Advanced ozone treatment of heavy oil refining wastewater by activated carbon supported iron oxide

The catalytic ozonation of heavy oil refining wastewater (HORW) was investigated over activated carbon supported iron oxides (FAC) catalysts using activated carbon (AC) as the reference. The catalyst was characterized by chemical analysis, XRD, N₂ adsorption–desorption and SEM. A significant increase in COD removal efficiency was observed in FAC + ozone compared with AC + ozone due to more hydroxyl radicals, identified by tert-butyl alcohol (TBA). The composition analysis of organic pollutant in HORW by FT-ICR MS discovered organic pollutants chain scission and oxidation process during the treatment. A great improvement of biodegradability for treated HORW had been obtained. The investigation uncovered the catalytic potential of FAC catalysts for ozonation of HORW.     

Kinetics of 1,3,6-naphthalenetrisulphonic acid ozonation in presence of activated carbon

Processes based on the simultaneous use of ozone and activated carbon have proven very effective for removing contaminants of high toxicity and low biodegradability. The present study is aimed to determine the kinetic constants involved in this purification process and their relationship with the surface chemistry of the activated carbon. For this purpose, the ozonation of 1,3,6-naphthalenetrisulphonic acid (NTS), selected as model compound, was carried out in the presence of different activated carbons. Determination of the Weisz-Prater parameter (C_WP) revealed that intraparticular diffusion limitations exist in the system for particles >500 μm. The degradation kinetics of NTS in the presence of activated carbon depends on the concentrations of both, the contaminant and the dissolved ozone, with a global reaction order of 2. The heterogeneous reaction constants were determined using a model that allowed quantification of the capacity of the activated carbon to increase the NTS degradation rate and of the chemical surface properties responsible for this increase. The basicity of the activated carbon is mainly responsible for the catalytic activity of the carbon in NTS ozonation, even though, mineral matter contributes positively to the catalytic activity.     

Ozonation of C.I. Reactive Yellow 3 and Further Decrease in Dissolved Organic Carbon Concentration by Post-Biodegradation

Using C.I. Reactive Yellow 3 as the target compound, the effect of the combined use of ozonation and post-biodegradation on the decrease in dissolved organic carbon (DOC) concentration was investigated, and the synergistic effect (the difference in the amounts of DOC removed by the biological process between solutions with and without ozonation) was estimated. A decrease in DOC concentration was observed during ozonation and ΔO₃/ΔDOC was decreased from 16.0 to 5.2 with increasing ozonation time. Moreover, an enhancement of biodegradability was shown. A further decrease in DOC concentration was observed during the biodegradation after ozonation. The total amount of DOC removed by the combined method was increased from 73.6 mg at 30 min to 159.9 mg at 4 h. The synergistic effect was in the range of 22.7 to 39.2 mg. BOD₅ was a better indicator of the synergistic effect than BOD₅/DOC.     

Optimum Ozone Dosage of Preozonation and Characteristic Change of Refractory Organics in Landfill Leachate

Preozonation on landfill leachate was carried out. COD removal rate has an obvious inflection at ozone dosage 0.186 mg_O3/mg_COD in ozonation process. Seven sets of identical O₃-SBR combined process under different ozone dosages were studied. The results indicated that the best COD removal rate of synergetic effect is also at 0.186 mg_O3/mg_COD. New organic substances produced after ozonation was confirmed by an excitation-emission matrix (EEM). Carbon dioxide production increased from 36.3 mg to 75.7 mg after ozonation, confirming that biodegradability of refractory organics in landfill leachate was enhanced. All the arguments indicated that the inflection point of COD removal by ozonation has a great significance for preozonation.     

Systematic Analysis of the Biochemical Characteristics of Activated Sludge During Ozonation for Lowering of Biomass Production

Properties of activated sludge during ozonation were analyzed. The structure and surface characteristics altered with the increase of ozone dosage. At low ozone dosage, the floc structure was completely dismantled. Floc fragments reformed through reflocculation at an ozone dosage greater than 0.20 g O₃·g^?1 mixed liquor suspended solids (MLSS). Inactivation of microorganisms in the activated sludge mixture was caused by ozonation. Microbial growth decreased by up to 65% compared to the control. Simultaneously, 92.5% of nucleotide and 97.4% of protein in microbial cells of the sludge were released. Organic substance, nitrogen and phosphorus were released from the sludge during the ozonation process. The initial value of soluble chemical oxygen demand (SCOD) was 72 mg·L^?1. When the ozone dosage was 0.12 g O₃·g^?1 MLSS, the value of SCOD rapidly reached 925 mg·L^?1, increased by almost 12-fold. Simultaneously, 54.7% of MLSS was reduced. The composition of MLSS was changed, indicating that the inner water of cells and volatile organic substance decreased during the ozonation process.     

