Process Unit Operations - Adsorption

EX 1
For each separation process try to identify the corresponding difference in properties of the
compounds to be separated:

Separation Process Difference in properties of the compounds

Distillation
Absorption
Extraction
Adsorption

EX 2
Write the adsorption rate of a single component according to the following hypothesis:
1. Very low concentration of the adsorbate molecules on the adsorbent surface
2. The number of molecules absorbed increases to the point at which further adsorption is
hindered by lack of space on the adsorbent surface.

EX 3
Sketch the adsorption isotherm of Langmuir in the following cases:
1. k1/k2 >> 1
2. k1/k2 ~ 1
3. k1/k2 << 1

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 Process Unit Operations - Adsorption

EX 4
Spherical particles of 15 nm diameter and density 2290 kg/m3 are pressed together to form a pellet.
The following equilibrium data were obtained for the sorption of nitrogen at 77 K. Obtain estimates
of the surface area of the pellet from the adsorption isotherm and compare the estimates with the
geometric surface.
P/P0 0.1 0.2 0.3 0.4 0.5 0.6 0.7 0.8 0.9
m3 liq N2 ×
66.7 75.2 83.9 93.4 108.4 130 150.2 202 348
106/kg solid

where P is the pressure of the sorbate and P0 is its vapour pressure at 77 K.

Use the following data: density of liquid nitrogen = 808 kg/m3, area occupied by one adsorbed
molecule of nitrogen = 0.162 nm2.
x x 1
As a remainder, Langmuir equation for gases is = + , BET equation for gases at low
V A V0 KV0
x 1 B −1
pressures is = + x
VA (1 − x ) BV0 BV0

PROBLEM 25/02/2016
Single stage contact adsorption is used to remove an impurity from a liquid stream (35 kg/h), whose
properties can be considered equivalent to those of water.
The adsorption isotherm at 25 °C in the working range is well fitted by the Langmuir equation, with
the adsorption equilibrium constant K=0.05 L/mg. The concentration of the impurity is reduced
from 35 mg/L to 3.5 mg/L. The adsorption unit is operated at 25 °C. The initial concentration of
adsorbate in the contact stage is 10 % of the saturation concentration at its operating conditions,
because of incomplete regeneration. The concentration of active sites of the solid is of 20 mg of
equivalent impurity per kg of solid.
a) What is the mass of solid fed per hour to the contact stage to satisfy the operating
conditions, in the hypothesis of full solid saturation?

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 Process Unit Operations - Adsorption

EX 13
Multistage, repeated single contact adsorption, as schematized in the figure, is used to remove an
impurity from a liquid stream (25 kg/h), whose properties can be considered equivalent to those of
water.
The adsorption isotherm at 25 °C in the working range is well fitted by the Langmuir equation, with
the adsorption equilibrium constant K=0.05 L/mg. The concentration of the impurity is reduced
from 35 mg/L to 1.0 mg/L using 4 contact stages. The adsorption units are operated at 25 °C and all
contain the same amount of solid. The initial concentration of adsorbate in each stage is 10 % of
the saturation concentration at its operating conditions, because of incomplete regeneration. The
concentration of active sites of the solid is of 20 mg of equivalent impurity per kg of solid.
a) What is the concentration of impurities in the liquid at the exit of each adsorption stage?
b) What is the mass of solid fed per hour to each contact stage to satisfy the operating
conditions, in the hypothesis of full solid saturation?

PROBLEM 04/02/2016
Multistage, repeated single contact adsorption, as schematized in the figure, is used to remove an
impurity from a liquid stream (25 kg/h), whose properties can be considered equivalent to those of
water.
The adsorption isotherm at 25 °C in the working range is well fitted by the Langmuir equation, with
the adsorption equilibrium constant K=0.05 L/mg. The concentration of the impurity is reduced
from 35 mg/L to 1.0 mg/L using 4 contact stages. The adsorption units are operated at 25 °C and all
contain the same amount of solid. The initial concentration of adsorbate in each stage is 10 % of the
saturation concentration at its operating conditions, because of incomplete regeneration.
The concentration of active sites of the solid is of 20 mg of equivalent impurity per kg of solid.
a) What is the concentration of impurity in the liquid at the exit of each adsorption stage?
b) What is the mass of solid fed per hour to each contact stage to satisfy the operating
conditions, in the hypothesis of full solid saturation?

