CME3033 Separation Processes 2

Tutorial Questions – Adsorption (3)

6. Ideal Adsorption

28 L s-1 of a gas mixture containing 40 mol% propane and 60 mol% propene at

250 kPa and 298 K is fed to a bed of activated carbon. The bed is 5 m long and
contains 3630 kg of adsorbent. Using the multicomponent adsorption isotherm
from Question 2 (find it in: Adsorption Tutorial Questions (1) document) and
assuming ideal adsorption, calculate the length of the equilibrium section for
propane and propene after 18 minutes of adsorption. Which wave front will
emerge from the bed first?

Answers:
propane LES = 4.37 m
propene LES = 0.54 m
propane will emerge first
Solution
If propane is component 1 and propene is component 2, then the solid loadings
in equilibrium with the gas feed are given by:
Propane
𝒒𝒎,𝟏 × 𝑲𝟏 × 𝒑𝟏
𝒒𝟏 =
𝟏 + 𝑲𝟏 𝒑𝟏 + 𝑲𝟐 𝒑𝟐

𝟐. 𝟕𝟑𝟓 × 𝟗. 𝟓 × 𝟏𝟎−𝟓 × 𝟎. 𝟒 × 𝟐𝟓𝟎, 𝟎𝟎𝟎

𝒒𝟏 =
𝟏 + 𝟗. 𝟓 × 𝟏𝟎−𝟓 × 𝟎. 𝟒 × 𝟐𝟓𝟎, 𝟎𝟎𝟎 + 𝟎. 𝟔 × 𝟑. 𝟖 × 𝟏𝟎−𝟒 × 𝟐𝟓𝟎, 𝟎𝟎𝟎

𝒒𝟏 = 𝟎. 𝟑𝟖𝟓 𝒎𝒎𝒐𝒍 𝒈−𝟏 (𝒐𝒓 𝒎𝒐𝒍 𝒌𝒈−𝟏 )

Propene
𝒒𝒎,𝟐 × 𝑲𝟐 × 𝒑𝟐
𝒒𝟐 =
𝟏 + 𝑲𝟏 𝒑𝟏 + 𝑲𝟐 𝒑𝟐

𝟓. 𝟓𝟒𝟑 × 𝟑. 𝟖 × 𝟏𝟎−𝟒 × 𝟎. 𝟔 × 𝟐𝟓𝟎, 𝟎𝟎𝟎

𝒒𝟐 =
𝟏 + 𝟗. 𝟓 × 𝟏𝟎−𝟓 × 𝟎. 𝟒 × 𝟐𝟓𝟎, 𝟎𝟎𝟎 + 𝟎. 𝟔 × 𝟑. 𝟖 × 𝟏𝟎−𝟒 × 𝟐𝟓𝟎, 𝟎𝟎𝟎

𝒒𝟐 = 𝟒. 𝟔𝟖𝟐 𝒎𝒎𝒐𝒍 𝒈−𝟏 (𝒐𝒓 𝒎𝒐𝒍 𝒌𝒈−𝟏 )

The concentration of each component in feed is calculated using:

𝒚𝒊 𝒑
𝒄𝒊 =
𝑹𝑻
For propane:
𝟎. 𝟒 × 𝟐𝟓𝟎, 𝟎𝟎𝟎
𝒄𝑭,𝟏 = = 𝟒𝟎. 𝟒 𝒎𝒐𝒍 𝒎𝟑 = 𝟎. 𝟎𝟒𝟎𝟒 𝒎𝒐𝒍 𝑳−𝟏
𝟖. 𝟑𝟏𝟒 × 𝟐𝟗𝟖
For propene:
𝟎. 𝟔 × 𝟐𝟓𝟎, 𝟎𝟎𝟎
𝒄𝑭,𝟐 = = 𝟔𝟎. 𝟓 𝒎𝒐𝒍 𝒎𝟑 = 𝟎. 𝟎𝟔𝟎𝟓 𝒎𝒐𝒍 𝑳−𝟏
𝟖. 𝟑𝟏𝟒 × 𝟐𝟗𝟖

A mass balance is used to determine the length of the equilibrium section (LES):
𝒂𝒎𝒐𝒖𝒏𝒕 𝒐𝒇 𝒂𝒅𝒔𝒐𝒓𝒃𝒂𝒕𝒆 𝒂𝒎𝒐𝒖𝒏𝒕 𝒂𝒅𝒔𝒐𝒓𝒃𝒆𝒅
( )=( )
𝒇𝒆𝒅 𝒕𝒐 𝒕𝒉𝒆 𝒃𝒆𝒅 𝒊𝒏 𝒕 𝒔𝒆𝒄𝒐𝒏𝒅𝒔 𝒃𝒚 𝒕𝒉𝒆 𝒔𝒐𝒍𝒊𝒅𝒔 𝒊𝒏 𝒕𝒉𝒆 𝒃𝒆𝒅

