CME3033/37 Separation Processes 2

Assignment 2: Slurry Bed Adsorption

Adsorption is a mass transfer process widely used in practice to remove substances from

the fluid phases (gases or liquids). You can also see how natural process in different

environmental compartments. The most general definition describes adsorption as an

enrichment of chemical species of a fluid phase on the surface of a liquid or a solid. In the

treatment of water, it has been shown that Adsorption is an effective elimination process for

a multiplicity of solutes. In this case, the molecules or ions are extracted from the aqueous

solution by adsorption on solid surfaces.

Solid surfaces are characterized by energy-rich active sites that are capable of interact with

solutes in the adjacent aqueous phase due to their electronic properties and specific space

Typically, active sites have different energies, or in other words the surface is energetically

heterogeneous. The solid material that provides the surface for adsorption is called

adsorbent; the species that will be adsorbed will be they call adsorbate. By changing the

properties of the liquid phase (for example concentration, temperature, pH), adsorbed

species can be released from the surface and transfer back to the liquid phase. This inverse

process is known as desorption.

Adsorbent particles have a finite capacity for fluid phase molecules and therefore extended

contact with a feedstock will ultimately lead to the creation of a thermodynamic

equilibrium between the solid and fluid phases. At this equilibrium condition the rates of

adsorption and desorption are equal and the net loading on the solid cannot increase further.

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Slurry bed adsorption it is our case to study: Air is fed at atmospheric pressure and -100ºC

to a semi continuous slurry bed adsorber containing zeolite 10X adsorbent. The feed flow

rate of air is 0.08 m3s-1. The air leaving the adsorber should contain no more than 10 mol%

nitrogen. The semi continuous slurry bed contains 1200 kg of adsorbent and has a volume

of 10 m3. The volumetric mass transfer coefficient (KLa) for the zeolite is 0.4 s-1. It needs to

calculate the time required for the outlet mole fraction of nitrogen to rise above the

specified value (𝑋𝑜𝑢𝑡 = 0.10). In addition, I can assume that the Langmuir isotherm is

applicable and the adsorption data for nitrogen and oxygen is given in the next Table 1.

Table 1. Adsorption data for nitrogen and oxygen on zeolite 10X.

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Fitting an isotherm to the adsorption equilibrium data

If a quantity q of a gas or vapour is adsorbed by a porous solid at constant temperature and

the steady state equilibrium partial pressure is p (or concentration c) then the function q(p)

is the adsorption isotherm. Isotherms can take one of several forms (known as types I to V)

illustrated by Figure 1. Each of these types is observed in practice but by far the most

common are types I, II and IV. An inherent property of type I isotherms is that adsorption

is limited to the completion of a single monolayer of adsorbate at the adsorbent surface.

Type I isotherms are observed for the adsorption of gases on microporous solids whose

pore sizes are not much larger than the molecular diameter of the adsorbate; complete

filling of these narrow pores then corresponds to the completion of a molecular monolayer.

Figure 1. The five types of adsorption isotherms.

Type I isotherm represents the Langmuir isotherm, this isotherm describes adsorbate–

adsorbent systems in which the extent of adsorbate coverage is limited to one molecular

layer at or before a relative pressure of unity is reached. Although the isotherm, proposed

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originally by Langmuir (1918), is more usually appropriate for the description of

chemisorption (when an ionic or covalent chemical bond is formed between adsorbent and

adsorbate), the equation is nevertheless obeyed at moderately low coverages by a number

of systems and can, moreover, be readily extended to describe the behaviour of binary

adsorbate systems. The isotherm was formulated on the basis of a dynamic equilibrium

between the adsorbed phase and the gaseous or vapour phase. It was argued that the rate at

which adsorbate gas molecules strike a surface of an adsorbent is proportional to the

product of the partial pressure p of the gas and the fraction (1 − 𝜃) of surface remaining

uncovered by adsorbate and therefore available as adsorption sites. Langmuir further

supposed that the rate of desorption from the surface is directly proportional to the

fractional surface coverage 𝜃 and that the rates of adsorption and desorption are equal at

equilibrium. Thus

𝑘𝑎 𝑝(1 − 𝜃) = 𝑘𝑑 𝜃

Where 𝑘𝑎 and 𝑘𝑑 are the respective rate constants for adsorption and desorption,

respectively. The more usual form of the equation is written

𝑞 𝑏𝑝
𝜃= =
𝑞𝑚 (1 + 𝑏𝑝 )

where b is ka/kd and qm is the quantity q of adsorbate adsorbed in a single monolayer. The

ratio q/qm can be measured and expressed in different ways. For the present we will choose

to represent the ratio by the number of moles of a component adsorbed compared with the

number of moles of that component which could be adsorbed in a monolayer.

