Electrochemical conversion of carbon dioxide: effect of the cell and of the operating parameters on the performances of the process.

Recycling technologies of CO2 allow to introduce renewable energy in the chemical and energy chain, storing a renewable energy in the chemical form. In this context, electrochemical conversion of CO2 is considered one of the more interesting approaches, using excess electric energy from intermittent renewable sources. (1) Furthermore, products can be selectively controlled by changing the operating conditions of electrolysis. In particular, in the last years, an increasing attention has been devoted to the electrochemical conversion of CO2 to formic acid or formate in water. (2,3,4) The main hurdle of the reduction of CO2 from water solution is the low CO2 solubility in water. In this work,…

Electrochemical Abatement of Organic Pollutants in Continuous-Reaction Systems through the Assembly of Microfluidic Cells in Series

The electrochemical treatment of wastewater contaminated by organic pollutants was performed under a continuous mode by using, for the first time, various micro-electrochemical cells in series. A synthetic solution of acid orange 7 (AO7), a largely used azoic dye, was chosen as model wastewater. Both the electro-Fenton (EF) method with a cheap compact graphite cathode and electrochemical oxidation (EO) at a boron-doped diamond (BDD) anode were used. EO gave higher abatement of total organic carbon (TOC), but drastically higher energetic consumptions than EF. It is worth mentioning that very different operating conditions were set for EF and EO to optimize their performances. The utilization…

Effect of air pressure on the electro-generation of H2O2 and the abatement of organic pollutants in water by electro-Fenton process

Abstract The electro-generation of H 2 O 2 and the abatement of the model organic pollutant Acid Orange 7 (AO7) in water by an electro-Fenton process were performed under moderate air pressures (up to 11 bar) for the first time to our knowledge. An increase of the pressure gave rise to a drastic enhancement of the concentration of hydrogen peroxide. In systems pressurized with air at 11 bar, the electro reduction of oxygen at a graphite cathode gave rise to a concentration of H 2 O 2 of about 12 mM, about one order of magnitude higher than that achieved at atmospheric pressure. This result is attributed to the mass transfer intensification induced by the higher local concentration of molecu…

Electrochemical Processe s and Apparatuses for the Abatement of Acid Orange 7 in Water

We have studied the electrochemical treatment of aqu eous solutions contaminated by Acid Orange 7 (AO7) by electro-Fenton process (EF). The main object ive was to evaluate how the electrochemical route affects the performances of the d egradation process. EF process was carried out in a number of very different reactors: conventional bench scale electrochem ical cell, microfluidic electrochemical reactor, microbial fuel cell and stack for reverse electrodialysis processes. The utilisation of micro devices allowed to work without the addition of a supporting elec trolyte and improved the performances of EF. Microbial fuel cell did not need the supply of electric energy bu t our device requir…

NEW ELECTROCHEMICAL MICROFLUIC DEVICES FOR THE SYNTHESIS OF CHEMICALS AND THE TREATMENT OF WASTE WATERS

Abatement of Acid Orange 7 in macro and micro reactors. Effect of the electrocatalytic route

Abstract The electrochemical treatment of aqueous solutions contaminated by Acid Orange 7 (AO7) was widely studied with the main objective to evaluate as the electrocatalytic route affects the performances of the degradation process in macro and microfluidic cells. Direct anodic oxidation (EO), electro-Fenton (EF), electro-generation of active chlorine (IOAC) and coupled processes were investigated in macro and microfluidic reactors in order to select more effective conditions for the treatment of such compound. The effect of numerous operative parameters (such as nature of the electrode materials, coupling of processes, flow rate, current density and inter-electrode distance) on the perfor…

Electrochemical treatment of real wastewater with low conductivity

In the last years, many efforts have been devoted to the development of electrochemical processes for the effective treatment of wastewater contaminated by organic pollutants resistant to conventional biological processes and/or toxic for microorganisms [1–5]. It was shown that some electrochemical approaches, including the direct anodic oxidation at suitable anodes such as boron-doped diamond (BDD) and/or electro-Fenton (EF) at suitable operating conditions and cells [1–6] could allow treating effectively a very large number of organic pollutants. However, most of the investigations were performed using synthetic wastewater. Hence, it is now mandatory to study the problems connected to the…

ELECTROCHEMICAL CONVERSION OF DICHLOROACETIC ACID TO CHLOROACETIC ACID IN A MICROFLUIDIC STACK AND IN A SERIES OF MICROFLUIDIC REACTORS

