Electrocatalytic hydrogenation of acetophenone using a Polymer Electrolyte Membrane Electrochemical Reactor

The use of a solid polymeric electrolyte, spe, is not commonly found in organic electrosynthesis despite its inherent advantages such as the possible elimination of the electrolyte entailing simpler purification processes, a smaller sized reactor and lower energetic costs. In order to test if it were possible to use a spe in industrial organic electrosynthesis, we studied the synthesis of 1-phenylethanol through the electrochemical hydrogenation of acetophenone using Pd/C 30 wt% with different loadings as cathode and a hydrogen gas diffusion anode. A Polymer Electrolyte Membrane Electrochemical Reactor, PEMER, with a fuel cell structure was chosen to carry out electrochemical reduction with a view to simplifying an industrial scale-up of the electrochemical process. We studied the influence of current density and cathode catalyst loading on this electroorganic synthesis. Selectivity for 1-phenylethanol was around 90% with only ethylbenzene and hydrogen detected as by-products.

Performance Assessment of a Polymer Electrolyte Membrane Electrochemical Reactor under Alkaline Conditions – A Case Study with the Electrooxidation of Alcohols

A novel polymer electrolyte membrane electrochemical reactor (PEMER) configuration has been employed for the direct electrooxidation of propargyl alcohol (PGA), a model primary alcohol, towards its carboxylic acid derivatives in alkaline medium. The PEMER configuration comprised of an anode and cathode based on nanoparticulate Ni and Pt electrocatalysts, respectively, supported on carbonaceous substrates. The electrooxidation of PGA was performed in 1.0 M NaOH, where a cathode based on a gas diffusion electrode was manufactured for the reduction of oxygen in alkaline conditions. The performance of a novel alkaline anion-exchange membrane based on Chitosan (CS) and Poly(vinyl) alcohol (PVA) in a 50:50 composition ratio doped with a 5 wt.% of poly (4-vinylpyridine) organic ionomer cross-linked, methyl chloride quaternary salt resin (4VP) was assessed as solid polymer electrolyte. The influence of 4VP anionic ionomer loading of 7, 12 and 20 wt.% incorporated into the electrocatalytic layers was examined by SEM and cyclic voltammetry (CV) upon the optimisation of the electroactive area, the mechanical stability and cohesion of the catalytic ink onto the carbonaceous substrate for both electrodes. The performance of the 4VP/CS:PVA membrane was compared with the commercial alkaline anion-exchange membrane FAA −a membrane generally used in direct alcohol alkaline fuel cells- in terms of polarisation plots in alkaline conditions. Furthermore, preparative electrolyses of the electrooxidation of PGA was performed under alkaline conditions of 1 M NaOH at constant current density of 20 mA cm−2 using a PEMER configuration to provide proof of the principle of the feasibility of the electrooxidation of other alcohols in alkaline media. PGA conversion to Z isomers of 3-(2-propynoxy)-2-propenoic acid (Z-PPA) was circa 0.77, with average current efficiency of 0.32. Alkaline stability of the membranes within the PEMER configuration was finally evaluated after the electrooxidation of PGA.

Electrochemical oxidation of wastewater containing aromatic amines using a flow electrolytic reactor

Aromatic amines are environmental pollutants and represent one of the most important classes of industrial and natural chemicals. Some types of complex effluents containing these chemical species, mainly those originated from chemicals plants are not fully efficiently treated by conventional processes. In this work, the use of electrochemical technology through an electrolytic pilot scale flow reactor is considered for treatment of wastewater of a chemical industry manufacturer of antioxidant and anti-ozonant substances used in rubber. Experimental results showed that was possible to remove between 65% and 95% of apparent colour and chemical oxygen demand removal between 30 and 90% in 60 min of treatment, with energy consumption rate from 26 kWh m-3 to 31 kWh m-3. Absorbance, total organic carbon and toxicity analyses resulted in no formation of toxic by-products. The results suggest that the presented electrochemical process is a suitable method for treating this type of wastewater, mainly when pre-treated by aeration. Copyright © 2013 Inderscience Enterprises Ltd.

