Pretreatment of Afyon alcaloide factory's wastewater by wet air oxidation (WAO)

In this study, pretreatment of Afyon (Turkey) alcaloide factory wastewater, a typical high strength industrial wastewater (chemical oxygen demand (COD)=26.65 kgm(-3), biological oxygen demand (BOD(5))=3.95 kgm(-3)), was carried out by wet air oxidation process. The process was performed in a 0.75 litre specially designed bubble reactor. Experiments were conducted to see the advantages of one-stage and two-stage oxidation and the effects of pressure, pH, temperature, catalyst type, catalyst loading and air or oxygen as gas source on the oxidation of the wastewater. In addition, BOD(5)/COD ratios of the effluents, which are generally regarded as an important index of biodegradability of a high-strength industrial wastewater, were determined at the end of some runs. After a 2h oxidation (T=150 degrees C, P=0.65 MPa, airflowrate=1.57 x 10(-5)m(3)s(-1), pH=7.0), the BOD(5)/COD ratio was increased from 0.15 to above 0.5 by using the salts of metals such as Co(2+),Fe(2+),Fe(2+)+Ni(2+),Cu(2+)+Mn(2+) as catalyst.     

Heterogeneous catalytic wet peroxide oxidation systems for the treatment of an industrial pharmaceutical wastewater

The aim of this work was to assess the treatment of wastewater coming from a pharmaceutical plant through a continuous heterogeneous catalytic wet peroxide oxidation (CWPO) process using an Fe₂O₃/SBA-15 nanocomposite catalyst. This catalyst was preliminary tested in a batch stirred tank reactor (STR), to elucidate the influence of significant parameters on the oxidation system, such as temperature, initial oxidant concentration and initial pH of the reaction medium. In that case, a temperature of 80 °C using an initial oxidant concentration corresponding to twice the theoretical stoichiometric amount for complete carbon depletion and initial pH of ca. 3 allow TOC degradation of around 50% after 200 min of contact time. Thereafter, the powder catalyst was extruded with bentonite to prepare pellets that could be used in a fixed bed reactor (FBR). Results in the up-flow FBR indicate that the catalyst shows high activity in terms of TOC mineralization (ca. 60% under steady-state conditions), with an excellent use of the oxidant and high stability of the supported iron species. The activity of the catalyst is kept constant, at least, for 55 h of reaction. Furthermore, the BOD₅/COD ratio is increased from 0.20 to 0.30, whereas the average oxidation stage (AOS) changed from 0.70 to 2.35. These two parameters show a high oxidation degree of organic compounds in the outlet effluent, which enhances its biodegradability, and favours the possibility of a subsequent coupling with a conventional biological treatment.     

Oxidation of phenolic compounds by ozone and ozone + u.v. radiation: A comparative study

This study was designed to investigate the reaction mechanisms of oxidation of various phenolic compounds by ozone and ozone + u.v. radiation at pH 2.5, 7.0 and 9.0. Experimental results indicated that the molecular ozone is the predominant oxidant only at acidic pH; at neutral and basic pH, in the absence or presence of u.v. radiation, free radical reaction is the major pathway in the oxidation of phenolic compounds. The overall removal of phenols and the removal of TOC increase with increasing pH during ozonation with or without u.v. light. For a specific pH, the removal rates of phenol and TOC are highest for ozone + u.v. light followed by ozone and then u.v. light alone.     

Horseradish peroxidase immobilized on aluminium-pillared inter-layered clay for the catalytic oxidation of phenolic wastewater

Horseradish peroxidase (HRP) was successfully immobilized on aluminum-pillared inter-layered clay (Al-PILC) to obtain enzyme-clay complex for the treatment of wastewater polluted with phenolic compounds. The immobilized HRP exerted a perfect phenol removal by precipitation or transforming to other products over a broader pH range from 4.5 to 9.3. The addition of polyethylene glycol (PEG) could significantly enhance the phenol removal efficiency, and reduce the amount of immobilized enzyme required to achieve a high removal efficiency of over 90%. When the mass ratio of PEG/phenol and the molar ratio of hydrogen peroxide/phenol were 0.4 and 1.5, respectively, the oxidation of phenol could be completed within short retention time after the initiation of reaction in the absence of buffer. HRP immobilized on Al-PILC had better storage stability compared with free enzyme. However, the re-usability of the immobilized enzyme was not very satisfactory. In the fourth repeated test, the immobilized enzyme lost its catalytic performance. Further research should focus on the improvement of re-usability.     