The electrochemical conversion of dichloroacetic acid to chloracetic acid was performed in three different micro devices: a simple micro fluidic cell; a microfluidic stack equipped with various electrode chambers in series and three micro fluidic cells in series. The electrochemical synthesis of chloracetic acid was performed successfully with high yields and selectivity under a single-pass mode without supporting electrolyte at low cell voltages. An increase of the productivity and of the final concentration of the target product was achieved by using a stack with two or three electrode chambers in series. The utilization of three micro reactors in series open interesting new perspectives,…

ELECTROCHEMICAL MICROREACTORS FOR SYNTHESIS OF CHEMICALS AND ABATEMENT OF ORGANIC POLLUTTANTS

Electrochemical methods can offer new sustainable routes for both the synthesis of chemicals and the abatement of organic pollutants resistant to biological processes. These methods use a clean reagent, the electron, and very mild operative conditions (ambient temperature and atmospheric pressure) with limited operative costs. However, electrochemical processes present some important disadvantages when performed in conventional reactors. In particular, to achieve reasonable cell voltages when the medium has not an adequate conductivity, one needs adding to the system a supporting electrolyte. This is certainly a main obstacle for a wide application of electrochemical tools. Indeed, adding c…

ELECTROCHEMICAL ABATEMENT OF ORGANIC POLLUTANTS IN WATER IN MICROFLUIDIC DEVICES

Electro-generation of H2O2 and abatement of organic pollutant in water by an electro-Fenton process in a microfluidic reactor

The electro-generation of H2O2 and the abatement of the model organic pollutant Acid Orange 7 (AO7) in water by an electro-Fenton process were performed both in a conventional undivided macro cell and, for the first time, in a microfluidic reactor. Under optimized operative conditions, the reduction of oxygen in the microdevice gave rise, using graphite cathode, to a concentration of H2O2 of about 6 mM, one order of magnitude higher than that achieved in conventional cells. Similarly, when electro-Fenton was performed in the microfluidic reactor a dramatic increase of the abatement of COD was achieved with respect to that obtained in a conventional cell. Keywords: Wastewater treatments, Mic…

ELECTROCHEMICAL REDUCTION OF CARBON DIOXIDE TO FORMIC ACID AT TIN CATHODE IN DIVIDED AND UNDIVIDED CELLS: EFFECT OF OPERATING PARAMETERS

The electrochemical reduction of carbon dioxide is considered a relevant topic for both the synthesis of chemicals and the decrease of global warming. Electrochemical processes could utilize excess energy from intermittent renewable sources to convert carbon dioxide in various products such as CO, formate and formic acid, methane and ethylene in water and oxalic acid, formic acid, CO as well as carboxylic acids (by reaction with suitable reagents such as aromatic ketones or benzylic halides) in aprotic solvents [1-3]. It has been shown that the selectivity of the process dramatically depends on the nature of the cathode. Four distinct classes of metal catalysts have been identified on the b…

Effect of air pressure on the electro-Fenton process at carbon felt electrodes

Abstract The effect of air pressure on electro-Fenton (PrEF process) was evaluated using two organic substances (maleic acid and Acid Orange 7) as model organic pollutants. First experiments were performed using a conventional carbon felt (CF) cathode. At room pressure, a slow removal of maleic acid was obtained, together with the generation of formic acid. Conversely, using pressurized air, the removal of maleic acid was dramatically accelerated and the formation of formic acid was not detected. The utilization of a carbon felt modified by the deposition of carbon black + PTFE mixture (MCF) and of pressurized air allowed to achieve even faster and almost total (>95%) removal of total organ…

ELECTROSYNTHESIS IN MICROFLUIDIC CELLS: PRELIMINARY INVESTIGATIONS

ELECTROCHEMICAL ABATEMENT OF AZO 7 IN WATER SOLUTION IN MACRO AND MICRO CELLS

STUDIO DI PROCESSI ELETTROCHIMICI PER L’ABBATTIMENTO DI INQUINANTI ORGANICI IN ACQUA IN MACRO E MICRO REATTORI

ELECTROCHEMICAL MICROREACTORS FOR THE ABATEMENT OF ORGANIC POLLUTANTS IN WATER SOLUTION

Electrochemical methods can offer new sustainable routes for the abatement of organic pollutants resistant to biological processes. These methods use a clean reagent, the electron, and very mild operative conditions (ambient temperature and atmospheric pressure) with limited operative costs. However, electrochemical processes present some important disadvantages when performed in conventional reactors. In particular, to achieve reasonable cell voltages when the medium has not an adequate conductivity, one needs adding to the system a supporting electrolyte. This is certainly a main obstacle for a wide application of electrochemical tools. Indeed, adding chemicals is often a problematic issu…