Toxicity and Biodegradability Behavior of Xenobiotic Chemicals Before and After Ozonation: A Case Study with Commercial Textile Tannins

Ozonation of a natural tannin (NT; COD_o?=?1195 mg/L; TOC_o?=?342 mg/L; BOD_5,o?=?86 mg/L) and a synthetic tannin ST; COD_o?=?465 mg/L; TOC_o?=?55 mg/L; BOD_5,o?=?6 mg/L) being frequently applied in the polyamide dyeing process was investigated. Synthetic wastewater samples containing these tannins individually were prepared and subjected to ozonation at varying ozone doses (625– 1250 mgO₃/L wastewater), at pH?=?3.5 (the application pH of tannins) and pH?=?7.0 at an ozone dose of 1125 mgO₃/L wastewater. The collective environmental parameters COD, TOC, BOD₅, UV₂₅₄ and UV₂₈₀ (UV absorbance at 254 nm and 280 nm, representing aromatic and unsaturated moieties, respectively) were followed during ozonation. Changes in the biodegradability of the tannins were evaluated in terms of BOD₅ measurements conducted before and after ozonation. In addition, activated sludge inhibition tests employing heterotrophic biomass were run to elucidate the inhibitory effect of raw and ozonated textile tannins towards activated sludge biomass. Partial oxidation (45% COD removal at an ozone dose of 750 mg O₃/L wastewater and pH?=?3.5) of ST was sufficient to achieve elimination of its inhibitory effect towards heterotrophic biomass and acceptable biodegradability improvement, whereas the inhibitory effect and biodegradability of NT could not be reduced via ozonation under the same reaction conditions.     

Integration of continuous biological and chemical (ozone) treatment of domestic wastewater: 1. Biodegradation and post‐ozonation

The continuous treatment of domestic wastewater by an activated sludge process and by an integrated biological–chemical (ozone) oxidation process were studied in this work. Chemical oxygen demand (COD), biochemical oxygen demand (BOD), absorbance at 254 nm (UV₂₅₄) and nitrogenous compound content were the parameters followed in order to evaluate the performance of the two processes. Experimental data showed that both UV₂₅₄ and COD reductions are improved in the combined biological–chemical oxidation procedure. Thus, reductions of 59.1% and 37.2% corresponding to COD and UV₂₅₄, respectively were observed after the biological process (hydraulic retention time = 5 h; mixed liquor volatile suspended solids concentration = 3142 g m⁻³) compared with 71.0% and 78.4% obtained when a post‐ozonation step ( D _O3 = 41.7 g m⁻³) was included. During conventional activated sludge treatment, appropriate nitrification levels are only achieved with high hydraulic retention time and/or biomass concentration. Ozonation after the secondary treatment, however, allows improved nitrogen content reduction with total nitrite elimination. Post‐ozonation also leads to a higher biodegradability of the treated wastewater. Thus, the ultimate BOD/COD ratio goes from 0.16 after biological oxidation to 0.34 after post‐ozonation with 41.7 g O₃ m⁻³. © 1999 Society of Chemical Industry     

Ozonation of Dyestuffs and Intermediates and Further Decrease in Dissolved Organic Carbon by Post-Biodegradation

Four each of water-soluble dyestuffs, intermediates and reference compounds were examined to determine the effect of the combined use of ozonation and post-biodegradation on the decrease in the amount of dissolved organic carbon (DOC) and the synergistic effect induced by ozonation. The amount of DOC removed by ozonation was increased initially with increasing ozonation time, and showed a plateau thereafter. The amount of ozone required to remove 1 mg of DOC (ΔO₃/ΔDOC) ranged from 5.2 to 18.6 mgO₃/mgC for the dyestuffs and the intermediates. The DOC concentrations of all the ozonized solutions were decreased with incubation time. In the case of the dyestuffs and the intermediates, the total amounts of DOC removed were increased with increasing ozonation time and showed a plateau thereafter. The synergistic effect (the ozonation-induced increase in the amount of DOC removed by the biological process) was dependent on the initial biodegradability, and was observed in all the dyestuffs and the intermediates in the range of 0.2 to 42.7 mgDOC. On the other hand, no synergistic effect was observed in the reference compounds of high biodegradability.     

