Effect of biogenic substrate concentration on the performance of sequencing batch reactor treating 4-CP and 2,4-DCP mixtures

Effect of a biogenic substrate (peptone) concentration on the performance of sequencing batch reactor (SBR) treating 220 mg/l 4-chlorophenol (4-CP) and 110 mg/l 2,4-dichlorophenol (2,4-DCP) mixtures was investigated. In this context, peptone concentration was gradually decreased from 300 mg/l to null in which chlorophenols were fed to the reactor as sole carbon and energy sources. By this way, the effect of peptone concentration on observed yield coefficient (Y), biomass concentration, chlorophenols and COD removal performances were investigated. Decreasing peptone concentration accompanied with lower biomass concentration led to increase in peak chlorophenol and COD concentrations within the reactor during each SBR cycle. This, in turn, caused noteworthy declines in the removal rates as chlorophenol degradations followed Haldane substrate inhibition model. Also, increased peak chlorophenol concentrations led to the accumulation of 5-chloro-2-hydroxymuconic semialdehyde (CHMS), which is -meta cleavage product of 4-CP. Despite the decreased removal rates, complete chlorophenols and CHMS degradation, in addition to high COD removal efficiencies (>90%), were observed for all studied conditions, even chlorophenols were added as sole carbon and energy sources. Another significant point is that 2,4-DCP at slightly elevated concentrations (>20 mg/l) within the reactor caused a strong competitive inhibition on 4-CP degradation. In SBR, feeding the influent to the reactor within a certain period (i.e. filling period) provided dilution of coming wastewater, which decreased the chlorophenols concentrations to which microorganisms were exposed. Therefore, use of SBR may help to avoid both self and competitive inhibitions in the treatment of 4-CP and 2,4-DCP mixture especially in the presence high biogenic substrate concentrations. In addition, isolation and identification studies have indicated that Pseudomonas sp. and Pseudomonas stutzeri were dominant species in the acclimated mixed culture.     

Liquid phase hydrodechlorination of chlorophenols at lower temperature on a novel Pd catalyst

Pd catalyst supported on mesoporous silica-carbon nano-composite (Pd/MSCN) was prepared by the method of wet impregnation, and its activity for hydrodechlorination (HDC) of 2-chlorophenol, 4-chlorophenol and 2,4-dichlorophenol was evaluated at 258-313 K under ordinary hydrogen pressure by using triethylamine (Et(3)N) as a base additive. XRD analysis indicates that Pd/MSCN catalyst possesses the ordered mesostructure. Meanwhile, the results from TEM and H(2) chemisorption analysis indicate the high dispersion of Pd on MSCN with Pd nanoparticles whose average size is 3.2 nm. For the first time, the high activity of nano-size Pd on MSCN for HDC of chlorophenols was observed at 258 K. In addition, it was found that the inhibition effect of Et(3)N on HDC existed obviously, and can be efficiently reduced by stepwise addition of Et(3)N. The correlations of the dielectric constants of base and the polarity of solvent to the activity of Pd/MSCN for HDC of chlorophenols were obtained.     

Comparison treatment of various chlorophenols by electro-Fenton method: relationship between chlorine content and degradation

This study describes a comparative degradation of various chlorophenols by electro-Fenton method. Chloride released and reaction intermediate products were determined by ionic chromatography (IC) and gas chromatography/mass spectrometry (GC/MS). Using pentachlorophenol (PCP) as the model compound, we investigated the effects of cell voltage, electrolyte concentration and pH to optimize the degradation conditions. It was noted that the addition of small quantities of Fe3+ or Fe2+ significantly accelerated the degradation rate. Under the optimal conditions, electro-Fenton method was used to treat various chlorophenols including PCP, 4-chlorophenol (4-CP), 2,4-dichlorophenol (2,4-DCP), 2,4,6-trichlorophenol (2,4,6-TCP) and their mixture aqueous solutions. Their pseudo first-order degradation rate constants at the first stages were calculated and compared, which gave the following sequence: 2,4-DCP>2,4,6-TCP>PCP>4-CP. The relationship between the chlorine content and degradation rate was discussed and compared with other advanced oxidation processes. Finally, we proposed the degradation pathways of different chlorophenols.     

Photocatalytic decomposition of 4-chlorophenol over oxide catalysts.