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 Process Unit Operations - Adsorption

EX 5
One of the causes of deterioration of clarified juices of fruits is non-enzymatic browning due to the
formation of melanoidins that can be eliminated from the juice by adsorption on activated carbon.
The degree of non-enzymatic browning of a juice can be evaluated by measuring its absorbance at a
wavelength of 420 nm (A420). In an experimental series at the laboratory, different amounts of
activated carbon (particles of 1 mm of mean diameter) are mixed with loads of 10° Brix juice,
whose A420 is 0.646, until reaching equilibrium. Data obtained are given in the following table:
A420
0.646 0.532 0.491 0.385 0.288 0.180
absorbance/kg of solution
b
0 0.01 0.02 0.06 0.12 0.26
kg of carbon/kg of solution

Determine:
(a) data of the equilibrium isotherm as a table;
(b) the number of stages required, operating under repeated single contact, if it is desired to
decrease the A420 of the juice down to a value of 0.200, using in each stage 0.025 kg of
carbon per each kg of 10°Brix juice;
(c) the flow of carbon that should be fed to a countercurrent moving-bed column with a juice
flow of 1000 kg/h, if it operates with a carbon flow that is double the minimum, and it is
desired to obtain juice with an A420 value not higher than 0.2.

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 Process Unit Operations - Adsorption

EX 6
Adsorption on BPL carbon is used to treat an airstream containing 0.2 % n-hexane at 20 °C.
1. Estimate the equilibrium capacity for a bed operating at 20 °C.
2. How much would the capacity decrease if the heat of adsorption raised the bed temperature
to 40 °C?

[Generalized correlations: for a given class of materials, the amount adsorbed depends on
(T/V)log(fs/f), where T is the adsorption temperature (K), V is the molar volume of the liquid at the
boiling point (cm3/mol), fs is the fugacity of the saturated liquid at adsorption temperature, and f is
the fugacity of the vapor. For adsorption at atmospheric temperature, the partial pressure and
vapor pressure can be used for the fugacities. The volume adsorbed is converted to mass by
assuming the adsorbed liquid has the same density as liquid at the boiling point]

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 Process Unit Operations - Adsorption

EX 7
The adsorption of n-butanol from air was studied in a small fixed bed (10.16 cm diameter) with 300
and 600 g carbon, corresponding to bed lengths of 8 and 16 cm.
The following data were obtained on Columbia JXC 4/6 carbon are as follows:
u0 = 58 cm/s; Dp = 0.37 cm; C0 = 365 ppm; S = 1194 m2/g; T = 25 °C; ρb = 0.461 g/cm3; P = 737
mmHg; ε = 0.457.
300 g 600 g
t (h) C/C0 t (h) C/C0
1 0.005 5 0.0019
1.5 0.01 5.5 0.003
2 0.027 6 0.0079
2.4 0.050 6.5 0.018
2.8 0.10 7 0.039
3.3 0.20 7.5 0.077
4 0.29 8 0.15
5 0.56 8.5 0.24

1. From the following data for effluent concentration, estimate the saturation capacity of the
carbon and the fraction of bed used at c/c0 = 0.05;
2. Predict the break point time for a bed length of 32 cm.

EX 8
Using the breakthrough data in EX 7,
1. Determine N and Kc a for a 8-cm bed, assuming irreversible adsorption
2. Compare Kc a with the predicted kc a for the external film.
Initially, assume equal internal and external resistances to mass transfer.