Optimization of phenol removal from wastewater by activation of persulfate and ultrasonic waves in the presence of biochar catalyst modified by lanthanum chloride

In this paper, the effects of phenol concentration, pH, catalyst dose, persulfate concentration, temperature and contact time on the phenol removal from wastewater by activation of persulfate (S₂O₈^?2) in the presence of biochar modified by lanthanum chloride and ultrasonic waves (US) are optimized. Experimental design and optimization were carried out by response surface methodology. The optimum conditions for the maximum phenol removal were obtained pH of 4, phenol concentration of 86 mg/L, catalyst dose of 43 mg/L, persulfate concentration of 86 mg/L, temperature of 41 °C and contact time of 63 min. The optimum phenol removal from synthetic wastewater was attained 97.68%. Phenol removal by the mentioned system was fitted with the first‐order kinetic model. The combination of the ingredients of ‘S₂O₈^?2/US/Biochar‐LaCl₃’ system had a synergistic effect on the phenol removal.     

Electro‐oxidation of phenol in petroleum wastewater using a novel pilot‐scale electrochemical cell with graphite and stainless‐steel electrodes

This work investigated the removal of phenol from petroleum wastewater by the electro‐oxidation process. The experimental design was developed on a pilot‐scale electro‐oxidation system equipped with a cylindrical shape of graphite electrodes as an anode and stainless‐steel electrodes as a cathode. An initial study was performed based on operating variables such as current density and time on real petroleum wastewater. The optimum conditions were obtained as a current density of 3 mA/cm² and time 15 min. Under these applied optimum conditions, complete phenol removal from an initial concentration of about 6.8 mg/L was achieved. Also, 50–60% removal of organic matter in terms of chemical oxygen demand (COD) and biological oxygen demand (BOD). The removal of organic matter using electro‐oxidation requires a long reaction time. Also, the economic study indicated that the energy consumption was determined to be 0.79 kWh/m³ and the operating cost was 0.051 $/m³ which is very economical compared with conventional methods.     

TiO2 and Fe (III) photocatalytic ozonation processes of a mixture of emergent contaminants of water

A mixture of three emergent contaminants: testosterone (TST), bisphenol A (BPA) and acetaminophen (AAP) has been treated with different photocatalytic oxidation systems. Homogeneous catalysts as Fe(III) alone or complexed with oxalate or citrate ions, heterogeneous catalysts as titania, and oxidants such as hydrogen peroxide and/or ozone have been used to constitute the oxidation systems. For the radiation type, black light lamps mainly emitting at 365 nm have been used. The effects of pH (3 and 6.5) have been investigated due to the importance of this variable both in ozone and Fe(III) systems. Removal of initial compounds and mineralization (total organic carbon: TOC) were followed among other parameters. For the initial compounds removal ozonation alone, in many cases, allows the highest elimination rates, regardless of the presence or absence of UVA light and catalyst. For mineralization, however, ozone photocatalytic processes clearly leads to the highest oxidation rates.     

微波强化Fenton氧化处理垃圾渗滤液的研究

以负载铁(Ⅱ)的颗粒活性炭(GAC)为催化剂,采用微波强化Fenton氧化处理老龄垃圾渗滤液,考察了对垃圾渗滤液的处理效果及微波的作用机理。结果表明,微波对Fenton氧化反应有催化作用,且可促进渗滤液中胶体的絮凝,微波作用时间是影响处理效果的主要因素;当GAC的铁负载量为33.32mg/g、微波功率为720W、微波时间为30min时,对COD和NH3-N的去除率最高,分别达到了95.64%和88.63%;COD主要通过催化氧化作用被去除,而NH3-N主要通过絮凝、吸附作用被去除;另外,微波可使GAC再生,提高了GAC的利用率。     

