Indirect Electrochemical Oxidation of Phenol in the Presence of Chloride for Wastewater Treatment

Electrochemical oxidation of phenol using a Ti/TiO₂‐RuO₂‐IrO₂ anode in the presence of chloride as the supporting electrolyte was investigated. The experiments were performed in an undivided batch reactor. Preliminary investigations showed that only a small fraction of phenol was oxidized by direct electrolysis, while complete degradation of phenol was achieved by indirect electrochemical oxidation using chloride as a supporting electrolyte. The effect of operating parameters such as initial pH, supporting electrolyte concentration, phenol concentration, and charge input was studied using Box‐Behnken second order composite experimental design. The effect of current density on COD removal was studied separately. TOC removal and AOX formation were studied for selected conditions. It was found that the formation of chlorinated organic compounds was pronounced at the beginning of electrolysis, but it was reduced to lower levels by extended electrolysis.     

Abatement of 4-Chlorophenol in Aqueous Phase by Ozonation Coupled with a Sequencing Batch Biofilm Reactor (SBBR)

The aim of this work was to assess the mineralization of 100 and 200 mg L^?1 4-chlorophenol (4-CP) solutions by ozonation-biological treatment. The results show that starting from a 4-CP initial concentration from 100 to 500 mg L^?1 and using an ozone flow rate of 5.44 and 7.57 g h^?1, 4-CP was completely removed. A kinetic constant around 9·10^?2 min^?1 was calculated for the ozone direct attack. The biodegradability (BOD₅/COD) of the pre-ozonated solutions increased from 0 until a range between 0.2–0.37. The combination of the ozonation and aerobic biological treatment in an aerobic sequencing batch biofilm reactor (SBBR) gave an abatement of more than 90% of the initial TOC.     

Selectivity of Rhodium‐Catalyzed Hydroformylation of 1‐Octene during Batch and Semi‐Batch Reaction using Trifluoromethyl‐Substituted Ligands

The regioselectivity of catalysts generated in situ from dicarbonyl rhodium(I)(2,4‐pentanedione) and trifluoromethyl‐substituted triphenylphosphine ligands has been evaluated during the hydroformylation of 1‐octene. The influence of batch or semi‐batch operation, the solvent, and the number of trifluoromethyl substituents has been investigated. During batch operation in a supercritical carbon dioxide (CO₂)‐rich system the differential n:iso ratio increases from approximately 4 to a value of 12–16 at about 90–95 % conversion for the catalyst based on bis[3,5‐bis(trifluoromethyl)phenyl]phenylphosphine. For semi‐batch conditions using hexane a constant n:iso ratio is obtained over a broad conversion range. Batch hydroformylation in neat 1‐octene is faster than in a supercritical CO₂‐rich, one‐phase system, with a similar overall selectivity as observed in the supercritical case. The results provide further directions for the development of ligands that are especially designed for the separation of homogeneous catalysts in continuously operated hydroformylation in scCO₂.     

An optimization and modeling approach for H2O2/UV‐C oxidation of a commercial non‐ionic textile surfactant using central composite design

BACKGROUND: Industrial surfactants are biologically complex organics that are difficult to degrade and may cause ecotoxicological risks in the environment. Until now, many scientific reports have been devoted to the effective treatment of surfactants employing advanced oxidation processes, but there is no available experimental study dealing with the optimization and statistical design of surfactant oxidation with the well‐established H₂O₂/UV‐C process. RESULTS: Considering the major factors influencing H₂O₂/UV‐C performance as well as their interactions, the reaction conditions required for the complete oxidation of a commercial non‐ionic textile surfactant, an alkyl ethoxylate, were modeled and optimized using central composite design‐response surface methodology (CCD‐RSM). Experimental results revealed that for an aqueous non‐ionic surfactant solution at an initial chemical oxygen demand (COD) of 450 mg L^?1, the most appropriate H₂O₂/UV‐C treatment conditions to achieve full mineralization at an initial pH of 10.5 were 47 mmol L^?1 H₂O₂ and a reaction time of 86 min (corresponding to a UV dose of 30 kWh m^?3). CONCLUSION: CCD allowed the development of empirical polynomial equations (quadratic models) that successfully predicted COD and TOC removal efficiencies under all experimental conditions employed in the present work. The process variable treatment time, followed by the initial COD content of the aqueous surfactant solution were found to be the main parameters affecting treatment performance, whereas the initial H₂O₂ concentration had the least influence on advanced oxidation efficiencies. The H₂O₂ concentration and surfactant COD were found to be more important for TOC abatement compared with COD abatement. Copyright © 2009 Society of Chemical Industry     

