic performance of CuO for CB combustion.Besides,CuCe(6:1)/MCM-41 also displays good durability for CB combustion,both in the humid condition and in the presence of benzene,making it a promising catalytic material for the elimination of chlorinated VOCs.