Catalytic wet oxidation of phenol over a Pt/TiO catalyst

Wet oxidation of phenol by air or oxygen over a Pt/TiO₂ catalyst is studied in a batch reactor in the temperature range 150–200°C, pressure range 34–82 atm, and a catalyst loading range of 0–4 g catalyst L⁻¹. The catalyst was powdered 4.45% Pt/TiO₂ with a maximum particle size of 105 μm. Results show complete oxidation of phenol and almost complete total organic carbon (TOC) removal. Small amounts of stable organic acids are formed in side reactions of the phenol degradation pathway and are not readily degraded. Experimental results show that the reaction rate decreases by increased oxygen concentration. Theoretical rate expressions are derived, based on postulated oxidation and TOC reduction mechanisms.     

Catalytic wet oxidation of o-chlorophenol at mild temperatures under alkaline conditions

Wet oxidation of a 100 ppm aqueous solution of o-chlorophenol (o-CP) was performed in a lab-scale batch reactor using 3% Ru/TiO(2) catalyst at 373 and 413 K, and a partial oxygen pressure of 0.1 MPa. The experiments were conducted by varying the initial pH values of o-CP solution from pH 6.3 to 9.8 and 11.8. From the results, it was revealed that the catalytic decomposition of o-CP occurred most effectively at 413 K and at the initial pH of 9.8. Complete decomposition and dechlorination of o-CP were almost achieved within 1h, and about 85% of TOC was removed in 3.0 h. On the other hand, the catalytic wet oxidation of o-CP at a higher pH value of 11.8 was not effective in the removal of TOC. The incomplete removal of TOC at the initial pH of 11.8 is likely attributed to a low pK(a) of carboxylic acids formed during the wet oxidation of o-CP.     

Catalytic wet oxidation of phenol in a trickle bed reactor over a Pt/TiO2 catalyst

Catalytic wet oxidation of phenol was studied in a batch and a trickle bed reactor using 4.45% Pt/TiO2 catalyst in the temperature range 150-205 degrees C. Kinetic data were obtained from batch reactor studies and used to model the reaction kinetics for phenol disappearance and for total organic carbon disappearance. Trickle bed experiments were then performed to generate data from a heterogeneous flow reactor. Catalyst deactivation was observed in the trickle bed reactor, although the exact cause was not determined. Deactivation was observed to linearly increase with the cumulative amount of phenol that had passed over the catalyst bed. Trickle bed reactor modeling was performed using a three-phase heterogeneous model. Model parameters were determined from literature correlations, batch derived kinetic data, and trickle bed derived catalyst deactivation data. The model equations were solved using orthogonal collocations on finite elements. Trickle bed performance was successfully predicted using the batch derived kinetic model and the three-phase reactor model. Thus, using the kinetics determined from limited data in the batch mode, it is possible to predict continuous flow multiphase reactor performance.     

Degradation of phenolic waste waters over Ni-oxide

The low-temperature oxidation of phenol in an aqueous phase in the presence of Ni-oxide system has been studied. The effects of pH, temperature and the catalyst amount on the efficiency of the oxidation process have been investigated. The results obtained show that phenol is completely oxidized to harmless products--carboxylic acids and CO2 at ambient temperature and pH 6.0-7.0. The simple scheme for this synthesis of the Ni-oxide system and its regeneration is a prerequisite for its application to the purification of waste waters containing toxic compounds.     

Heterogeneous catalytic degradation of cyanide using copper-impregnated pumice and hydrogen peroxide

The main objective of this research was to investigate the oxidative destruction of free cyanide with hydrogen peroxide and copper-impregnated pumice as a heterogeneous catalyst. Original or copper-impregnated pumices added alone were not effective adsorbents of negatively charged cyanide ions due to incompatible surface interactions. Peroxide and original pumices added together were also ineffective in removing cyanide. However, for all of the three natural pumices tested with various particle size fractions, the use of copper-impregnated pumices and peroxide together significantly enhanced both the initial rate and extent of cyanide removal. Although copper-impregnated specific surface area was the major factor affecting the rate and extent of cyanide destruction for a particular pumice source with similar surface chemistries, the type of surface chemistry (i.e., specific functional groups) within different pumice sources also appears to be a very important factor. Lower rates and extents of cyanide removals were observed at pH 11 compared to pH 8 probably because of the negative impacts of alkaline conditions in terms of scavenging peroxide and forming more negatively charged pumice surfaces. Both the initial rate and ultimate extent of cyanide removals were generally higher at a temperature of 20 degrees C compared with those found at 10 degrees C. The use of copper-impregnated pumice as a light, cheap, readily available, natural, and porous heterogeneous catalyst either in completely mixed/suspended or fixed-bed reactor configurations may be an effective treatment technology for cyanide removal from solution. This new approach may minimize downstream metal removal problems experienced in conventional cyanide oxidation technologies.     