Purification of Polluted Source Water with Ozonoation and Biological Activated Carbon

In order to determine effective processes for purifying polluted source waters 1n Harbin City, various processes consisting of ozonation, sand filtration, and/or GAC filtration and adsorption, i.e., ozonation ( “O₃” Process), ozonatlon/sand filtration ( “O₃ + SF” Process), ozonation/biological activated carbon ( “O₃ + BAC” Process), ozonation/sand filtration/biological activated carbon ( “O₃ + SF + BAC” Process), and granular activated carbon (“GAC” Process) were tested In an 8 m³/d capacity pilot plant. In addition, a small plant of 500 L/d capacity was used to conduct comparative studies between the two processes “GAC” and “O₃ + BAC”, as well as two types of carbon.     

Removal of Color and Organic Matter in Industrial Phosphoric Acid by Ozone: Effect on Activated Carbon Treatment

Industrial phosphoric acid at 42-45% P₂O₅ and containing organic matter (OM) in the range of 220 mg/L to 300 mg/L is treated by combined ozonation and activated carbon. Ozonation alone removes the initial dark color of the acid and eliminates the organic content. Adsorption on activated carbon alone can reduce OM levels by 80% for more than 25 g/kg P₂O₅. We find that a preozonation noticeably enhances activated carbon efficiency and reduces its specific consumption. Isoconversion curves are plotted in specific ozone and activated carbon ratio space.     

Application of Individual and Simultaneous Ozonation and Adsorption Processes in Batch and Fixed-Bed Reactors for Phenol Removal

Ozonation, adsorption onto activated carbon and catalytic ozonation in batch and in a fixed-bed reactor for the removal/degradation of phenol and COD were investigated. In the case of batch ozonation the oxidation capacity was greater than 6.9 g of phenol/g O₃, while the continuous ozonation system degraded 40% of the phenol and reduced the COD by 27.9%. The adsorption process provided over 99% removal for phenol and COD; however, it treated only 5 L compared with 17 L for the combined process, which also increased the total area and pore volume of the activated carbon, due to the formation of pores and a widening of micropores.     

Decomposition of hydrogen peroxide in the presence of activated carbons with different characteristics

BACKGROUND: Catalytic ozonation promoted by activated carbon is a promising advanced oxidation process used in water treatment. Hydrogen peroxide generated as a by‐product from the reaction of ozone with some surface groups on the activated carbon or from the oxidation of some organic compounds present in the water being treated seems to play a key role in the catalytic ozonation process. Hydrogen peroxide decomposition promoted by two granular activated carbons (GAC) of different characteristics (Hydraffin P110 and Chemviron SSP‐4) has been studied in a batch reactor. The operating variables investigated were the stirring speed, temperature, pH and particle size. Also, the influence of metals on the GAC surface, that can catalyze hydrogen peroxide decomposition, was observed. RESULTS: Chemviron SSP‐4 showed a higher activity to decompose hydrogen peroxide than HydraffinP110 (70 and 50% of hydrogen peroxide removed after 2 h process, respectively). Regardless of the activated carbon used, hydrogen peroxide decomposition was clearly controlled by the mass transfer, although temperature and pH conditions exerted a remarkable influence on the process. Catalytic ozonation in the presence of activated carbon and hydrogen peroxide greatly improved the mineralization of oxalic acid (a very recalcitrant target compound). About 70% TOC (total organic carbon) depletion was observed after 1 h reaction in this combined system, much higher than the mineralization achieved by the single processes used. CONCLUSIONS: Of the two activated carbons studied, Chemviron SSP‐4 with an acidic nature presented a higher activity to decompose hydrogen peroxide. However the influence of the operating variables was quite similar in both cases. Experiments carried out in the presence of tert‐butanol confirmed the appearance of radical species. A kinetic study indicated that the process was controlled by the internal mass transfer and the chemical reaction on the surface of the activated carbon. The catalytic activity of hydrogen peroxide in oxalic acid ozonation promoted by activated carbon (O₃/AC/H₂O₂) was also studied. The results revealed the synergetic activity of the system O₃/AC/H₂O₂ to remove oxalic acid. Copyright © 2010 Society of Chemical Industry     