Hydrothermal Carbonization of Biomass: Major Organic Components of the Aqueous Phase

Process waters obtained from hydrothermal carbonization (HTC) of wheat straw, a biogas digestate derived thereof, and four woody biomass feedstocks were quantified regarding the total organic carbon (TOC) and selected organic compounds. HTC runs revealed that TOC loads were largely unaffected by process severity or type of feedstock whereas the C₂–C₆ fatty acids, determined by GC, displayed clear effects of temperature and feedstock. HPLC demonstrated simultaneously the initial increase and subsequent consumption of cellulose‐derived furfural and 5‐hydroxymethylfurfural as well as the increase of the lignin‐derived 2‐methoxyphenol. 2‐Methylbenzofuran, an example for a substance potentially harmful to aquatic biota, was observed in high concentration in the HTC liquor from wheat straw‐based feedstocks.     

Beneficial combination of wet oxidation,membrane separation and biodegradation processes for treatment of polymer processing wastewaters

The treatment of a model wastewater containing polyethylene glycol of molecular weight (MW) 10 000 by means of combined chemical oxidative pretreatment, membrane separation and biological post‐treatment was investigated. Wet oxidation was employed as a chemical pretreatment process to convert the original, high MW polymer to lower MW compounds in an attempt to improve the biotreatability of the waste‐water. The partially oxidized effluents formed during wet oxidation at temperatures up to 403 K were separated by nanofiltration where larger molecules were recycled into the wet oxidation reactor, while the permeate leaving the filtration step was treated biologically. At a biological residence time (τ_B) of 12 h and 3 h, the resulting total organic carbon (TOC) removal in the biological step was as high as 94% and 87%, respectively. Conversely, a continuous aerobic biological process was found inadequate to completely mineralize the original wastewater, since at τ_b of 96 h only about 60% to 70% TOC removal was achieved, while at τ_b of 12 h the original wastewater was practically non‐biockgradable.     

Behaviors of polyelectrolyte AAm/AMPS/bentonite composite hydrogels in uptake of uranyl ions from aqueous solutions

Uranyl ion (UO₂²⁺) sorption properties of polyelectrolyte composite hydrogels made by the polymerization of acrylamide (AAm) with 2‐acrylamido‐2‐methyl‐1‐propanesulfonic acid (AMPS) and clay such as bentonite (Bent) were investigated as a function of composition to find materials with swelling and uranyl ion sorption properties. Highly swollen AAm/AMPS hydrogels and AAm/AMPS/Bent composite hydrogels were prepared by free radical solution polymerization in aqueous solutions of AAm with AMPS as co‐monomer and two multifunctional crosslinkers such as ethylene glycol dimethacrylate (EGDMA) and 1,4 butanediol dimethacrylate (BDMA). Swelling experiments were performed in water at 25°C, gravimetrically. The influence of AMPS content in hydrogels was examined. Uranyl ion adsorption from aqueous solutions was studied by batch sorption technique at 25°C. The effect of uranyl ion concentration and mass of AMPS on the uranyl ion adsorption were examined. Finally, adsorption capacity (the amount of sorbed uranyl ion per gram of dry hydrogel) (q) was calculated to be 0.67 × 10⁻³–2.11 × 10⁻³ mol uranyl ion per gram for the hydrogels. Removal effiency of uranyl ions (RE%) was changed range 9.05–29.92%. The values of partition ratio (K_d) of uranyl ions was calculated to be 0.10–0.43 for AAm/AMPS hydrogels and AAm/AMPS/Bent composite hydrogels, respectively. POLYM. COMPOS., 2011. © 2011 Society of Plastics Engineers     

Batch Liquid‐Liquid Extraction of Phenol from Aqueous Solutions

The aim of this work is the study of batch liquid‐liquid extraction of phenol from aqueous solutions in a bench‐scale well‐mixed reactor. The influence of the ratio of phase volumes, temperature, and rotational speed on phenol removal (0.72–1.1 % w/w) was investigated using methyl isobutyl ketone as an extracting solvent. For this purpose, the ratio of phase volumes were set at 0.1 and 0.2, the temperature at 10, 20, and 30 °C, and the rotational speed at 300, 400, and 500 rpm. A physical model based on the material balance of the phases as well as the equation of mass flux between the phases allowed the estimation of the overall coefficient of mass transfer coupled with the superficial area. Moreover, it proved to fit, satisfactorily well, the experimental data of residual phenol concentration in the organic phase versus time under all the conditions investigated.     