Continuous electrochemical treatment of phenolic wastewater in a tubular reactor

The electrochemical treatment of phenolic wastewater in a continuous tubular reactor, constructed from a stainless steel tube with a cylindrical carbon anode at the centre, was investigated in this study, being first in literature. The effects of residence time on phenol removal was studied at 25 degrees C, 120 g l(-1) electrolyte concentration for 450 and 3100 mg l(-1) phenol feed concentrations with 61.4 and 54.7 mA cm(-2) current densities, respectively. The change in phenol concentration and pH of the reaction medium was monitored in every run and GC/MS analyses were performed to determine the fate of intermediate products formed during the electrochemical reaction in a specified batch run. During the electrolysis mono, di- and tri-substituted chlorinated phenol products were initially formed and consumed along with phenol thereafter mainly by polymerization mechanism. For 10 and 20 min of residence time phenol removal was 56% and 78%, respectively, with 450 mg l(-1) phenol feed concentration and above 40 min of residence time all phenol was consumed within the column. For 1, 1.5, 2 and 3h of residence time, phenol removal achieved was 42%, 71%, 81% and 98%, respectively, at 3100 mg l(-1) phenol feed concentration. It is noteworthy that more than 95% of the initial phenol was converted into a non-passivating polymer without hazardous end products in a comparatively fast and energy-efficient process, being a safe treatment.     

A comparative study on treatment of wastewaters with various biodegradability and various pH values using single‐chamber microbial fuel cells

This work assessed the performance of a single‐chamber microbial fuel cell (MFC) with various substrates. Primary settled domestic wastewaters were used to simulate wastewaters of high biodegradability; while phenol‐based wastewaters and benzene‐based wastewaters were used to simulate wastewaters of low biodegradability. Experiments were performed at initial pH values of 6, 7 and 8. The maximum voltage production, power density and removal of substrate were obtained using primary settled domestic wastewater, whereas the lowest values were obtained using phenol‐based wastewater. The maximum chemical oxygen demand removal efficiency, phenol removal efficiency and benzene removal efficiency were 80.8, 63.3 and 77.8%, respectively. The performance of the MFC was enhanced by increasing the influent pH. The lowest coulombic efficiencies were obtained from phenol‐based wastewater and benzene‐based wastewater, which indicated that electrogenic bacteria were not the primary microorganisms responsible for the biodegradation of low biodegradable wastewater.     

Treatment of olefin plant spent caustic by combination of neutralization and Fenton reaction

Spent caustic from olefin plants contains much H2S and some mercaptans, phenols and oil. A new treatment process of spent caustic by neutralization followed by oxidation with Fenton's reagent (Fe2+/H2O2) was successfully developed. Over 90% of dissolved H2S were converted to gas phase by neutralization at pH = 5 and T = 70 degrees, and the vent gas stream could be introduced to sulfur recovery plant. The neutralized liquid was oxidized with OH. free radical, which was provided by a Fenton's reagent. The residual sulfides in the neutralized spent caustic were oxidized to less than 0.1 mg/L. The total COD removal of spent caustic is over 99.5% and the final COD value of the effluent can be lower than 100 mg/L under the following oxidation conditions: reaction time = 50 min, T = 90 degrees, Fe2+ = 100 mg/L, and a stoichiometric H2O2/COD = 1.1. The value is better than the 800 mg/L value obtained by common WAO process. The optimum pH of the Fenton reaction is around 2 for this process, and the oxidation step can maintain a pH value in the range of 1.8-2.4. Moreover, the iron catalyst can be recycled without affecting process effectiveness thus preventing secondary pollution.     