Electrochemical synthesis at pre-pilot scale of 1-phenylethanol by cathodic reduction of acetophenone using a solid polymer electrolyte

The pre-pilot scale synthesis of 1-phenylethanol was carried out by the cathodic hydrogenation of acetophenone in a 100 cm2 (geometric area) Polymer Electrolyte Membrane Electrochemical Reactor. The cathode was a Pd/C electrode. Hydrogen oxidation on a gas diffusion electrode was chosen as anodic reaction in order to take advantage of the hydrogen evolved during the reduction. This hydrogen oxidation provides the protons needed for the synthesis. The synthesis performed with only a solid polymer electrolyte, spe, has lower fractional conversion although a higher selectivity than that carried out using a support–electrolyte–solvent together with a spe. However, the difference between these two cases is rather small and since the work-up and purification of the final product are much easier when only a spe is used, this last process was chosen for the pre-pilot electrochemical synthesis of 1-phenylethanol.

Degradação eletroquímica do cloranfenicol em reator de fluxo

This paper reports a study of electrochemical degradation of the chloramphenicol antibiotic in aqueous medium using a flow-by reactor with DSA® anode. The process efficiency was monitored by chloramphenicol concentration analysis with liquid chromatography (HPLC) during the experiments. Analysis of Total Organic Carbon (TOC) was performed to estimate the degradation degree and Ion Chromatography (IC) was performed to determinate inorganic ions formed during the eletrochemical degradation process. In electrochemical flow-by reactor, 52% of chloramphenicol was degraded, with 12% TOC reduction. IC analysis showed the production of chloride ions (25 mg L-1), nitrate ions (6 mg L-1) and nitrite ions (4.5 mg L-1).

Estudo da degradação de ranitidina via H2O2 eletrogerado/Fenton em um reator eletroquímico com eletrodos de difusão gasosa

The study of the electrochemical degradation of the ranitidine was developed using an electrochemical reactor with a gas diffusion electrode (GDE) as cathode. The electrolysis experiments was performed at constant current (1 < A < 10) and flow rate of 200 L h-1. The process of drug degradation, chemical/electrochemical and electro-Fenton ways, using electrochemical reactor showed best efficiency at current values of > 4 A. The process reached a production of 630 mg L-1 of the H2O2 at 7 A. The ranitidine concentrations was reduced in 99.9% (HPLC) and chemical oxygen demand (COD) was reduced in 86.7% by electro-Fenton.

Avaliação da degradação do diclofenaco sódico utilizando H2O2/fenton em reator eletroquímico

This paper describes a degradation study of the anti-inflammatory sodium diclofenac in aqueous medium using an electro-chemical flow reactor with a gas diffusion electrode as cathode. Two degradation processes were compared: by H2O2 electro-generated and H2O2 electro-generated/Fe(II). Concentration of sodium diclofenac was determined during the experiments by HPLC. The changes in chemical oxigen demand (COD) were also evaluated. Under the specific reaction conditions, 350 mg L-1 of H2O2 was electro-generated and 99.2% of sodium diclofenac was degradated, with 27.4% COD reduction. At the same conditions, but using Fe(II), drug degradation was 99.4% and the COD reduction was 63.2%.

Degradação eletroquímica do cloranfenicol em reator de fluxo

This paper reports a study of electrochemical degradation of the chloramphenicol antibiotic in aqueous medium using a flow-by reactor with DSA® anode. The process efficiency was monitored by chloramphenicol concentration analysis with liquid chromatography (HPLC) during the experiments. Analysis of Total Organic Carbon (TOC) was performed to estimate the degradation degree and Ion Chromatography (IC) was performed to determinate inorganic ions formed during the eletrochemical degradation process. In electrochemical flow-by reactor, 52% of chloramphenicol was degraded, with 12% TOC reduction. IC analysis showed the production of chloride ions (25 mg L-1), nitrate ions (6 mg L-1) and nitrite ions (4.5 mg L-1).

Degradação de corantes têxteis e remediação de resíduos de tingimento por processos Fenton, foto-Fenton e eletro-Fenton

In this work the degradation of textile dyes were evaluated, using Fenton, photo-Fenton and electro-Fenton processes. Under optimized conditions Fenton and photo-Fenton processes showed high decolorization capacity of the model dyes. The electro-Fenton process was carried out in an undivided electrochemical reactor (1000 mL) equipped with a carbon-felt cathode (253 cm²) and a platinum gauze anode (6 cm²). Under optimal conditions (J: 1.6 mA cm-2, Na2SO4: 0.075 mol L-1, pH: 3) H2O2 concentration of about 60 mg L-1 was observed. The addition of Fe2+ (15 mg L-1) induces Fenton reactions that permit almost total decolorization of textile dyes.