EX 9
Adsorption on activated carbon is being considered to treat a process airstream that has 0.12 % vol
of methyl ethyl ketone (MEK). The gas is at 25 °C and 1 atm, and the flow is 16000 ft3/min.
1. If BPL 4×10-mesh carbon is used, predict the saturation capacity and the working capacity
if the average bed temperature is 35 °C and the regeneration is stopped when m = 1/3 msat.
2. What gas velocity and bed size could be used to give a reasonable cycle time if the length of
unused bed (LUB) is 0.5 ft? How much carbon is needed?
Data: bed = 30 lb/ft3; MEK,l = 0.75 g/cm3 at boiling point (79.6 °C); P°= 151 torr at 35 °C;
molecular weight = 72.1 g/mol.

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 Process Unit Operations - Adsorption

EX 10
Water contaminated with 1.2 ppm TCE is to be purified in a fixed bed of 20×50-mesh Ambersorb
563.
1. For a bed length of 2 ft and a flow rate of 4.5 gal/min·ft2, estimate the breakthrough time if the
length of unused bed is 0.6 ft.
2. What is the
effective
capacity in
volume
treated per
unit bed
volume?

The adsorbent
is regenerated
by steam to
remove 85 % of
the TCE.
The bulk density
of the adsorbent
is 0.53 g/cm3.

EX 11
An industry that processes navel oranges obtains juice that contains 110 ppm of limonene that gives
it a bitter taste. With the objective of eliminating the bitter taste from the juice, a 100 kg/h juice
stream is fed to a cylindrical column (0.15 m2 of cross section) that contains a synthetic molecular
sieve that adsorbs limonene. The adsorbent solid has a density of 950 kg/m3 of packing, with a
volumetric transfer coefficient equal to 20 h–1, and maximum retention capacity of 60 mg of
limonene per kg of adsorbent. The density of the juice can be considered 1000 kg/m 3. The
adsorption isotherm in the concentration range at which the column operates can be considered
favorable. It can be assumed that the breakthrough curve is symmetrical.
If 25 min are required for limonene in the juice stream to begin leaving the column, calculate:
1. The height that the adsorbent bed should have
2. The height of unused bed.

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 Process Unit Operations - Adsorption

Graphical solutions of the mass transfer equations:

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 Process Unit Operations - Adsorption

EX 12
Air at 5 °C and 1 atm, with a humidity of 0.00267 kg water / kg dry air has to be dehumidified by
passage through a fixed bed of silica gel.
The depth of the adsorbent bed is 0.61 m. The air passes through the bed with a superficial mass
velocity of 0.1295 kg/m2 s, and the adsorption is assumed to be isothermal.
The breakpoint is considered as the time when the effluent air has a humidity of 0.0001 kg water /
kg dry air.
Estimate:
1. The time required to reach the breakpoint;
2. The length of unused bed.
Dp = 0.5 cm; ρb = 0.450 g/cm3; ε = 0.47.

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 Process Unit Operations - Adsorption

PROBLEM 11/01/2016
Ethanol, contaminated with 0.03 kmol/m3 of a fatty acid, is to be purified by passing it through a
fixed bed of activated carbon, which will adsorb the acid but not the solvent. The operation is
carried out under isothermal conditions (25 °C), in a bed of 0.15 m diameter to give 3600 s of
operation time when the fluid is fed at 5 × 10−5 m3/s.
The bed is initially free of adsorbate, the intergranular voidage is 0.4, the bed density bed = 500
kg/m3, the particle diameter is 0.5 cm.
The adsorption isotherm, in the range of operation, can be considered linear:
ms = 0.01 C
where C and ms refer to concentrations in the liquid phase (kmol/m3) and in the adsorbent
(kmol/kg), respectively.
In the hypothesis of external film control to mass transfer, calculate:
a. The required bed length (m);
b. The length of unused bed (m).
(Diffusivity of the fatty acid in ethanol = 1.03·10-5 cm2/s)

PROBLEM 10/01/2017
Air at 25 °C and 1 atm, with a humidity of 5 g water / kg dry air has to be dehumidified by passage
through a fixed bed of zeolites, with the equilibrium capacity of H2O being reported in figure.
The air flow rate is 2500 m3/h, and the adsorption is assumed to be isothermal.
The breakpoint is considered as the time when the effluent air has a humidity of 0.2 g water / kg dry
air. An operation time of 1 h is desired. Estimate:
a) The length of unused bed;
b) The mass of zeolites in the bed.
[Dp = 0.45 cm; ρb = 0.67 g/cm3; ε = 0.47; assume the air velocity in the bed]