4-Chlorophenol in the presence of catalysts was decomposed in aqueous solution by a 125 W medium pressure mercury lamp in a thermostated quartz batch photoreactor, and the organic bound chlorine was catalytically converted into the environmentally less harmful inorganic chloride. Differences in the concentration of 4-chlorophenol and of the intermediates, such as hydroquinone and quinone, are followed by HPLC. The best catalyst among a homolog series for the photo-decomposition of 4-chlorophenol was selected as finely dispersed platinum oxide on a TiO2 semiconductor support, and kinetic parameters of the Langmuir-Hinshelwood type decomposition reaction were reported for the selected catalyst. A simple mechanism of substrate degradation in accord with the chosen kinetic model was postulated. The developed process may serve photooxidative removal of chlorophenols in wastewater without using costly oxidants.     

Rate constants for the reactions of ozone with chlorophenols in aqueous solutions

The oxidation by ozone of several chlorophenols (CPs): 4-chlorophenol, 2,4-dichlorophenol, 2,4,6-trichlorophenol, 2,3,4, 6-tetrachlorophenol, tetracholorocatechol (3,4,5, 6-tetrachloro-2-hydroxy phenol) and 4-chloroguaiacol (4-chloro-2-methoxy phenol), is studied in order to provide values of the overall rate constant for the reaction between ozone and these chlorophenols. Single ozonation experiments of 4-chlorophenol were conducted in an homogeneous system, and ozonation reactions of CP mixtures were performed in a heterogeneous system, leading to the evaluation of the overall ozonation rate constants in acidic aqueous solutions. These second order rate constants increase several order of magnitude with the pH as does the degree of deprotonation of the dissolved compounds (i.e. from 10(3) to 10(9)l/(mols) for different CPs). The specific rate constants for the ozonation of the non-dissociated and dissociated forms of the studied CPs are also determined and reported. The values obtained allow calculation of the overall rate constants and prediction of the reactivities of the several CPs at different operating conditions in the whole range of pH.     

Photochemical treatment of 2-chlorophenol aqueous solutions using ultraviolet radiation, hydrogen peroxide and photo-Fenton reaction

In the present work, the photochemical oxidation of 2-chlorophenol aqueous solutions in a batch recycle photochemical reactor using ultraviolet irradiation and hydrogen peroxide was studied. Specifically, the effect of hydrogen peroxide initial concentration (0-10316 mg L(-1)) and 2-chlorophenol initial concentration (150-3000 mg L(-1)) was examined. The process was attended via total organic carbon (TOC), 2-chlorophenol, chloride ion, acetic acid, formic acid and pH measurements. The conversion of 2-chlorophenol observed was always much higher than the corresponding total organic carbon removal, whereas the increase in hydrogen peroxide amount in the solution led to higher values of 2-chlorophenol conversion and total organic carbon removal. Finally, the photo-Fenton reaction was applied to the oxidation of 2-chlorophenol, leading to a higher degree of mineralization of the parent compound.     

Photocatalytic decomposition of 2-chlorophenol in aqueous solution by UV/TiO2 process with applied external bias voltage

The decomposition of 2-chlorophenol by UV/TiO2 process with the application of external bias voltage was examined in this study. Experiments were conducted in a batch reactor using TiO2-coated titanium sheet as anode and platinum sheet as cathode. The anode photocatalysis of 2-chlorophenol was totally inhibited for experiments conducted with the application of external anodic bias voltage lower than the flat band potential of TiO2. The decomposition rate of 2-chlorophenol was then increased with increasing external anodic bias voltage applied up to 0.0 V (versus SCE). The application of external bias voltage higher than 1.0 V did not markedly promote the photocatalysis of 2-chlorophenol possibly because the photocurrent induced was constant. Experimental results indicated that the decomposition of 2-chlorophenol was more effective for experiments conducted in acidic solutions due to the lower flat band potential of TiO2 and the higher photocurrent induced. The presence of electron scavengers in aqueous solution, such as oxygen molecules, may increase the decomposition rate of 2-chlorophenol. However, the effect of dissolved oxygen was diminished for experiments conducted with applied external bias voltage. The photocatalytic decomposition rate of 2-chlorophenol was enhanced linearly with the increasing UV light intensity when the external bias voltage was applied.     

