Experimental Coupling and Modelling of Wet Air Oxidation and Packed-Bed Biofilm Reactor As an Enhanced Phenol Removal Technology
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Experimental coupling and modelling of wet air oxidation and packed-bed biofilm reactor as an enhanced phenol removal technology 1 1 1 Marine Minière & Olivier Boutin & Audrey Soric Abstract Experimental coupling of wet air oxidation process Keywords Coupled process . Advanced oxidation process . and aerobic packed-bed biofilm reactor is presented. It has Wetair oxidation . Biological treatment . Biofilm packed bed . been tested on phenol as a model refractory compound. At Process modelling . Phenol 30 MPa and 250 °C, wet air oxidation batch experiments led to a phenol degradation of 97% and a total organic carbon removal of 84%. This total organic carbon was mainly due Nomenclature 2 to acetic acid. To study the interest of coupling processes, wet AF m air oxidation effluent was treated in a biological treatment Total biofilm surface area −1 process. This step was made up of two packed-bed biofilm BOD gBOD L reactors in series: the first one acclimated to phenol and the Biological oxygen demand second one to acetic acid. After biological treatment, phenol CO2(d) mol L−1 and total organic carbon removal was 99 and 97% respec- Dissolved oxygen concentration in WAO Hdq −1 tively. Thanks to parameters from literature, previous CWAO mol L studies (kinetic and thermodynamic) and experimental Hydroquinone concentration in WAO AcAc −1 data from this work (hydrodynamic parameters and CWAO mol L biomass characteristics), both treatment steps were Acetic acid concentration in WAO PhOH −1 modelled. This modelling allows the simulation of the CWAO mol L coupling process. Experimental results were finally well Phenol concentration in WAO PhOH −3 reproduced by the continuous coupled process model: relative C0 gm error on phenol removal efficiency was 1 and 5.5% for wet Phenol concentration at the packing/biofilm air oxidation process and packed-bed biofilm reactor interface PhOH −3 respectively. CB gm Phenol concentration in bulk liquid PhOH −3 CF gm Phenol concentration at the biofilm/boundary * Olivier Boutin layer interface [email protected] PhOH −3 Cin gm 1 Aix Marseille Univ, CNRS, Centrale Marseille, M2P2, Phenol concentration in the influent Marseille, France −1 COD gCOD L Chemical oxygen demand PhOH 2 −1 DF m s Phenol diffusion coefficient in biofilm PhOH 2 −1 DL m s Phenol diffusion coefficient in water dP m Packing characteristic size pharmaceuticals, are still refractory to conventional treat- PhOH −2 −1 jF gphenol m s ments. Moreover, environmental protection involves more Phenol flux and more stringent regulations on pollutant discharge in aquat- kLmol−1 s−1 ic environment. Phenol oxidation rate constant One way to improve pollutant removal with limiting extra −1 kPhOH ms costs is to combine different processes in order to benefit from Phenol mass transfer coefficient their advantages and to overcome their drawbacks. This could −3 Ki gm create complementary and synergistic effects. An interesting Phenol inhibition constant coupled process is the combination of chemical and biological −3 KPhOH gm processes. During the last 40 years, more than 200 studies Phenol affinity constant have been published about chemical–biological-coupled pro- LL m cesses. Four literature reviews (Guieysse and Norvill 2014; Boundary layer length Scott and Ollis 1995; Mantzavinos and Psillaki 2004;Oller Qm3 s−1 et al. 2011) relate the evolution of this field from 1976 to 2013. Phenol flow rate Moreover, integrated processes have also gained more and R Ratio of phenol diffusion coefficient in biofilm more attention (Di laconi 2012). According to the effluent, on phenol diffusion coefficient in water one of the two following sequences is more relevant: −3 −1 rgCOD-X m s Bacteria growth rate & Biological–chemical treatments aim at degrading biode- PhOH −3 −1 r gphenol m s gradable compounds and mineralizing remaining com- Phenol consumption rate pounds which are refractory to biodegradation. These Re Reynolds number coupled processes are suitable for effluents with high con- Sc Schmidt number centration of biodegradable compounds and low concen- Sh Sherwood number tration of hardly biodegradable compounds, such as pulp −3 XH gCOD-X m and paper mill effluents (Assalin et al. 2009)orlandfill Biofilm density leachates (Lei et al. 2007). They are also suitable if the −3 XV kgVS m biological treatment of an effluent leads to specific metab- Biofilm density used in R calculation olites inhibiting bacterial activity: a chemical post- −1 YX/H gCOD-X gphenol treatment allows their oxidation. Heterotrophic biomass yield & Chemical–biological treatments are the oxidation of hard- zm ly biodegradable or inhibitory compounds into more bio- Distance from packing