Cerium(IV)-mediated electrochemical oxidation process for destruction of organic pollutants in a batch and a continuous flow reactor

The mediated electrochemical oxidation (MEO) process with Ce(IV) and nitric acid as the oxidizing medium was employed for the destruction of various model organic pollutants in batch and continuous organic feeding modes. A near complete destruction was observed for all the model organic pollutants studied. The effects of organic concentration, temperature, concentration of Ce(IV), concentration of nitric acid and feeding time on the organic destruction efficiency were investigated. Under the experimental conditions of 80 °C and 0.95 M Ce(IV) in 3 M nitric acid, nearly 90% destruction was achieved based on CO₂ production and 95% based on TOC and COD nearly for all the organic compounds studied in batch organic addition. In the case of continuous organic addition with in situ electroregeneration of Ce(IV) by the electrochemical cell a good destruction efficiency was obtained. For long term organic feeding (120 min) the destruction efficiency was found to be 85% based on CO₂ evolution and 98–99% based on TOC and COD analyses. A model was proposed for calculating the CO₂ formation constant during the continuous process of organic addition. The model predicted a steady state CO₂ evolution pattern for the destruction process during continuous organic feeding. The experimental results obtained confirmed the predicted trends for the destruction process. The changes in enthalpy, entropy, activation energy and free energy for EDTA degradation were found to be 26.7 kJ/mol, −230 J/(mol·K), 29.7 kJ/mol, and 118 kJ/mol respectively.     

Acid–base properties of ion exchangers. I. Optimising of potentiometric titration of ion exchangers exemplified by carboxylic acid resins

The aim of this work was to determined conditions for fast titration the ion exchanger in the one-sample experiment allowing obtaining its equilibrium titration curve. Carboxylic acid ion exchangers KB-4 and Dowex MAC-3 were taken as examples. They were titrated under different conditions with NaOH, KOH and Ba(OH)₂. The forward and backward titration of concentrated immersions of finely ground ion exchanger in the electrolyte solutions with 20-min intervals between additions of the titrants of high concentration gave close results, identical to the results of the batch experiment if concentration of the supporting electrolyte was sufficiently high (1 M). It appeared possible to obtain equilibrium potentiometric titration curves in one working day and use this method for express control of properties of ion exchangers.     

Effect of Fe2+ and Fe0 Applied Photo‐Fenton Processes on Sludge Disintegration

The disintegration of waste active sludge was investigated by photo‐Fenton processes. A batch study was conducted to evaluate parameters, such as Fe²⁺ and Fe⁰ ions and H₂O₂, governing the activated sludge integration by the photo‐Fenton process. Under optimum conditions, the concentration of soluble chemical oxygen demand (SCOD) with the classical Fenton process (CFP) increased very rapidly in the first five minutes due to the sufficient presence of reaction components in the medium, and then the rate of increase declined. In the modified Fenton process (FTP), the SCOD concentration increased more slowly as metallic iron powder must first be dissolved. The photo‐Fenton process proved to be a feasible and efficient process for the disintegration of waste sludge.     

Succinic Acid Production in Fed‐Batch Fermentation of Anaerobiospirillum succiniciproducens Using Glycerol as Carbon Source

Considering glycerol as an inexpensive alternative carbon source, the optimal glycerol concentration for succinic acid production with Anaerobiospirillum succiniciproducens was identified in shake‐flask trials. The addition of a defined amount of glucose improved the growth and succinic acid productivity significantly. In fed‐batch processes with glycerol as sole substrate, a maximum succinic acid concentration and product substrate yield were obtained. The addition of glucose led to a 2.5‐fold increased succinic acid concentration whereas the product substrate yield remained nearly constant.     

Batch kinetics and modelling of propionic acid fermentation

Batch propionic acid fermentation kinetics was studied using five different initial concentrations of lactose (i.e., 37 g/L, 45g/L, 50g/L, 57 g/L and 73 g/L) at constant temperature (30°C) and pH (6.5) under anaerobic conditions using Propionibacterium acidipropionici (ATCC 4875). When the initial substrate concentration was 37 g/L, 45 g/L, 50 g/L, 57 g/L and 73 g/L, then, correspondingly, 16 g/L, 19 g/L, 22.25 g/L, 25.3 g/L and 26.3 g/L of propionic acid was accumulated in the fermentation broth. Increasing the supply of lactose in the fermentation medium led to the accumulation of by products succinate, acetate and pyruvate. Maximum propionate yield (0.44 g/g) and comparatively lesser impurities (byproducts) were achieved with 57 g/L initial lactose concentration. The batch growth kinetics was eventually used to develop and test a mathematical model for propionic acid fermentation by P. acidipropionici at pH 6.5 and S_o = 57 g/L. Y_X/S^max was found to be the most sensitive parameter of the model. The same model also successfully simulated the batch kinetics observed at S_o = 37 g/L. However the model failed to simulate the fermentation kinetics observed at S_o = 73 g/L. The developed model can be used for process optimization studies.     