超高交联树脂对氯酚类化合物的吸附性能

通过静态吸附研究,比较了Am berlite XAD-4和ZH-01吸附树脂对水溶液中2-氯苯酚、2,4-二氯苯酚、2,4,6-三氯苯酚的吸附热力学特性。结果表明,在288 K~318 K和研究的浓度范围内,ZH-01、XAD-4对氯酚类化合物的吸附平衡数据符合F reund lich和L angm u ir吸附等温方程。2-氯苯酚在两树脂上的吸附为放热过程,是单分子层的物理吸附;而2,4-二氯苯酚和2,4,6-三氯苯酚在XAD-4吸附是单分子层物理吸附,在ZH-01的吸附属单分子层吸热过渡化学吸附,主要是毛细管凝聚和微孔填充作用造成的吸附。并计算了氯酚类化合物在两树脂上的吸附焓变、自由能变、吸附熵变,对吸附行为进行了合理的解释。     

Photo-electrocatalytic degradation of 4-chlorophenol over sputter deposited Ti oxide films

Ti oxide films with thicknesses in the 1.9–8.0 μm range were sputter deposited onto electrically conductive transparent glass substrates. X-ray diffraction indicated a dominating rutile structure. The films were used to investigate photo-electrocatalytic degradation of 4-chlorophenol in water solution, employing a specially designed reactor. UV light was used for the photocatalysis, and a bias potential was applied for avoiding electron-hole recombination. The photocurrent and the kinetics of the catalytic reaction were tested with potentiostatic and spectrophotometric measurements. The reaction products were investigated using different arrangements of a Ti oxide working electrode and a Pt counter electrode. UV irradiation through the glass substrate yielded an enhancement of the reaction kinetics for increased film thicknesses and applied bias potential.     

电感耦合等离子体对HDPE粉体的表面处理

用搅拌式电感耦合等离子体反应器对高密度聚乙烯（HDPE）粉体进行表面处理,采用水接触角、红外光谱（FT-IR）和X射线光电子能谱（XPS）对等离子体处理前后HDPE粉体的水接触角、表面成分的变化进行分析。实验结果表明,随着等离子体处理时间延长和放电功率增加,水接触角减小。在功率100W处理30min后,水接触角从处理前...     

Determination of chlorophenols in soils using accelerated solvent extraction combined with solid-phase microextraction

A method for the determination of chlorophenols in soil samples using accelerated solvent extraction (ASE) with water as the solvent combined with solid-phase microextraction (SPME) and GC/MS has been developed. Important ASE parameters, such as extraction temperature and time, were optimized using a spiked wetland soil. The effect of small amounts of organic modifiers on the extraction yields was studied. An extraction temperature of 125 degrees C and 10 min extractions performed three times proved optimal. Two ASE-SPME procedures without and with an organic modifier (5% acetonitrile) were evaluated with respect to precision and detection limits (LOD). The reproducibility of replicate water extractions/SPME determinations (n = 6) was in the range 7-20% relative standard deviation for the nine chlorophenols investigated. LOD values in the low-ppb range were achieved for all chlorophenols. The ASE-SPME procedure presented here was applied to the determination of chlorophenols in soil samples taken from contaminated areas near Bitterfeld, Germany.     

Modeling of adsorption isotherms of phenol and chlorophenols onto granular activated carbon. Part I. Two-parameter models and equations allowing determination of thermodynamic parameters

The adsorption equilibrium isotherms of five phenolic compounds from aqueous solutions onto granular activated carbon (GAC) were studied and modeled. Phenol (Ph), 2-chlorophenol (2-CP), 4-chlorophenol (4-CP), 2,4-dichlorophenol (DCP), and 2,4,6-trichlorophenol (TCP) were chosen for the adsorption tests. To predict the adsorption isotherms and to determine the characteristic parameters for process design, seven isotherm models: Langmuir (five linear forms), Freundlich, Elovich, Temkin, Fowler-Guggenheim, Kiselev, and Hill-de Boer models were applied to experimental data. The results reveal that the adsorption isotherm models fitted the data in the order: Fowler-Guggenheim>Hill-de Boer>Temkin>Freundlich>Kiselev>Langmuir isotherms. Adsorption isotherms modeling shows that the interaction of phenolic compounds with activated carbon surface is localized monolayer adsorption, that is adsorbed molecules are adsorbed at definite, localized sites. Each site can accommodate only one molecule. The interaction among adsorbed molecules is repulsive and there is no association between them, adsorption is carried out on energetically different sites and is an exothermic process. Uptake of phenols increases in the order Ph<2-CP<4-CP相似文献   