Ozone-Based Advanced Oxidation Processes for the Decomposition of N-Methyl-2-Pyrolidone in Aqueous Medium

The present study investigates the decomposition of N-Methyl-2-Pyrolidone (NMP) using conventional ozonation (O₃), ozonation in the presence of UV light (UV/O₃), hydrogen peroxide (O₃/H₂O₂), and UV/H₂O₂ processes under various experimental conditions. The influence of solution pH, ozone gas flow dosage, and H₂O₂ dosage on the degradation of NMP was studied. All ozone-based advanced oxidation processes (AOPs) were efficient in alkaline medium, whereas the UV/H₂O₂ process was efficient in acidic medium. Increasing ozone gas flow dosage would accelerate the degradation of NMP up to certain level beyond which no positive effect was observed in ozonation as well as UV light enhanced ozonation processes. Hydrogen peroxide dosage strongly influenced the degradation of NMP and a hydrogen peroxide dosage of 0.75 g/L and 0.5 g/L was found to be the optimum dosage in UV/H₂O₂ and O₃/H₂O₂ processes, respectively. The UV/O₃ process was most efficient in TOC removal. Overall it can be concluded that ozonation and ozone-based AOPs are promising processes for an efficient removal of NMP in wastewater.     

A Preliminary Study of the Efficiency And Mechanism of the Removal in the Ozonation and Bac Process

A preliminary study on removing THMs from chlorinated water by ozonation ( “O₃” process) and granular activated carbon bed filtration and adsorption (AC process) was carried out. It was found that the chloroform content in chlorinated water was reduced to some extent by ozonation at low dosages, but then it increased steeply with time, and finally reached much higher than the original values.     

Purification of Phenolic Wastewater Using Aerobic Bio-oxidation Combined with Activated Carbon Treatment and Ozonation

The combined process – aerobic bio-oxidation with activated carbon addition and ozonation was studied (ABO/AC/O3). The performance of the process was compared with conventional aerobic bio-oxidation (ABO). The studies were carried out in two continuous and periodic reactors to evaluate the purification efficiencies (in terms of COD, BOD and resorcinols removal), excess sludge generation and stability of the bioreactors against shock loadings. The parameters in continuous combined process were as follows: organics loading was 620 mgCOD/(day·L), activated carbon concentration 1g/L and ozone dose 2.45 mgO₃/L (mg ozone per liter of treated water). In periodic reactors the combined process was studied at lower activated carbon concentration and ozone dose (0.3 g/L and 0.57 mg/L respectively).

The results indicated that compared with conventional ABO, the co-effect of AC addition and short-termed (less than 1 week) or intermittent ozonation improved the removal of COD and BOD, while the longer period of ozonation resulted in reduction of excess sludge concentration in the bioreactor. The impact of AC and ozone on the ABO in the combined process did not concern only increased biomass activity, but AC and ozone improved also settleability of activated sludge and enhanced stability of the bioreactor to shock loadings.     

Manganese-Based Catalysts for the Catalytic Remediation of Phenolic Acids by Ozone

Manganese-based catalysts supported on Al₂O₃, TiO₂, ZrO₂ and CeO₂ were tested for the catalytic ozonation of a simulated wastewater involving phenolic acids. Comparing the Mn-Ce catalysts preparation method, wetness impregnation and co-precipitation, the last one showed to be more active. Moreover, the increase of Mn/Ce molar proportion from 22/78 to 70/30 increased the ozonation efficiency. The catalysts stability in terms of Mn leaching, carbon adsorption and effluent biodegradability was evaluated. Mn-Ce-O (70/30) CP shows to be the most suitable catalyst to improve phenolic wastewaters catalytic remediation by ozone.     