Reduction of oxygen to H2O2 at carbon felt cathode in undivided cells. Effect of the ratio between the anode and the cathode surfaces and of other operative parameters

Abstract In the last years, the electrochemical conversion of oxygen to hydrogen peroxide at carbon felt has been largely studied in order to define a new route for the production of H2O2 and to optimize the electro-Fenton process, which is based on the cathodic generation of H2O2. In particular, many studies regarding electro-Fenton process were carried out in undivided cells in order to avoid the costs of the separator and to reduce the cell potentials. Hence, in order to optimize the cathodic conversion of oxygen to H2O2 in undivided cells, the effect of many parameters linked to the anodic process were here evaluated. In particular, it was demonstrated that the performances of the proce…

Electrochemical reduction of carbon dioxide to formic acid at a tin cathode in divided and undivided cells: effect of carbon dioxide pressure and other operating parameters

Abstract The reduction of carbon dioxide to formic acid at a tin cathode was studied in both divided and undivided cells. In the first stage of the study, the effect of some operating parameters, including the working potential and the nature of the supporting electrolyte and of the cathode, on both the cathodic reduction of CO2 and the anodic oxidation of formic acid was investigated in a divided cell. In a second stage, the reduction of carbon dioxide was performed in an undivided cell with the aim of studying the effect on the generation of formic acid of various operating parameters such as current density, cathode to anode area ratio, mixing rate and nature of the anode and of the supp…

Effect of pressure on the electrochemical generation of hydrogen peroxide in undivided cells on carbon felt electrodes

The electrochemical generation of H2O2can be performed in aqueous solutions by cathodic reduction at carbonaceous cathodes of oxygen coming from air. The performances of the process in terms of concentration of H2O2and current efficiency (CE) are limited by the low solubility of oxygen in water at atmospheric pressure. However, the solubility of oxygen can be increased upon enhancing the air pressure. The effect of pressure on the electrochemical generation of hydrogen peroxide was studied in undivided cells changing the pressure from 0 to 30 relative bar and the current density from 1 to 100 mA cm−2. Simple carbon felt and compact graphite cathodes were first used. A dramatic effect of…

ABATEMENT OF POLLUTANTS IN WATER BY DIFFERENT ELECTROCHEMICAL APPROACHES

Electrochemical Abatement of Organic Pollutants in Water by Electro- Fenton with Natural Heterogeneous Catalysts Under Pressure

In recent decades, electrochemical advanced oxidation processes (EAOPs) have proved as alternative technologies to conventional processes. Indeed, EAOPs can often allow to treat wastewater containing toxic and POPs. Among them, electro-Fenton (EF) is considered particularly promising for the treatment of recalcitrant organics, since it presents various advantages, including high abatements for many organic pollutants, simplicity of equipment and operations, relatively low cost and low consumption of chemicals. Recently, the utilization of some natural heterogeneous catalysts was proposed in order to avoid some disadvantages of the conventional EF process. In this frame, in this work EF proc…

STUDY OF CAPACITIVE ELECTRODES FOR REVERSE ELECTRODIALYSIS PROCESSES

It has been calculated that the energy dissipated wherever the rivers get to the sea this corresponds to an amount of about 2 TW of power [1]. Recovering part of this energy could attenuate the dependency of our economic system from fossil fuels. The techniques conceived to exploit this blue energy are grouped within the family of the salinity gradient technologies, where pressure-retarded osmosis (PRO) and reverse electrodialysis (RED) are regarded as the most established technologies [2]. Nevertheless, their power is limited respectively by various factors including the kinetics of electrodes reactions. Conversely, the use of capacitive electrodes proposed by Brogioli in 2009, does not se…

Electrochemical conversion of Carbon Dioxide: effect of operating parameters and of the reactor on the performances of the process.