Photocatalytic treatment of 4-chlorophenol in aqueous ZnO suspensions: Intermediates,influence of dosage and inorganic anions

The photocatalytically driven removal of eco-persistent 4-chlorophenol from water using ZnO is reported here. Kinetic dependence of transformation rate on operating variables such as initial 4-chlorophenol concentration and photocatalyst doses was investigated. A complete degradation of 4-chlorophenol at 50 mg L⁻¹ levels was realised in 3 h. Analytical profiles on 4-chlorophenol transformation were consistent with the best-line fit of the pseudo zero-order kinetics. The addition of small amounts of inorganic anions as SO₄²⁻, HPO₄⁻, S₂O₈²⁻ and Cl⁻ revealed two anion types: active site blockers and rate enhancers. Fortunately, Cl⁻ and SO₄²⁻ commonly encountered in contaminated waters enhanced the rate of 4-chlorophenol degradation. The reaction intermediates and route to 4-chlorophenol mineralisation were elucidated by combined RP-HPLC and GC–MS methods. In addition to previously reported pathway products of 4-chlorophenol photo-oxidation catechol was detected. A radical mechanism involving o-hydroxylation is proposed to account for the formation of catechol.     

Scale up of 2,4-dichlorophenol removal from aqueous solutions using Brassica napus hairy roots

Chlorophenols are harmful pollutants, frequently found in the effluents of several industries. For this reason, many environmental friendly technologies are being explored for their removal from industrial wastewaters. The aim of the present work was to study the scale up of 2,4-dichlorophenol (2,4-DCP) removal from synthetic wastewater, using Brassica napus hairy roots and H₂O₂ in a discontinuous stirred tank reactor. We have analyzed some operational conditions, because the scale up of such process was poorly studied. High removal efficiencies were obtained (98%) in a short time (30 min). When roots were re-used for six consecutive cycles, 2,4-DCP removal efficiency decreased from 98 to 86%, in the last cycle. After the removal process, the solutions obtained from the reactor were assessed for their toxicity using an acute test with Lactuca sativa L. seeds. Results suggested that the treated solution was less toxic than the parent solution, because neither inhibition of lettuce germination nor effects in root and hypocotyl lengths were observed. Therefore, we provide evidence that Brassica napus hairy roots could be effectively used to detoxify solutions containing 2,4-DCP and they have considerable potential for a large scale removal of this pollutant. Thus, this study could help to design a method for continuous and safe treatment of effluents containing chlorophenols.     

Kinetics of the degradation of 2-chlorophenol by ozonation at pH 3

Prediction of byproduct distribution during ozonation is of importance to the design of treatment process. In this study, degradation products in direct ozonation of 2-chlorophenol in aqueous solution were identified by employing the chemical derivatization technique, specifically, silylation. Transient distribution of degradation products, in a semi-batch reactor under three ozone dosages were identified and determined by HPLC analysis. An empirical degradation pathway was proposed to describe the ozonation reaction. A mathematical protocol consisting of 11 equations and 12 rate constants was developed to solve and optimize the kinetic parameters. Modeling results revealed that the empirical pathway was capable of predicting the ozonation reaction at the beginning phase under a higher ozone dosage (e.g., greater than 6mg/L(g)). The degree of agreement between predicted and experimental data decreased as the ozone dosage decreased to 1.2mg/L(g). Results suggested that there was a dosage-dependent pathway in the direct ozonation of 2-chlorophenol.     

Sputter-deposited Ti oxide films used for photoelectrocatalytic degradation of 4-chlorophenol

Ti oxide films were made by reactive magnetron sputtering under conditions yielding penniform structures with large porosity. X-ray diffractometry showed that rutile-like and anatase-like films were produced depending on the oxygen content in the sputter plasma. Rutherford backscattering spectrometry documented some oxygen overstoichiometry. Spectral optical measurements were used to analyze the absorption around the fundamental band gap and to give evidence of some hydration and hydroxylation in the films. The various Ti oxide films were brought in contact with 4-chlorophenol (4-CP), whose photo-electrocatalytically induced degradation under ultraviolet irradiation was investigated in a reactor allowing optical probing of 4-CP as well as of intermediate reaction products such as benzoquinone. A rutile-like structure was conducive to the degradation of 4-CP, which can be reconciled with the band gap being suitable for producing photoinduced holes capable to effecting oxidation of the pollutant.     