PROBLEM 06/02/2017
An air stream (20000 ft3/min, temperature of 25 °C, pressure of 1 atm), containing 0.16% of MEK
(molecular weight of 72.106 g/mol) is treated in a Calgon BPL active carbon bed (temperature of
the bed of 50 °C, bed density of 480.54 kg/m3).
The length of unused bed is 0.5 ft, and the gas velocity in the bed is 0.35 m/s. The bed is
regenerated to an adsorbate content per gram of solid of 25% of the saturation value under the
operating conditions.
a) Determine the saturation concentration in the bed;
b) Estimate the bed length for an operation based on two shifts per day.

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 Process Unit Operations - Adsorption

PROBLEM 12/04/2017
An ethanol stream (1500 L/h), contaminated with 0.04 mol/L of a fatty acid, is purified by passing it
through a fixed bed of activated carbon, which adsorbs selectively the acid.
The operation is carried out under isothermal conditions (25 °C), in a fixed bed of 1.0 m diameter.
The desired operation time is 6 h. The bed initially contains 10 % of the saturation adsorbate
concentration, due to incomplete regeneration. The intergranular voidage of the bed is 0.4, the bed
density bed = 400 kg/m3, the particle diameter is 0.4 cm.
The adsorption isotherm, in the range of operation, can be considered of Langmuir type, with a
constant of 0.4 m3/kmol, and a site density on the activated carbon of 0.01 kmol/kg.
Calculate:
a. The required bed length (m);
b. The length of unused bed (m).
(Diffusivity of the fatty acid in ethanol = 1.03·10-5 cm2/s)

PROBLEM 15/04/2021
Hexane is to be recovered from a natural
gas with silica gel. Molecular weight of
the natural gas is 17.85 g/mol, the
pressure is 55.4 atm, temperature is 50°C,
and the content of n-hexane is 0.725 %
mol. The bed is 2.5 m deep and the
superficial velocity is 0.06 m/s.
The particle mean diameter of the
adsorbent is 4 mm, the bed density is 840
kg/m3, and the bed voidage is 0.37.
In the hypothesis of irreversible
adsorption, and for a desired minimum
operation time of 20 min, calculate:
a) The overall external mass
transfer coefficient (m/s);
b) The breakpoint time (min);
c) The breakthrough time (min);
d) The length of unused bed (m).

Figure 15.11. Effect of temperature on molecular sieve type

5A (A), silica gel (B) and activated alumina (C) at the hexane
vapor pressure of interest for the problem.

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Process Unit Operations - Adsorption

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 Process Unit Operations - Adsorption

PROBLEM 16/06/2021
An ethanol stream (9600 kg/h), contaminated with trace concentration of citral (MW = 152.24 g/mol), is
purified through selective adsorption in a fixed bed (1.4 m in diameter) of activated carbon. The initial
concentration of citral in the ethanol stream is of 0.02 mol/L.
The adsorption isotherm, in the range of operation, can be considered of Langmuir type, with an equilibrium
constant of 7.5 m3/kmol, and a site density on the activated carbon of 0.023 kmol/kg.
The operation is carried out under isothermal conditions (25°C), with a desired operation time of 18 h. The
bed initially contains 3.4 % of the saturation adsorbate concentration, due to incomplete regeneration. The
intergranular voidage of the bed is 0.36, the bed density bed = 460 kg/m3, the particle diameter is 0.25 cm.
The desired concentration of citral in the purified ethanol streams is required to be below 0.002 mol/L.
You are asked to:
a. Determine if, under the operating conditions of the column, the equilibrium conditions can be better
approximated by the “linear adsorption isotherm” or to the “irreversible adsorption isotherm” case;
b. Calculate the external and internal specific mass transfer coefficients of citral to the activated carbon
(m/s)
c. Calculate the required bed length (m) and the length of unused bed (m).
(Diffusivity of citral in ethanol = 1.25·10-5 cm2/s)

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