Electrochemical Conversion of Dichloroacetic Acid to Chloroacetic Acid in Conventional Cell and in Two Microfluidic Reactors

The electrochemical conversion of dichloroacetic acid to chloracetic acid is investigated in conventional cells and in microreactors. Two different microreactors are used: the first is a filter press cell equipped with PTFE micrometric spacers, easy to assemble and disassemble and available for a large variety of electrodes and solvents; the second is made using an adhesive spacer, micromilling and press and could easily be developed on an industrial scale. The electrochemical synthesis is performed successfully in the microreactors equipped with a graphite cathode under proper operative conditions. The performance of the process strongly depends on the nature of the cathode and, for micror…

Electrochemical treatment of aqueous solutions of organic pollutants by electro-Fenton with natural heterogeneous catalysts under pressure using Ti/IrO2-Ta2O5 or BDD anodes

The treatment of toxic organic pollutants by electro-Fenton (EF) presents some drawbacks such as the necessity to work at low pH and the low solubility of oxygen in water contacted with air or oxygen at room pressure that results often in slow and relatively low abatements. Here, the coupled adoption of natural heterogeneous catalysts and of relatively high pressure was proposed in order to improve the performances of EF for the treatment of organic pollutants. Caffeic acid (CA) and 3-chlorophenol were used as model resistant organic pollutants. EF process was performed using both conventional homogeneous FeSO4 and natural heterogeneous catalysts (pyrite, chalcopyrite, Fe2O3 and Fe3O4) as i…

Electrochemical treatment of real wastewater. Part 1: Effluents with low conductivity

Abstract The treatment of a real wastewater characterized by low conductivity was performed by anodic oxidation at boron doped diamond (BDD) in both conventional and microfluidic cells. The electrolyses carried out in conventional cells without supporting electrolyte were characterized by very high TOC removals but excessively high energetic consumptions and operating costs. The addition of sodium sulphate, as supporting electrolyte, allowed to strongly reduce the cell potentials and consequently the energetic consumptions and the operating costs. However, under various operating conditions, the addition of Na2SO4 caused a lower removal of the TOC. The best results in terms of both TOC remo…

Development of an Electrochemical Process for the Simultaneous Treatment of Wastewater and the Conversion of Carbon Dioxide to Higher Value Products

Many researchers have shown that selected anodic processes allow effective treatment of a very large amount of wastewater contaminated by pollutants resistant to biological processes. In the meantime, various authors have also shown that carbon dioxide can be converted into higher value products, such as formic acid or synthesis gas, by cathodic reduction at suitable cathodes. These two processes present interesting economic potential that, however, still needs to be improved for further development at an industrial level. Herein, these two kinds of process are combined in the same cell to improve their economic feasibility. In particular, the anodic treatment of wastewater at a boron-doped…

Electrochemical treatment of organic pollutants in macro and micro reactors

Electrochemical treatment of real wastewater with low or high conductivity

In the last years, many efforts have been devoted to the development of electrochemical processes for the effective treatment of wastewater contaminated by organic pollutants resistant to conventional biological processes and/or toxic for microorganisms [1–5]. It was shown that some electrochemical approaches, including the direct anodic oxidation at suitable anodes such as boron-doped diamond (BDD) and/or electro-Fenton (EF) at suitable operating conditions and cells [1–6] can allow to treat effectively a very large number of organic pollutants. However, most of the investigations were performed using synthetic wastewater. Hence, it is now mandatory to study the problems connected to the p…

ABATEMENT OF ACID ORANGE 7 IN WATER BY DIFFERENT ELECTROCHEMICAL APPROACHES

Very large amounts of synthetic dyes are discharged in the environment from industrial effluents [1]. Due to their large-scale production and extensive application, synthetic dyes can cause considerable nonaesthetic pollution and are serious health-risk factors [2]. Dyes are commonly classified from their chromophore group. The majority of these compounds consumed at industrial scale are azo (–N=N–) derivatives that represent more than 50% of the all dyes used in textile industries, although antraquinone, indigoide, triphenylmethyl, xanthene, sulphur and phtalocyanine derivatives are frequently utilized [3]. Since dyes usually present high stability under sunlight and resistance to microbia…

ELECTROCHEMICAL TREATMENT OF WASTE WATERS CONTAMINATED BY ORGANIC POLLUTANTS: A LOOK ON SOME NEW APPROACHES

Recent researches have demonstrated that electrochemical methods offer an attractive alternative to traditional routes for treating wastewaters containing toxic or/and refractory organic pollutants. These methods use a clean reagent, as the electron, very mild operative conditions (ambient temperature and pressure) and can be run with limited operative costs. Despite of the above mentioned advantages, electrochemical processes present some important disadvantages such as: • the cost of some electrodic materials such as silver (for reduction processes) and boron doped diamond (for oxidation ones). On the other hand, the cost of silver based electrodic materials can be considerably lowered by…