Atomic oxygen generation by in-situ plasma and post-plasma in dielectric barrier discharges for surface treatment

Atomic oxygen (AO) generation is experimentally and numerically investigated for in-situ plasma and post-plasma produced by dielectric barrier discharges (DBDs) for surface treatment. The AO generation in in-situ plasma inside a DBD reactor is closely related to the plasma characteristics depending on the applied voltage and O₂ additive concentration, while the AO density distribution along the post-plasma ejected outside the reactor exit is influenced by the AO generation in the in-situ plasma, gas flow rate, and effluent distance. Contact angle measurements show that the metal surface characteristics, which are treated by in-situ plasma and post-plasma, respectively, are distinctive from each other depending on the AO densities.     

Pyrolysis of waste using a hybrid argon–water stabilized torch

An experimental plasmachemical reactor equipped with the novel IPP-ASCR hybrid gas–water stabilized DC torch (160 kW) has recently been started at IPP Prague for the innovative and environmentally friendly plasma treatment of waste streams with a view to their sustainable energetic and chemical valorization and to a reduction of the emission of greenhouse gases. Since the process energy is provided by direct heat transfer from plasma, gases of widely varying chemical composition may be used. The use of electrical energy also reduces the gas flows and requirements for exhaust-gas treatment, and offers control over the chemistry. Pyrolysis of biomass was experimentally studied using wood chips as a model substance. Syngas with a high content of hydrogen and CO was produced. The influence of adding CO₂ for increase of oxygen content in the reactor was investigated.     

Removal of phenol and chlorophenols from water with reusable dye-affinity hollow fibers

Reactive Green HE 4BD carrying polyamide hollow fibers were investigated as dye-affinity adsorbents for removal of chlorophenols (i.e., phenol, o-chlorophenol, p-chlorophenol and 2,4,6-trichlorophenol). Adsorption rates of chlorophenols were very high. Equilibrium was achieved in about 30 min. The applicability of two kinetic models including pseudo-first order and pseudo-second order model was estimated on the basis of comparative analysis of the corresponding rate parameters, equilibrium capacity and correlation coefficients. Results suggest that chemisorption process could be the rate-limiting step in the adsorption process. The maximum adsorption values of chlorophenols onto the Reactive Green HE 4BD carrying hollow fibers were 145.9 micromol/g for phenol, 179.2 micromol/g for 2,4,6-trichlorophenol, 194.5 micromol/g for p-chlorophenol and 202.8 micromol/g for o-chlorophenol. The affinity order was as follows: o-chlorophenol>p-chlorophenol>2,4,6-trichlorophenol>phenol. The adsorption capacity of chlorophenols decreased with increasing pH. Desorption of chlorophenols was achieved using methanol solution (30%, v/v). The Reactive Green HE 4BD-carrying hollow fibers are suitable for repeated use for more than 10 cycles without noticeable loss of adsorption capacity.     

Pyrolysis/gasification of biomass for synthetic fuel production using a hybrid gas-water stabilized plasma torch

An experimental plasma-chemical reactor equipped with a novel hybrid gas-water stabilized torch is available at IPP Prague for the innovative and environmentally friendly plasma treatment of waste streams with a view to their sustainable energetic and chemical valorization and to a reduction of the emission of greenhouse gases. Gasification/pyrolysis of biomass was experimentally studied using crushed wood as a model substance. The experimental results demonstrate homogeneous heating of the reactor volume and proper mixing of plasma with treated material in spite of the low plasma mass flow rate and constricted plasma jet. The conditions within the reactor ensure complete destruction of the tested substance. The economical viability, environmental performance and safety of biofuels/hydrogen produced from syngas resulting from the plasma-thermochemical gasification of a very broad range of second generation biomass feedstock will be investigated. The performance of several types of plasma torches and of possible combinations of torches will be compared. The final biofuels will be tested in the existing Internal Combustion Engine (ICE) test stands.