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.
 Figure 7: Adsorption isotherms of typical solvents

Please look carefully at solvent No. 2. It is toluene. We will come across toluene again when we
speak about the plant examples.

To remove the solvent, the contaminated air flows through an activated carbon bed. Figure 8
shows the idealized breakthrough curve as a function of the gas volume to be treated. 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.
• Next follows the adsorbate reduction in the so called adsorption ormass transfer zone
(MTZ).
• The outlet zone of the adsorber filling is still unloaded at this time.

With increasing adsorption time the adsorption zone moves through the activated carbon bed. If
the top of the MTZ reaches the adsorber end breakthrough occurs. The adsorption step will be
stopped if a pre-determined solvent concentration in the exhaust gas is exceeded. Then the
activated carbon bed has to be regenerated. If the passage of the fluid is continued on still further,
the exit concentration continues to rise until it becomes the same as the inlet concentration.
 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. 9).

Direct steaming of the activated carbon bed is the most widely used regeneration technique,
because it is cheap and simple. Steam is very effective in raising the bed tem perature quickly and
is easily condensed to recover the solvent as a liquid. A certain flow is also required to reduce the
partial pressure of the adsorbate and carry out the solvent of the activated carbon bed. The
amount of steam required depends on the interaction between solvent and activated carbon.

Figure 9 shows schematically the principle of steam desorption.

 Figure 9: Principle of steam desorption

First, the temperature of the activated carbon is increased to appprox. 100°C. This temperature
increase reduces the equilibrium load of the activated carbon. Further reduction of the residual
load is obtained by the flushing effect of the steam and the declining toluene partial pressure. The
load difference between spent and regenerated activated carbon - we call it "working capacity" -
will be available for the next adsorption cycle.

Desorption of the adsorbed solvents starts after a certain delay, i.e. after the activated carbon bed
has heated up. 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. The desorption time is optimized by consideration both of the acceptable residual load
and the specific steam consumption.

When designing a recovery plant,the engineer now tries to consider as for as possible these bases
of adsorption technology.
 Figure 10: Desorption efficiency and steam consumption

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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

2. Activated Carbon

Contents

Activated carbon is the tradename for highly porous products, made of carbonaceous raw
materials, with a large internal surface of 400-1600 m2/g and a large pore volume of more than 30
cm3/100 g.

Above all, the large internal surface of more than 1000 m2/g is significant. The total surface of 200
mt of activated carbon - the content of a larger solvent recovery plant corresponds to the surface of
the Federal Republic of Germany.

All activated carbon qualities are characterised by their widely ramified pore system(Figure 2)
giving access to what are called macropores (diam = >25 nm), a large number of mesopores (diam
= 2-25 nm), and micropores (diam = <2 nm). The pore volumedistribution is an important variable
that affects carbon performance.

Figure 2: Activated carbon model

The projection shows schematically the pore system, important for adsorption and desorption. The
large specific surfaces are created predominantly by the micropores. As to the shape of activated
carbon, there is a difference between powdered, granular, and shaped activated carbon qualities.

Due to the mainly hydrophobic surface properties, activated carbon adsorbs preferably organic
substances and other non-polar compounds from the gaseous and liquid phase . For solvent
recovery in Europe, mainly cylindrically-shaped activated carbons with a diameter of 4 mm are
used, because they assure a low pressure drop across the adsorber system. Some physio-
chemical properties of three typical activated carbons for solvent recovery can be taken from
Figure 3.

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

 Figure 3: Activated Carbon for Solvent Recovery

Now, how are activated carbons made?

In the years 1900 to 1902 the Ostreijko patents were issued. These patents are the basis for the
manufacture of activated carbon according to present-day definitions.

Ostreijko discovered the two basic principles of activated carbon production which are still valid
today, namely:

• chemical activation and

• gas activation.

By chemical activation, predominantly powdered activated carbons are made. And these qualities
are often used for waste water treatment. Granular products and pellets for gas purification are
predominantly made by gas activation. Commercially, wood, peat, lignite, hardcoal, oil products,
charcoal, and coconut shells serve as feedstock.

Carbo-Tech GmbH produces activated carbon pellets by gas activation from specially de-ashed
hardcoal. May I just shortly describe our manufacturing processes:

A simplified flow sheet of the process is given in Figure 4. Initially, the hardcoal feed is finely
ground and then subjected to partial air-oxidation; subsequently, the coal dust is mixed with a
binder. The binder is added to achieve a plastic coal/binder mixture in order to produce shaped
extrudates of the desired diameter. These extrudates are then subjected to a carbonization step in
a rotary kiln where they are heated to about 900°C. The extrudates are transformed to activated
coke. In a subsequent activation step the carbon skeleton of the activated coke is partially gasified
by steam activation in a multistep fluidized-bed oven.

Figure 4: Flow sheet of the manufacturing processes

It has become standard to term the resulting loss of weight "degree of activation". A lower degree
of activation yields an activated carbon with a high proportion of micro pores, whereas with
increasing degree of activation the portion of mesopores and macropores increases.

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.

Now a short glance on the activated carbon market:

As results from Figure 5, worldwide

• 15O,000 t/a of powdered,

• 170,000 t/a granulates, 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.