Batch and fixed‐bed column adsorption of Cu(II), Pb(II) and Cd(II) from aqueous solution onto functionalised SBA‐15 mesoporous silica

Functionalised SBA‐15 mesoporous silica with polyamidoamine groups (PAMAM‐SBA‐15) was successfully prepared with the structure characterised by X‐ray diffraction, nitrogen adsorption–desorption, Fourier transform infrared spectra and thermogravimetric analysis. PAMAM‐SBA‐15 was applied as adsorbent for Cu(II), Pb(II) and Cd(II) ions removal from aqueous solution. The effects of the solution pH, adsorbent dosage and metal ion concentration were studied under the batch mode. The Langmuir model was fitted favourably to the experimental data. The maximum sorptive capacities were determined to be 1.74 mmol g^?1 for Cu(II), 1.16 mmol g^?1 for Pb(II) and 0.97 mmol g^?1 for Cd(II). The overall sorption process was fast and its kinetics was fitted well to a pseudo‐first‐order kinetic model. The mean free energy of sorption, calculated from the Dubinin–Radushkevich isotherm, indicated that the sorption of lead and copper, with E > 16 kJ mol^?1, followed the sorption mechanism by particle diffusion. The adsorbent could be regenerated three times without significant varying its sorption capacity. A series of column tests were performed to determine the breakthrough curves with varying bed heights and flow rates. The breakthrough data gave a good fit to the Thomas model. Maximum sorption capacity of 1.6, 1.3 and 1.0 mmol g^?1 were found for Cu(II), Pb(II) and Cd(II), respectively, at flow rate of 0.4 mL min^?1 and bed height of 8 cm, which corresponds to 83%, 75% and 73% of metallic ion removal, respectively, which very close to the value determined in the batch process. Bed depth service time model could describe the breakthrough data from the column experiments properly. © 2012 Canadian Society for Chemical Engineering     

Adsorption Equilibrium and Kinetics of the Parex' Feed and Desorbent Streams from Batch Experiments

The adsorption of the main components of the Parex process, i.e., p‐xylene, m‐xylene, o‐xylene, ethylbenzene, p‐diethylbenzene, and toluene, was studied in a batch adsorber operating under the conditions of an industrial unit (177 °C, 9 bar). Prior to each experiment, the faujasitic‐type adsorbent was pretreated under helium flow to control the hydration level of the adsorbent. The experimental uptake curves were used to determine adsorption equilibrium data, which were fitted with Langmuir‐type isotherms. A mathematical model in which the macropore diffusion is the rate‐controlling mechanism, satisfactorily describes the experimental uptake curves.     

Electrochemical mineralization of sodium dodecylbenzenesulfonate at boron doped diamond anodes

Results are reported of the electrochemical oxidation of sodium dodecylbenzenesulfonate (SDBS), a common surfactant, at boron-doped diamond anodes. The measured critical micelle concentration (CMC) for SDBS in water at 24 °C was almost 150 mg dm⁻³, but this decreased to almost 30 mg dm⁻³ in 0.1 M sodium sulfate. Cyclic voltammetry of a boron doped diamond (BDD) electrode in aqueous SDBS solutions exhibited oxidation current densities at very positive potentials; however, solutions of monomers at concentrations <CMC gave rise to higher current densities than in higher concentration solutions that formed micelles. Galvanostatic electrolyses, with samples analyzed for Total Organic Carbon (TOC) and Chemical Oxygen Demand (COD), were performed in an electrolytic flow cell without separator, operating in batch recycle mode, using solutions containing SDBS at initial concentrations of 25 and 250 ppm. SDBS in basic media (pH = 12) exhibited lower TOC removal rates than in acidic or neutral solutions, due to concurrent oxidation of dissolved carbonates at potentials less positive than required for water oxidation, as evident in cyclic voltammograms. Decreasing the [electrolyte]/[surfactant] ratio from 200 to 10 increased TOC removal rates. For solutions containing monomers, TOC removal rates also increased with flow rate in the second part of the electrolysis, corresponding to reaction of smaller, fragmented organic compounds. When COD removal from a solution containing SDBS micelles was mass transport controlled, current efficiencies were constant at ca. 50%, due to dimerisation of hydroxyl radical to H₂O₂ and its oxidation to dioxygen.     

