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PURIFICATION OF AIR, WATER AND OFF GAS · SOLVENT RECOVERY

Activated Carbon for Solvent Recovery

K. -D. Henning J. Degel

Paper presented at the Meeting of the European Rotogravure Association Engineers
GroupMulhouse/France. 20/21 March 1990

Activated Carbon for Solvent Recovery

3. Fundamentals of Adsorption and Desorption

Contents

To understand the adsorptive solvent recovery we have to consider some fundamentals of
adsorption and desorption (Figure 6). Adsorption is the term for the enrichment of gaseous or
dissolved substances (the adsorbate) on the boundary surface of a solid (the adsorbent). On their
surfaces adsorbents have what we call active centers where the binding forces between the
individual atoms of the solid structure are not completely saturated. At these active centers an
adsorption of foreign molecules takes place.

Figure 6: Fundamentals of adsorption and desorption

The adsorption process generally is of an exothermal nature. With increasing temperature and
decreasing adsorbate concentration the adsorption capacity decreases. For the design of
adsorption processes it is important to know the adsorption capacity at constant temperature in
relation to the adsorbate concentration.

Figure 7 shows the relation, termed adsorption isotherm, in the known representation according to
Freundlich. The equilibrium loads of five typical solvents in relation to the solvent concentration
were plotted. It is shown that various solvents are adsorbeddifferently depending on the strength of
the interaction forces between adsorbate andadsorbent.

• Next follows the adsorbate reduction in the so called adsorption ormass transfer zone (MTZ). the contaminated air flows through an activated carbon bed. Figure 7: Adsorption isotherms of typical solvents Please look carefully at solvent No. Then the activated carbon bed has to be regenerated. If the passage of the fluid is continued on still further. With increasing adsorption time the adsorption zone moves through the activated carbon bed. the exit concentration continues to rise until it becomes the same as the inlet concentration. . • The outlet zone of the adsorber filling is still unloaded at this time. We will come across toluene again when we speak about the plant examples. Figure 8 shows the idealized breakthrough curve as a function of the gas volume to be treated. If the top of the MTZ reaches the adsorber end breakthrough occurs. 2. The adsorption step will be stopped if a pre-determined solvent concentration in the exhaust gas is exceeded. To remove the solvent. It is toluene. After short working time the activated carbon bed is subdivided into threezones: • On the inlet side of the adsorber the equilibrium load corresponding tothe inlet concentration co is achieved.

because it is cheap and simple. A certain flow is also required to reduce the partial pressure of the adsorbate and carry out the solvent of the activated carbon bed. Steam is very effective in raising the bed tem perature quickly and is easily condensed to recover the solvent as a liquid. The amount of steam required depends on the interaction between solvent and activated carbon. 9). Figure 8: Idealized breakthrough curve of a fixed bed adsorber To reverse the adsorption mechanism the equilibrium must be reversed by increasingthe temperature and decreasing the solvent concentration by purging (Figure. . Direct steaming of the activated carbon bed is the most widely used regeneration technique. Figure 9 shows schematically the principle of steam desorption.

the temperature of the activated carbon is increased to appprox. When designing a recovery plant. 100°C.the engineer now tries to consider as for as possible these bases of adsorption technology. Further reduction of the residual load is obtained by the flushing effect of the steam and the declining toluene partial pressure. Figure 9: Principle of steam desorption First. Desorption of the adsorbed solvents starts after a certain delay. The load difference between spent and regenerated activated carbon .e. after the activated carbon bed has heated up.we call it "working capacity" - will be available for the next adsorption cycle. The specific steam consumption increases strongly with decreasing residual load of the activated carbon (Figure 10). For reasons of cost effectiveness desorption is not run completely. This temperature increase reduces the equilibrium load of the activated carbon. The desorption time is optimized by consideration both of the acceptable residual load and the specific steam consumption. . i.