Effects of Ozonation on AOC Content of Humic Finnish Groundwater

The effects of ozonation on assimilable organic carbon (AOC) content of humic groundwater were investigated in batch experiments on three different groundwaters used as drinking water in Finland. All water samples had quite high concentrations of iron (range 2–10 mg/L) and manganese (range 0.1–0.2 mg/L) and therefore combined ozonation and filtration is a possible water purification method. The ozone dosage used varied from 0 to 16.6 mgO₃/L (ΔO₃/TOC?=?0–1.6). The ozone treatment increased the AOC concentration in the groundwater samples to different degrees. For example, an ozone dose of 3.9 mg/L increased the AOC concentration in different water as follows: from 49 μg/L to 55/L, from 7 μg/L to 119 μg/L and from 23 μg/L to 226 μg/L.     

Effect of Catalytic Ozonation Coupling with Activated Carbon Adsorption on Organic Compounds Removal Treating RO Concentrate from Coal Gasification Wastewater

This paper reports a novel system of catalytic ozonation coupling with activated carbon adsorption for removing the organic compounds treating in the RO concentrate from coal gasification wastewater. The effect of ozone dosage, catalyst dosage, reaction time, influence pH, and temperature on organic compounds removal were examined for the processes. In the catalytic ozonation process, increasing solution pH, dosages ozone, and catalyst were statistically significant for improving the performance. In addition, the high salinity with chloride concentration of 15 g/L could reduce the catalyst specific surface area by 18%. Thus, high salinity showed negative influence on the catalytic effect in TOC removal. Regarding activated carbon adsorption process, modified activated carbon by NaOH revealed advantages in adsorbing organic compounds treating catalytic ozonation effluent. With the ozone dosage of 120 mg/L, catalyst dosage of 2.0 g/L, catalytic ozonation reaction time of 1 h, and modified activated carbon adsorption time of 1 h, the average TOC removal efficiencies were maintained at the stable level of 58% with the TOC concentration of 26 mg/L.     

pH Effect on Ozonation of Ampicillin: Kinetic Study and Toxicity Assessment

Ampicillin (AP) is a penicillin-type antibiotic and one of the most widely used bacteriostatic antibiotics in human and veterinary medicine. A kinetic study was performed under different pH conditions (5, 7.2, and 9) to determine the degradation efficiency of AP by ozonation. The second-order rate constants for the direct reaction of AP with ozone were measured to be 2.2 ?5.4×10⁵ M^?1s^?1 under the pH conditions tested. The rate constants were greater at higher pH. The potential toxicity of the AP intermediates formed after ozonation under the various pH conditions were examined using a bioluminescence assay on Vibrio fischeri species. The biodegradability of the AP degraded products was also determined by measuring the BOD₅/COD of the ozonated samples under the different pH conditions. A lower biodegradability and acute toxicity was observed at the lowest pH (pH 5). These results suggest that higher pH conditions are needed for the removal of AP by ozonation in order to mitigate the residual toxicity that can remain even after complete removal of the parent compound by ozonation.     

Ozonation of complex industrial park wastewater: effects on the change of wastewater characteristics

BACKGROUND: Ozonation of complex industrial park wastewater was carried out in a semi‐batch reactor. The variation of wastewater characteristics was evaluated based on the analysis of 5‐day biochemical oxygen demand (BOD₅) concentration, BOD₅/chemical oxygen demand (COD) ratio, COD fractionation, and dissolved organic carbon (DOC) molecular size distribution before and after ozonation. RESULTS: The experimental results indicated that low efficiency of COD removal with increasing tendency of BOD₅ concentration generally appeared after ozonation. Also, the BOD₅/COD ratio increased from an initial of 0.27 to a maximum of 0.38. The COD fractionation tests revealed that most of the inert soluble COD was transformed to biodegradable soluble COD at 30 min of reaction time. Additionally, the DOC molecular size distribution tests showed that the fraction larger than 500 kDa was significantly decreased and the fraction smaller than 2 kDa was increased when the reaction time was prolonged to 240 min. CONCLUSION: This study verified that partial oxidation of the complex industrial park wastewater by ozonation could enhance wastewater biodegradability. The biodegradability enhancement was primarily because the inert soluble COD fraction was converted to the biodegradable soluble COD and the high molecular weight fraction of DOC was shifted toward the low molecular weight fraction. Copyright © 2009 Society of Chemical Industry