The electrochemical regeneration of activated carbon based adsorbents involves the removal of molecules adsorbed onto the surface of the adsorbent with the use of an electric current in an electrochemical cell restoring the carbon's adsorptive capacity. Electrochemical regeneration represents an alternative to thermal regeneration commonly used in waste water treatment applications. Common adsorbents include powdered activated carbon (PAC), granular activated carbon (GAC) and activated carbon fibre.
In waste water treatment, the most commonly used adsorbent is granular activated carbon (GAC), often used as to treat both liquid and gas phase volatile organic compounds and organic pollutants. [1] [2] Activated carbon beds vary in lifetime depending on the concentration of the pollutant(s) being removed, their associated adsorption isotherms, inlet flow rates and required discharge consents. Life- times of these beds can range between hours and months. Activated carbon is often landfilled at the end of its useful life but sometimes it is possible to regenerate it restoring its adsorptive capacity allowing it to be re-used. Thermal regeneration is the most prolific regeneration technique but has drawbacks in terms of high energy and commercial costs and a significant carbon footprint. [3] These drawbacks have encouraged research into alternative regeneration techniques such as electrochemical regeneration.
Once the adsorptive capacity of the activated carbon bed has been exhausted by the adsorption of pollutant molecules, the carbon is transferred to an electrochemical cell (to either the anode or the cathode) in which electrochemical regeneration can occur.
There are several mechanisms by which passing a current through the electrochemical cell can encourage pollutant desorption. Ions generated at the electrodes can change local pH conditions in the divided cell which affect the adsorption equilibrium and have been shown to promote desorption of organic pollutants such as phenols from the carbon surface. [3] [4] Other mechanisms include reactions between the ions generated and the adsorbed pollutants resulting in the formation of a species with a lower adsorptive affinity for activated carbon that subsequently desorb, or the oxidative destruction of the organics on the carbon surface. [5] It is agreed that the main mechanisms are based on desorption induced regeneration as electrochemical effects are confined to the surface of the porous carbons so cannot be responsible for bulk regeneration. [3] [6] The performance of different regeneration methods can be directly compared using the regeneration efficiency. This is defined as:
The cathode is the reducing electrode and generates OH− ions which increases local pH conditions. An increase in pH can have the effect of promoting the desorption of pollutants into solution where they can migrate to the anode and undergo oxidation hence destruction. Studies on cathodic regeneration have shown regeneration efficiencies for adsorbed organic pollutants such as phenols of the order of 85% based on regeneration times of 4 hours with applied currents between 10-100 mA. [3] However, due to mass transfer limitations between the cathode and anode, there is often residual pollutant left in the cathode unless large currents or long regeneration times are employed.
The anode is the oxidising electrode and as a result has a lower localised pH during electrolysis which also promotes desorption of some organic pollutants. Regeneration efficiencies of activated carbon in the anodic compartment are lower than that achievable in the cathodic compartment by between 5-20% for the same regeneration times and currents, [3] [6] however there is no observed residual organic due to the strong oxidising nature of the anode. [6]
For the bulk of carbonaceous adsorbents regeneration efficiency decreases over subsequent cycles as a result of pore blockages and damage to adsorption sites by the applied current. Decreases in regeneration efficiency are typically a further 2% per cycle. [3] Current leading edge research focuses on developing adsorbents able to regenerate 100% of their adsorptive capacity through electrochemical regeneration. [7] [8] [9]
Currently there are a very limited number of commercially available carbon based adsorption- electrochemical regeneration systems. One system that does exist uses a carbon adsorbent called Nyex in a continuous adsorption-regeneration system that uses electrochemical regeneration to adsorb and destroy organic pollutants. [10]
An electrode is an electrical conductor used to make contact with a nonmetallic part of a circuit. Electrodes are essential parts of batteries that can consist of a variety of materials (chemicals) depending on the type of battery.
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Activated carbon, also called activated charcoal, is a form of carbon commonly used to filter contaminants from water and air, among many other uses. It is processed (activated) to have small, low-volume pores that greatly increase the surface area available for adsorption or chemical reactions that can be thought of as a microscopic "sponge" structure. Activation is analogous to making popcorn from dried corn kernels: popcorn is light, fluffy, and its kernels have a high surface-area-to-volume ratio. Activated is sometimes replaced by active.
A solid oxide fuel cell is an electrochemical conversion device that produces electricity directly from oxidizing a fuel. Fuel cells are characterized by their electrolyte material; the SOFC has a solid oxide or ceramic electrolyte.
Heterogeneous catalysis is catalysis where the phase of catalysts differs from that of the reagents or products. The process contrasts with homogeneous catalysis where the reagents, products and catalyst exist in the same phase. Phase distinguishes between not only solid, liquid, and gas components, but also immiscible mixtures, or anywhere an interface is present.
Desorption is the physical process where adsorbed atoms or molecules are released from a surface into the surrounding vacuum or fluid. This occurs when a molecule gains enough energy to overcome the activation barrier and the binding energy that keep it attached to the surface.
In chemistry, photocatalysis is the acceleration of a photoreaction in the presence of a photocatalyst, the excited state of which "repeatedly interacts with the reaction partners forming reaction intermediates and regenerates itself after each cycle of such interactions." In many cases, the catalyst is a solid that upon irradiation with UV- or visible light generates electron–hole pairs that generate free radicals. Photocatalysts belong to three main groups; heterogeneous, homogeneous, and plasmonic antenna-reactor catalysts. The use of each catalysts depends on the preferred application and required catalysis reaction.
Brunauer–Emmett–Teller (BET) theory aims to explain the physical adsorption of gas molecules on a solid surface and serves as the basis for an important analysis technique for the measurement of the specific surface area of materials. The observations are very often referred to as physical adsorption or physisorption. In 1938, Stephen Brunauer, Paul Hugh Emmett, and Edward Teller presented their theory in the Journal of the American Chemical Society. BET theory applies to systems of multilayer adsorption that usually utilizes a probing gas (called the adsorbate) that does not react chemically with the adsorptive (the material upon which the gas attaches to) to quantify specific surface area. Nitrogen is the most commonly employed gaseous adsorbate for probing surface(s). For this reason, standard BET analysis is most often conducted at the boiling temperature of N2 (77 K). Other probing adsorbates are also utilized, albeit less often, allowing the measurement of surface area at different temperatures and measurement scales. These include argon, carbon dioxide, and water. Specific surface area is a scale-dependent property, with no single true value of specific surface area definable, and thus quantities of specific surface area determined through BET theory may depend on the adsorbate molecule utilized and its adsorption cross section.
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The lithium–air battery (Li–air) is a metal–air electrochemical cell or battery chemistry that uses oxidation of lithium at the anode and reduction of oxygen at the cathode to induce a current flow.
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Electrochemical regeneration of activated carbon adsorbents such as granular activated carbon present an alternative to thermal regeneration or land filling at the end of useful adsorbent life. Continuous adsorption-electrochemical regeneration encompasses the adsorption and regeneration steps, typically separated in the bulk of industrial processes due to long adsorption equilibrium times, into one continuous system. This is possible using a non-porous, electrically conducting carbon derivative called Nyex. The non-porosity of Nyex allows it to achieve its full adsorptive capacity within a few minutes and its electrical conductivity allows it to form part of the electrode in an electrochemical cell. As a result of its properties Nyex can undergo quick adsorption and fast electrochemical regeneration in a combined adsorption-electrochemical regeneration cell achieving 100% regeneration efficiency.
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