All activated carbon qualities are characterised by their widely ramified pore system(Figure 2) giving access to what are called macropores (diam = >25 nm). Figure 10: Desorption efficiency and steam consumption Previous page Next page Contents page Index PURIFICATION OF AIR. made of carbonaceous raw materials. Henning J.the content of a larger solvent recovery plant corresponds to the surface of the Federal Republic of Germany. 20/21 March 1990 Activated Carbon for Solvent Recovery 2. The total surface of 200 mt of activated carbon . Activated Carbon Contents Activated carbon is the tradename for highly porous products. Degel Paper presented at the Meeting of the European Rotogravure Association Engineers GroupMulhouse/France. -D. the large internal surface of more than 1000 m2/g is significant. Above all. with a large internal surface of 400-1600 m2/g and a large pore volume of more than 30 cm3/100 g. WATER AND OFF GAS · SOLVENT RECOVERY Activated Carbon for Solvent Recovery K. a large number of mesopores (diam .

granular. there is a difference between powdered. The large specific surfaces are created predominantly by the micropores. activated carbon adsorbs preferably organic substances and other non-polar compounds from the gaseous and liquid phase . AC-Type A35/4 C38/4 D43/4 Appearance cylindrically shaped Bulk density (shaked)(kg/m3) 350±20 380±20 430±20 Moisture content (%weight) <5 <5 <5 Ash content (%weight) <8 <6 <5 Particle diameter (mm) 4±10% 4±10% 4±10% Particle length (mm) 4-13 4-13 4-13 Surface area (BET) (m2/g) 1300±50 1250±50 1100±50 Carbon tetrachloride activity (%weight) 93±3 79±3 66±3 . Due to the mainly hydrophobic surface properties. Figure 2: Activated carbon model The projection shows schematically the pore system. and micropores (diam = <2 nm).= 2-25 nm). and shaped activated carbon qualities. important for adsorption and desorption. As to the shape of activated carbon. For solvent recovery in Europe. because they assure a low pressure drop across the adsorber system. The pore volumedistribution is an important variable that affects carbon performance. Some physio- chemical properties of three typical activated carbons for solvent recovery can be taken from Figure 3. mainly cylindrically-shaped activated carbons with a diameter of 4 mm are used.

Figure 4: Flow sheet of the manufacturing processes It has become standard to term the resulting loss of weight "degree of activation". Carbo-Tech GmbH produces activated carbon pellets by gas activation from specially de-ashed hardcoal. In a subsequent activation step the carbon skeleton of the activated coke is partially gasified by steam activation in a multistep fluidized-bed oven. Granular products and pellets for gas purification are predominantly made by gas activation. Initially. oil products. Figure 3: Activated Carbon for Solvent Recovery Now. subsequently. namely: • chemical activation and • gas activation. predominantly powdered activated carbons are made. May I just shortly describe our manufacturing processes: A simplified flow sheet of the process is given in Figure 4. wood. the hardcoal feed is finely ground and then subjected to partial air-oxidation. A lower degree of activation yields an activated carbon with a high proportion of micro pores. Now a short glance on the activated carbon market: . The extrudates are transformed to activated coke. The binder is added to achieve a plastic coal/binder mixture in order to produce shaped extrudates of the desired diameter. These patents are the basis for the manufacture of activated carbon according to present-day definitions. Commercially. how are activated carbons made? In the years 1900 to 1902 the Ostreijko patents were issued. hardcoal. These extrudates are then subjected to a carbonization step in a rotary kiln where they are heated to about 900°C. And these qualities are often used for waste water treatment. It is now left to the skill of the activated carbon manufacturers to control the steamgasification in a way to arrived exactly at the required pore system of the activated carbon. peat. charcoal. and coconut shells serve as feedstock. the coal dust is mixed with a binder. whereas with increasing degree of activation the portion of mesopores and macropores increases. Ostreijko discovered the two basic principles of activated carbon production which are still valid today. By chemical activation. lignite.

000 t/a granulates.000 t/a of powdered. worldwide • 15O. and • 30.000 t/a of pellets are produced. Figure 5: Activated Carbon World market After that glimpse on the market may I now discuss the use of activated carbon for solvent recovery.As results from Figure 5. • 170. .