degradable ones and then a degradation of those com- −1 μmax s pounds through a biological treatment. These coupled pro- Specific growth rate cesses allow saving energy or chemicals due to partial 2 −1 νwater m s oxidation in comparison with total chemical Water kinematic viscosity mineralisation. They are suitable for effluents containing a high fraction of hardly biodegradable compounds, such as petrochemical effluents (Ishak and Malakahmad 2013), Introduction as well as effluents containing toxic or inhibitory elements to micro-organism compounds, such as textile effluents Industrial wastewater treatment is a strong issue, as effluents with toxic dyes or pesticide effluents (Libra and Sosath could combine high organic waste concentration, refractory 2003;Parienteetal.2013). compounds at different concentrations and relatively low and intermittent flow rates. Chemical processes are known Chemical–biological processes are the most studied, as to be very efficient for the removal (oxidation) of many pol- they can treat effluents with high toxicity. Among chemical lutants. They often involve chemical and/or energy consump- and advanced oxidation processes, wet air oxidation tion (Guieysse and Norvill 2014). On the contrary, biological (WAO)—an oxidation process in subcritical water at high processes are low-energy and maintenance consumers, but temperature and pressure—is an efficient process with no they are only efficient for biodegradable organic compounds. chemical consumption (except oxygen or air). It can be They cannot easily remove highly toxic pollutants or refrac- optimised in terms of energy consumption (Lefevre et al. tory compounds in normal operating conditions (Guieysse and 2011). Verenich and Kallas (2002) showed that WAO as a Norvill 2014). Though a large range of processes are avail- pre-treatment could enhance biodegradability of pulp and pa- able, many pollutants, as for instance dyes, surfactants or per mill effluents from 24 to 89%. Moreover, this process can be economically viable for concentration of some relatively the whole process simulated in order to help the evaluation of high wastes, due to its high efficiency and short residence this coupling approach. time. However, an energy optimisation is needed in this case (Lefevre et al. 2011; Lefevre et al. 2012). Among biological processes, packed-bed biofilm reactors (PBBRs) are based on Materials and methods the biodegradation of pollutants by biomass attached on car- riers (Warnoc et al. 2005; Ranade et al. 2011). They are very Materials interesting since they need less space than suspended biomass reactors; they are easier to handle than fluidised bed High-purity phenol (>99%) and acetic acid of analytical grade bioreactors and also involve high sludge retention time were bought from Sigma-Aldrich and Carlo Erba Reagents leading to good efficiency. Zapata et al. (2010)successfully respectively. Pink dye Rhodamine WT (20 wt% rhodamine used a PBBR with a photo/Fenton pre-treatment for the de- in water) for residence time distribution (RTD) experiments contamination of pesticide-containing wastewater, achieving was bought from Acros Organics. Bioreactors were inoculated 84% of mineralisation. with samples of activated sludge from an urban wastewater In many research studies, authors target model compounds. treatment plant. For instance, several studies on chemical–biological coupling use phenol, which is found in many industrial effluents (win- Experimental setup ery, olive mill, petrochemistry, coking, refinery, etc.) and which is dangerous for human health (Busca et al. 2008). The experimental coupling of wet air oxidation with packed- Advanced oxidation process, coupled with biological process, bed biofilm reactors was carried out on a phenolic solution. is an interesting treatment for olive mill effluents containing First, oxidation of a phenolic solution was carried out in a high concentration of phenol (Mantzavinos and Kalogerakis batch WAO reactor. Then, the resulting effluent was 2005). For olive mill effluents, phenol concentrations can vary biodegraded by the means of two PBBRs in series. from 5.8 g L−1 (Rivas et al. 2001)to29gL−1 (Minh et al. 2008). Benitez et al. (1999) reached 84% of chemical oxygen Wet air oxidation step demand (COD) removal from an olive mill wastewater by coupling ozonation with an aerobic biological treatment. Figure 1 shows the wet air oxidation batch reactor (Top Although some studies give elements on the feasibility of Industrie, France). It was composed of a 152.8-mL stainless coupling chemical–biological processes for the treatment of steel reactor equipped with a stirrer (Rushton propeller, max- industrial effluents, they usually do not consider the whole imum speed 2000 rpm). It was connected to a volumetric and effective coupled process (Zapata et al. 2010;Wang pump allowing injection