Effects of chloride and sulfate on the rate of oxidation of ferrous ion by H2O2

The rates of oxidation of Fe(II) by H(2)O(2) in the presence of sodium perchlorate, sodium nitrate, sodium chloride and sodium sulfate salts (0-1M) have been compared in the study. Experiments were carried out in a batch reactor, in the dark, at pH <3, 25+/-0.5 degrees C and at controlled ionic strength (< or =1M). The experimental results showed that the rates of oxidation of Fe(II) in the presence of chloride, nitrate and perchlorate were identical. In the presence of sulfate, the rate of oxidation of Fe(II) was faster and depended on the pH and the concentration of sulfate. The pseudo second-order rate constants for the reaction of H(2)O(2) with Fe(2+), FeCl(+) and FeSO(4) were determined as 55+/-1, 55+/-1 and 78+/-3 M(-1) s(-1), respectively.     

Enhancing Fenton oxidation of TNT and RDX through pretreatment with zero-valent iron

The effect of reductive treatment with elemental iron on the rate and extent of TOC removal by Fenton oxidation was studied for the explosives 2,4,6-trinitrotoluene (TNT) and hexahydro-1,3,5-trinitro-1,3,5-triazine (RDX) using a completely stirred tank reactor (CSTR). The results support the hypothesis that TNT and RDX are reduced with elemental iron to products that are oxidized more rapidly and completely by Fenton's reagent. Iron pretreatment enhanced the extent of total organic carbon (TOC) removal by approximately 20% and 60% for TNT and RDX, respectively. Complete TOC removal was achieved for TNT and RDX solutions with iron pretreatment under optimal conditions. On the other hand, without iron pretreatment, complete TOC removal of TNT and RDX solutions was not achieved even with much higher H(2)O(2) and Fe(2+) concentrations. Nitrogen was recovered as NH(4)(+) and NO(3)(-) when Fe(0)-treated TNT and RDX solutions were subjected to Fenton oxidation. The bench-scale iron treatment-Fenton oxidation integrated system showed more than 95% TOC removal for TNT and RDX solutions under optimal conditions. These results suggest that the reduction products of TNT and RDX are more rapidly and completely degraded by Fenton oxidation and that a sequential iron treatment-Fenton oxidation process may be a viable technology for pink water treatment.     

Phenol oxidation kinetics in water solution using iron(3)-oxide-based nano-catalysts

The influence of inorganic ions (HCO(3), PO(4)/HPO(4)/H(2)PO(4), Cl, SO(4), Ca, Na and Mg) on the advanced chemical oxidation process of organic compounds dissolved in water is reported here. The catalytic behavior of iron(3)-oxide-based nano-particles was investigated together with inorganic ions and hydrogen peroxide concentrations, and pH level. Phenol was chosen as a typical organic contaminant for this study as a simulating pollutant. The limiting concentrations of radical scavengers making the oxidation process inefficient were identified. The strong effect of concentration of radical scavengers HCO(3), PO(4)/HPO(4)/H(2)PO(4), the nano-catalyst and hydrogen peroxide concentrations, and pH on the phenol oxidation rate and lag time period before reaction starts was determined. It was shown that Cl, SO(4), Ca, Na and Mg ions had no significant effect on the kinetics of phenol oxidation.     

Photosonochemical degradation of phenol in water

The combination of ultrasound (US) and photochemistry has been used to degrade an aqueous solution of phenol. It was considerably more effective than ultrasound or ultraviolet (UV) light alone. Based on the results of total organic carbon (TOC) removal, it was shown that the synergistic action of ultrasound and ultraviolet light existed. Identification of the first intermediates of the reaction (hydroquinone, catechol, benzoquinone and resorcin) indicates that OH radicals are involved in the photosonochemical degradation mechanisms. The effects of parameters such as pH, saturating gases, and Fe2+ on the photosonochemical degradation have been studied. The experimental results have shown that lower pH and higher concentration of dissolved oxygen favor the phenol degradation and that the presence of Fe2+ enhanced TOC removal of phenol solutions.