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 5
4.5
4
3.5
q (mol/Kg) 3 y = 0.6809x0.3325
2.5 R² = 0.981
2
1.5
1
0.5
0
0 50 100 150 200 250 300
Partial pressure (KPa)

Figure 2. Langmuir isotherm for Nitrogen

3.5

2.5
q (mol/kg)

2 y = 0.0874x0.7032
R² = 0.9945
1.5

0.5

0
0 50 100 150 200
partial pressure (KPa)

Figure 3. Langmuir isotherm for Oxygen

Linearization of the Langmuir equation, of which one form is

𝑝 1 𝑝
= 𝑏𝑞 + 𝑞
𝑞 𝑚 𝑚

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Will yield values of b and qm. For obedience to the Langmuir isotherm, values derived

from the slopes and intercepts of plots of p/q against p should remain constant over a wide

range of both partial pressures and temperature.

1.5

0.5
y = 0.7032x - 2.4374
Ln(q)

0 R² = 0.9945
0 1 2 3 4 5 6
-0.5

-1

-1.5
Ln(p)

Figure 4. Linearization for Langmuir isotherm for Oxygen.

1.5

y = 0.3325x - 0.3843
1 R² = 0.981
Ln(q)

0.5

0
0 1 2 3 4 5 6

-0.5
Ln(p)

Figure 5. Linearization for Langmuir isotherm for Nitrogen.

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Adsorption Calculation

Semi-continuous mode: (Appendix)

Adsorbent is retained in the vessel, but feed gas enters and exits the vessel as a fixed,

continuous flow rate

Both partial pressure, p, and loading, q, vary with time

𝑝𝐹 − 𝑝𝑜𝑢𝑡
= 𝑘𝐿 𝑎(𝑝𝑜𝑢𝑡 − 𝑝∗ )
𝑡

Therefore,

𝑝𝐹 − 𝑝𝑜𝑢𝑡 1 (𝑝𝐹 − 𝑝𝑜𝑢𝑡 )

𝑡= = [ ] (1)
𝑘𝐿 𝑎(𝑝𝑜𝑢𝑡 − 𝑝 ) 𝑘𝐿 𝑎 (𝑝𝑜𝑢𝑡 − 𝑝∗ )
∗

Variation of q in the batch of solids

𝑑𝑞
𝑆 = 𝑘𝐿 𝑎 × (𝑝𝑜𝑢𝑡 − 𝑝∗ ) × 𝑡 × 𝑄
𝑑𝑡

Where, 𝑆 is batch mass of adsorbent in suspension and 𝑄 is steady, volumetric-liquid flow

rate.

An appropriate adsorption isotherm relates 𝑝∗ to q, in our case Langmuir Isotherm.

Assuming Air entering composition is 𝑁2 = 79% 𝑎𝑛𝑑 𝑂2 = 21%, Pressure initial is

atmospheric 𝑃 = 101.3 𝐾𝑃𝑎.

From Figure 4,

ln(𝑞) = 0.3325 ln(𝑝 ∗) − 0.3843 (2)

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it will proceed to calculate 𝑝 ∗.

If

𝑚𝑜𝑙 𝑁𝑖𝑡𝑟𝑜𝑔𝑒𝑛 0.1 𝑚𝑜𝑙 𝑛𝑖𝑡𝑟𝑜𝑔𝑒𝑛

𝑞= = = 8.33 × 10−7
𝐾𝑔 𝑎𝑑𝑠𝑜𝑟𝑏𝑎𝑡𝑒𝑑 1200 𝑘𝑔 𝑧𝑒𝑜𝑙𝑖𝑡𝑒 10𝑋

Substituting to (2)

ln(8.33 × 10−7 ) = 0.3325 ln(𝑝 ∗) − 0.3843

𝑝 ∗ = 3.7122

Thus, getting back to equation (1)

1 0.79 ∗ 101.3 − 0.1 ∗ 101.3

𝑡= −1
[ ]
0.4 𝑠 (0.1 ∗ 101.3 − 3.7122)

𝑡 = 27.23 𝑠

In conclusion, the time required for the outlet mole fraction ( 10 mol% nitrogen) to rise will

be in 27.23 s approximately.

References

 Crittenden, B. & Thomas, W (1998), Adsorption Technology and Design, p. 99-

101,144-146, Butterworth-Heinemann.

 Lecture 8. Slurry and Fixed-Bed Adsorption Systems. Online Link:

https://www.cheric.org/files/education/cyberlecture/d201501/d201501-801.pdf