Electrocombustion of humic acid and removal of algae from aqueous solutions

This paper reports experiments involving the electrochemical combustion of humic acid (HA) and removal of algae from pond water. An electrochemical flow reactor with a boron-doped diamond film anode was used and constant current experiments were conducted in batch recirculation mode. The mass transfer characteristics of the electrochemical device were determined by voltammetric experiments in the potential region of water stability, followed by a controlled current experiment in the potential region of oxygen evolution. The average mass transfer coefficient was 5.2 x 10(-5) m s(-1). The pond water was then processed to remove HA and algae in the conditions in which the reaction combustion occurred under mass transfer control. To this end, the mass transfer coefficient was used to estimate the initial limiting current density applied in the electrolytic experiments. As expected, all the parameters analyzed here-solution absorbance at 270 nm, total phenol concentration and total organic carbon concentration-decayed according to first-order kinetics. Since the diamond film anode successfully incinerated organic matter, the electrochemical system proved to be predictable and programmable.

Tratamento eletroquímico de água produzida sintética para remoção de hidrocarbonetos policíclicos aromáticos

The aim of this work is the treatment of produced water from oil by using electrochemical technology. Produced water is a major waste generated during the process of exploration and production in the oil industry. Several approaches are being studied aiming at the treatment of this effluent; among them can be cited the biological process and chemical treatments such as advanced oxidation process and electrochemical treatments (electrooxidation, electroflotation, electrocoagulation, electrocoagulation). This work studies the application of electrochemical technology in the treatment of the synthetic produced water effluent through the action of the electron, in order to remove or transform the toxic and harmful substances from the environment by redox reactions in less toxic substances. For this reason, we used a synthetic wastewater, containing a mixture H2SO4 0,5M and 16 HPAs, which are: naphthalene, acenaphthylene, acenaphthene, fluorene, phenanthrene, anthracene, fluoranthene, pyrene, benzo (a) anthracene, chrysene, benzo(b)fluoranthene, benzo(k) fluoranthene, benzo(a)pyrene, indeno(1,2,3-cd)pyrene, dibenzo(a, h)anthracene, benzo(g, h, i)perylene. Bulk electrochemical oxidation experiments were performed using a batch electrochemical reactor containing a pair of parallel electrodes, coupled with a power supply using a magnetic stirrer for favoring the transfer mass control. As anodic material was used, a Dimensionally Stable Anode (DSA) of Ti/Pt, while as cathode was used a Ti electrode. Several samples were collected at specific times and after that, the analysis of these samples were carried out by using Gas Chromatography Coupled to Mass Spectrometry (GC - MS) in order to determine the percentage of removal. The results showed that it was possible to achieve the removal of HPAs about 80% (in some cases, more than 80%). In addition, as an indicator of the economic feasibility of electrochemical treatment the energy consumption was analyzed for each hour of electrolysis, and based on the value kWh charged by ANEEL, the costs were estimated. Thus, the treatment costs of this research were quite attractive

