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Activated Carbon Adsorption Mechanism

How the adsorbate is absorbed ?

Activated carbon can be considered as a material of phenomenal surface area made up of millions of pores – rather like a “molecular sponge”.  Activated carbon is a microporous inert carbon matrix with a very large internal surface (700 to 1 500 m²/g). The internal surface is ideal for adsorption. Activated carbon is made from materials containing amorphous carbon, such as wood, coal, peat, coconut shells… It is formed via a thermal process, where volatile components are removed from the carbon-laden material (raw material) in the presence of oxygen.

The process by which such a surface concentrates fluid molecules by chemical and/or physical forces is known as ADSORPTION (whereas, ABSORPTION is a process whereby fluid molecules are taken up by a liquid or solid and distributed throughout that liquid or solid).

In the physical adsorption process, molecules are held by the carbon’s surface by weak forces known as Van Der Waals Forces resulting from intermolecular attraction. The carbon and the adsorbate are thus unchanged chemically. However, in the process known as CHEMISORPTION molecules chemically react with the carbon’s surface (or an impregnant on the carbon’s surface) and are held by much stronger forces – chemical bonds.

In general terms, it is necessary to present the molecule to be adsorbed to a pore of comparable size.  In this way the attractive forces coupled with opposite wall effect will be at a maximum and should be greater than the energy of the molecule.

For example, a fine pored coconut shell carbon has poor decolorizing properties because color molecules tend to be larger molecular species and are thus denied access to a fine pore structure. In contrast, coconut shell carbons are particularly efficient in adsorbing small molecular species. Krypton and Xenon, for instance, are readily adsorbed by coconut shell carbon but readily desorb from large pored carbons such as wood.

Maximum adsorption capacity is determined by the degree of liquid packing that can occur in the pores. In very high vapor pressures, multi-layer adsorption can lead to capillary condensation even in mesopores (25A).

Activated Carbon Adsorption Capacity

The effectiveness at which activated carbon can remove contaminants from a stream is not based on the quantity of carbon, but, the activated carbon adsorption capacity. The greater the capacity, the more contaminants the activated carbon will be able to adsorb in volume. However, due to natural carbon’s limitations, it is not able to adsorb certain contaminants, as there molecular weight are to low to be treated through this process alone.

Active carbon is most effective against compounds that hold a high molecular weight and low solubility due to activated carbon having a high molecular weight as well. If there is ever an uncertainty if a specific contaminant will be removed in the adsorption process, referral is to be made to the solubility and molecular weight of said containment.

If adsorption capacity is plotted against pressure (for gases) or concentration (for liquids) at constant temperature, the curve so produced is known as an ISOTHERM. Adsorption increases with increased pressure and also with increasing molecular weight, within a series of a chemical family. Thus, methane (CH4) is less easily adsorbed than propane (C3H8).

Efficiency is determined by the type of pollutant, the type of activated carbon which is used and the temperature and humidity of the waste gases. An effective installation can be expected to realise a yield between 95 – 98 % for input concentrations of 500 – 2 000 ppm.

If effective, concentrations can typically be brought from 400 – 2 000 ppm to under 50 ppm.

In foundries, an end concentration of 20 mg/Nm³ VOC has been established

Mercury can be brought down to less than 0.05 mg/Nm³. Dioxins to less than 0.1 ng TEQ/Nm³ and, for odour and H2S, yields of 80 – 95 % have been established

 

 

This is a useful fact to remember when a particular system has a number of components.

Activated carbon adsorption mechanism

After equilibrium, it is generally found that, all else being equal, the higher molecular weight species of a multi-component system are preferentially adsorbed. Such a phenomenon is known as competitive or preferential adsorption – the initially adsorbed low molecular weight species desorbing from the surface and being replaced by higher molecular weight species. Physical adsorption in the vapor phase is affected by certain external parameters such as temperature and pressure.

The adsorption process is more efficient at lower temperatures and higher pressures since molecular species are less mobile under such conditions. Such an effect is also noticed in a system where moisture and an organic species are present. The moisture is readily accepted by the carbon surface but in time desorbs as the preferred organic molecules are selected by the surface.

This usually occurs due to differences in molecular size but can be also attributable to the difference in molecular charge. Generally speaking, carbon surfaces dislike any form of charge – since water is highly charged (ionic) relative to the majority of organic molecules the carbon would prefer the organic to be adsorbed.

Primary amines possess less charge on the nitrogen atom than secondary amines that in turn have less than tertiary amines. Thus, it is found that primary amines are more readily adsorbed than tertiary amines.

High levels of adsorption can be expected if the adsorbate is a reasonably large bulky molecule with no charge, whereas a small molecule with high charge would not be expected to be easily adsorbed.

Molecular shape also influences adsorption but this is usually of minor consideration. In certain situations, regardless of how the operating conditions can be varied, some species will only be physically adsorbed to a low level. (Examples are ammonia, sulfur dioxide, hydrogen sulfide, mercury vapor and methyl iodide). In such instances, the method frequently employed to enhance a carbon’s capability is to impregnate it with a particular compound that is chemically reactive towards the species required to be adsorbed.

Since carbon possesses such a large surface (a carbon granule the size of a “quarter” has a surface area in the order of ½ square mile!) coating of this essentially spreads out the impregnant over a vast area. This, therefore, greatly increases the chance of reaction since the adsorbate has a tremendous choice of reaction sites. When the adsorbate is removed in this way the effect is known as CHEMISORPTION.

Unlike physical adsorption the components of the system are changed chemically and the changed adsorbate chemically held by the carbon’s surface and desorption in the original form is nonexistent. This principle is applied in many industries, particularly in the catalysis field, where the ability of a catalyst can be greatly increased by spreading it over a carbon surface.

The effect of activated carbon on the adsorbate in water comes from two aspects: on the one hand, physical adsorption, the internal force of the activated carbon is in a balanced state under the force from all directions of the water body, and the external molecules are not balanced, so that the molecules adsorb to the activated carbon On the surface; on the other hand, it is chemical adsorption, because there is a chemical interaction between activated carbon and the adsorbed substance.

The adsorption of activated carbon on pollutants in water is the result of the combined action of the above two kinds of adsorption. There are four steps in the adsorption process of activated carbon on the adsorbate in water: first, due to the convection effect of the water body, the adsorbate diffuses onto the surface of the activated carbon; second, the adsorbate molecules diffuse into the large pores of the activated carbon through the liquid film; Third, the adsorbate molecules reach the micropores due to surface diffusion; fourth, the adsorbent molecules in water are adsorbed on the surface of the activated carbon pores.

Activated carbon adsorption equilibrium is a state of dynamic equilibrium. When the adsorption rate and the desorption rate of activated carbon in the solution are equal, that is, when the amount of activated carbon adsorption per unit time is equal to the amount of desorption, the concentration of the adsorbed substance in the solution and the concentration on the surface of the activated carbon will no longer change. For adsorption equilibrium.

Adsorption capacity and adsorption speed are two important indicators to measure the adsorption process of activated carbon. The adsorption capacity is reflected by the adsorption amount qe, which is mainly affected by the pore size and structure of activated carbon. In addition, temperature and pH value also affect the adsorption capacity of activated carbon.

Adsorption speed refers to the amount of material adsorbed per unit weight of adsorbent per unit time, which is mainly determined by the contact time of water and adsorbent. Because the adsorption reaction is an exothermic reaction, low temperature is usually beneficial to accelerate the adsorption rate.

 

Posted in Activated Carbons, Application, PROPERTIES AND QUALITY

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