Treatment of phenol formaldehyde production wastewater by electrooxidation-electrofenton successive processes

ABSTRACT

Treatments of phenol formaldehyde producing wastewater (PFPW) by electrooxidation (EO) and electro-Fenton (EF) successive processes were carried out in a batch electrolytic reactor using graphite (Gr) and stainless steel (Ss) electrodes. After the completion of the EO process, the wastewater was further treated with EF process. The influence of operating variables such as current density, operating time, initial pH_i and H₂O₂ concentration was evaluated for removals of phenol, TOC and COD in PFPW. Gr/Gr, Gr/Ss or Ss/Ss and Ss/Gr electrode pair were used as anode and cathode. The best removal efficiency in the EO process was obtained with Gr/Gr (93%) as compared to Gr/Ss (82%), Ss/Ss (63%) and Ss/Gr (55%). The removal efficiencies for the EO process using Gr-Gr electrode pair were obtained as 93% for phenol, 61% for COD and 44% for TOC at initial pH_i 7,5 g/L of NaCl, 50 mA/cm² and 5 h. In the EF process, the removal efficiencies at pH_i 3,5 mA/cm² and 30 mM H₂O₂ and 45 min were 100% for phenol, 76% for COD and 59% for TOC. This study provided that the successive processes are an effective method for the removal of phenolic compounds from the wastewater.     

Recrystallization of Salicylamide using a Batch Supercritical Antisolvent Process

Recrystallization of the nonsteroidal anti‐inflammatory drug salicylamide was investigated using a batch supercritical antisolvent (SAS) precipitation process. Carbon dioxide was used as the antisolvent, and acetone, ethanol and ethyl acetate were used as solvents. Particle morphology determined by SEM showed that particles with a regular shape were obtained from the SAS process. The crystal structure analyzed by XRD showed that the intensities of specific peaks were modified. No decomposition or deterioration was confirmed by DSC measurements where the melting temperature remained the same after SAS recrystallization. The effects of process parameters were investigated with acetone as the solvent. At a higher pressure of 110 bar, a higher saturation concentration of 90 %, and a lower temperature of 293 K, the length of the rectangular particles decreased to 50 μm. This showed a significant change from the irregular and broken particle shapes with particle sizes up to 200 μm before processing by SAS.     

Photo Assisted Fenton in a Batch and a Membrane Reactor for Degradation of Drugs in Water

Abstract

Some advanced oxidation processes (AOP's) such as Fenton H₂O₂/Fe²⁺, photo assisted Fenton UV/H₂O₂/Fe²⁺, UV photolysis, and photo assisted Fenton—like UV/O₂/Fe²⁺ have been tested for the degradation of Gemfibrozil in aqueous solution in a batch system and then in a membrane reactor. A nanofiltration/reverse osmosis type cross‐linked polyamide, UTC‐60 (Toray) membrane (19 cm²) was used. In the batch degradation tests, the gemfibrozil, used at 5 mg/L, was degraded by employing the four AOP's but numerous peaks of intermediates were observed at the HPLC. Indeed DOC analyses showed poor mineralization in the case of photolysis (3.1%) and UV/O₂/Fe (10%), while it was 62% using the photo assisted Fenton and 24% using the Fenton. Thus in the membrane reactor only the Fenton and the photo assisted Fenton were tested. Obtained results showed a drug degradation higher than 92%, a mineralization higher than 55%, and a membrane retention of the catalyst in solution higher than 95%.     

Batch production of biosurfactant with foam fractionation

Methods of producing the biosurfactant surfactin from cultures of Bacillus subtilis (BBK006) have been investigated. A reactor with integrated foam fractionation was designed and used in batch mode, and the performance compared with that of the same culture in shaken flasks. In the batch reactor, significant foaming occurred between 12.5 h and 14.5 h of culture time. During this period, the foam was routed through the foam fractionation column to a mechanical foam breaker, and a biosurfactant‐enriched foamate was collected. Concentration of surfactin in the foamate product was around 50 times greater than that in the culture medium. Using the integrated reactor, 136 mg L^?1 of surfactin was produced, significantly more than was achieved in shaken flasks (92 mg L^?1). The foam fractionation method allowed a real‐time measurement of the rate of surfactin production during growth. This showed that the maximum rate of production occurred at the interphase between log and stationary modes of growth, in contrast to previous work showing that surfactin is exclusively a secondary metabolite. The high value of surfactin yield in relation to biomass (Y_P/x = 0.262) indicated that surfactin was produced very efficiently by Bacillus subtilis (BBK006) in this integrated bioreactor. Copyright © 2006 Society of Chemical Industry