Conciliação entre modelos de mecanismos avançados de oxidação eletroquímica

Many pollutants dumped in waterways, such as dyes and pesticides, have become so ubiquitous that they represent a serious threat to human health. The electrochemical oxidation is presented as an alternative clean, efficient and economic degradation of wastewater containing organic compounds and a number of advantages of this technique is to just not make use of chemical reagents, since only electrical energy is consumed during the removal of pollutants organic. However, despite being a promising alternative, still needs some tweaking in order to obtain better efficiency in the elimination of persistent pollutants. Thus, this study sought a relationship between a recently discovered phenomenon that reflects the participation of dissolved oxygen in solution in the electrochemical oxidation process, as an anomaly, present a kinetic model that shows instantaneous current efficiency (ICE) above 100% limited by theory, manifested for some experiments with phenolic compounds with H2SO4 or HClO4 as supporting electrolyte with electrodes under anodic oxidation on boron doped diamond (BDD). Therefore it was necessary to reproduce the data ICE exposes the fault model, and thus the 2-naphthol was used as phenolic compound to be oxidised at concentrations of 9, 12 and 15 mmol L-1, and H2SO4 and HClO4 to 1 mol L-1 as a supporting electrolyte under a current density of 30 mA cm-2 in an electrochemical reactor for continuous flow disk configuration, and equipped with anodes DDB at room temperature (25 oC). Experiments were performed using N2 like as purge gas for eliminate oxygen dissolved in solution so that its influence in the system was studied. After exposure of the anomaly of the ICE model and investigation of its relationship with dissolved O2, the data could be treated, making it possible for confirmation. But not only that, the data obtained from eletranálise and spectroscopic analysis suggest the involvement of other strongly oxidizing species (O3 (ozone) and O radicals and O2 -), since the dissolved O2 can be consumed during the formation of new strong oxidizing species, not considered until now, something that needs to be investigated by more accurate methods that we may know a little more of this system. Currently the performance of the electrocatalytic process is established by a complex interaction between different parameters that can be optimized, so it is necessary to the implementation of theoretical models, which are the conceptual lens with which researchers see

Degradação eletroquímica do cloranfenicol em reator de fluxo

Fundação de Amparo à Pesquisa do Estado de São Paulo (FAPESP)

Electrolito sólido polimérico: desde las pilas de combustible hasta la electrosíntesis orgánica

En este trabajo, en primer lugar, se presenta una nueva técnica desarrollada en nuestro laboratorio para el estudio electroquímico de las capas catalíticas de las pilas de combustible en células de tres electrodos, centrándonos en el proceso de electroxidación de ácido fórmico como reacción de test. Gracias a esta técnica se han estudiado parámetros de construcción como % en peso del metal, relación Nafion / sólidos totales y recubrimiento catalítico comprobando como la adsorción irreversible de adátomos de Bi sobre Pt soportado sobre Vulcan XC-72 favorece este proceso y como puede caracterizarse la capa catalítica de una pila de combustible de ácido fórmico (DFAFC) de forma integral utilizando estudios de sistemas nanoparticulados de Pt-Pd soportados sobre Vulcan XC-72 en el seno de ésta. En segundo lugar se ha introducido el concepto de PEMER (Polymer Electrolyte Membrane Electrochemical Reactor). De esta forma, una configuración electródica propia de las pilas de combustible se utiliza en electrosíntesis orgánica. Como reacciones test se han testeado la formación de 1-feniletanol como producto mayoritario por hidrogenación electrocatalítica de la acetofenona sobre nanopartículas de Pd soportadas sobre Vulcan XC-72 como electrocatalizador y, utilizando Pb (catalizador no noble) soportado sobre Vulcan XC-72, se ha estudiado la ruptura del puente disulfuro de L-cistina y N,N-diacetil-L-cistina (NNDAC) para obtener L-cisteína y N-acetil- L-cisteína (NAC). En ambas reacciones, hidrogenación y ruptura del puente disulfuro, se han analizado tanto parámetros constructivos de la capa catalítica como parámetros de proceso tanto a escala laboratorio con el uso de un reactor comercial de 25 cm² como a escala pre-piloto con la construcción de un reactor de 100 cm².

Planar solid oxide fuel cell modeling and optimization targeting the stack's temperature gradient minimization

Minimization of undesirable temperature gradients in all dimensions of a planar solid oxide fuel cell (SOFC) is central to the thermal management and commercialization of this electrochemical reactor. This article explores the effective operating variables on the temperature gradient in a multilayer SOFC stack and presents a trade-off optimization. Three promising approaches are numerically tested via a model-based sensitivity analysis. The numerically efficient thermo-chemical model that had already been developed by the authors for the cell scale investigations (Tang et al. Chem. Eng. J. 2016, 290, 252-262) is integrated and extended in this work to allow further thermal studies at commercial scales. Initially, the most common approach for the minimization of stack's thermal inhomogeneity, i.e., usage of the excess air, is critically assessed. Subsequently, the adjustment of inlet gas temperatures is introduced as a complementary methodology to reduce the efficiency loss due to application of excess air. As another practical approach, regulation of the oxygen fraction in the cathode coolant stream is examined from both technical and economic viewpoints. Finally, a multiobjective optimization calculation is conducted to find an operating condition in which stack's efficiency and temperature gradient are maximum and minimum, respectively.