The solid in LES is in equilibrium with the feed, therefore adsorption

equilibrium isotherms can be used to calculate solid loadings based on feed
concentrations.
𝒂𝒎𝒐𝒖𝒏𝒕 𝒐𝒇 𝒂𝒅𝒔𝒐𝒓𝒃𝒂𝒕𝒆
( ) = 𝑸𝑭 × 𝒄𝑭,𝒊 × 𝒕
𝒇𝒆𝒅 𝒕𝒐 𝒕𝒉𝒆 𝒃𝒆𝒅 𝒊𝒏 𝒕 𝒔𝒆𝒄𝒐𝒏𝒅𝒔
where:
𝑸𝑭 is the feed flow (𝑳 𝒔−𝟏 ), 𝒄𝑭,𝒊 is the concentration of component i in the feed
(𝒎𝒐𝒍 𝑳−𝟏) and 𝒕 is time (𝒔).
 𝒂𝒎𝒐𝒖𝒏𝒕 𝒂𝒅𝒔𝒐𝒓𝒃𝒆𝒅 𝑳𝑬𝑺
( ) = 𝒒𝑭,𝒊 × 𝑺 × ( )
𝒃𝒚 𝒕𝒉𝒆 𝒔𝒐𝒍𝒊𝒅𝒔 𝒊𝒏 𝒕𝒉𝒆 𝒃𝒆𝒅 𝑳𝑩
where:
𝒒𝑭,𝒊 is loading of component i on solids ( 𝒎𝒐𝒍 𝒌𝒈−𝟏 ), 𝑺 is the mass of solid
adsorbent (𝒌𝒈) and 𝑳𝑩 is bed length (𝒎).

Mass balance becomes:

𝑳𝑬𝑺
𝑸𝑭 × 𝒄𝑭,𝒊 × 𝒕 = 𝒒𝑭,𝒊 × 𝑺 × ( )
𝑳𝑩
Time is 18 minutes:
𝒕 = 𝟏𝟖 × 𝟔𝟎 = 𝟏𝟎𝟖𝟎 𝒔

𝑳𝑬𝑺
Hence fractions of bed in equilibrium with the feed ( 𝑳 ) for propane and
𝑩
propene can be calculated as:

Propane
𝑳𝑬𝑺 𝑸𝑭 × 𝒄𝑭,𝟏 × 𝒕 𝟐𝟖 × 𝟎. 𝟎𝟒𝟎𝟒 × 𝟏𝟎𝟖𝟎
( ) = = = 𝟎. 𝟖𝟕𝟒
𝑳𝑩 𝟏 𝒒𝑭,𝟏 × 𝑺 𝟎. 𝟑𝟖𝟓 × 𝟑𝟔𝟑𝟎

𝑳𝑬𝑺𝟏 = 𝟎. 𝟖𝟕𝟒 × 𝟓

𝑳𝑬𝑺𝟏 = 𝟒. 𝟑𝟕 𝒎

Propene
𝑳𝑬𝑺 𝑸𝑭 × 𝒄𝑭,𝟐 × 𝒕 𝟐𝟖 × 𝟎. 𝟎𝟔𝟎𝟓 × 𝟏𝟎𝟖𝟎
( ) = = = 𝟎. 𝟏𝟎𝟖
𝑳𝑩 𝟐 𝒒𝑭,𝟐 × 𝑺 𝟒. 𝟔𝟖𝟐 × 𝟑𝟔𝟑𝟎

𝑳𝑬𝑺𝟐 = 𝟎. 𝟏𝟎𝟖 × 𝟓

𝑳𝑬𝑺𝟐 = 𝟎. 𝟓𝟒 𝒎
 7. Chromatography

The adsorption equilibria of pure hydrocarbon gases on silica are fitted using
the Toth isotherm (Equation 2).
In Equation 2, q is the adsorbent loading (mol kg-1), P is the pressure or partial
pressure (kPa) and b, m and t are experimentally determined constants. The
values of these constants for a range of hydrocarbon gases at 298.15 K are
given in Table 3.

𝒎𝑷
Toth Isotherm: 𝒒 = (𝒃+𝑷𝒕 )𝟏/𝒕 (Equation 2)

Table 3. Experimental constants for the Toth isotherm at 298 K

Compound b (kPat) t m (mol kg-1)
methane 16.3726 0.4390 15.2740
ethene 3.0142 0.3364 9.2691
ethane 1.5373 0.3086 16.2473
propene 0.5460 0.3226 9.6914
propane 0.6778 0.1651 13.7027
butane 0.4514 0.3424 5.2284
pentane 0.1068 0.2967 5.3260

a) A mixture of the gases at 101.3 kPa and 298 K containing 10 mol%

methane, 15 mol% ethene, 15 mol% ethane, 20 mol% propene, 15 mol%
propane, 15 mol% butane and 10 mol% pentane is to be separated using
a column packed with silica. The voidage of the bed is 0.52 and the
density of the adsorbent particles is 780 kg m-3. The carrier gas in the
column is nitrogen and its superficial velocity is 0.12 m s-1. Assuming
that the mixture behaves as an ideal gas, calculate the stoichiometric
wave front speed for each component.

b) If a 1 s pulse of sample is injected into a column 4 m, long calculate

the position of the hydrocarbon peaks after 5.5 minutes.

Answers:
Compound uW (m s-1) Li (mm) LT,i (mm)
methane 0.0034 1124 1121
ethene 0.0015 489 487
ethane 0.0005 178 177
propene 0.0009 285 284
propane 0.0014 465 463
butane 0.0012 398 396
pentane 0.0017 549 548
Li = position of the leading edge of peak after 5.5 minutes,
LT,i = position of the trailing edge
Solution
The speed of the stoichiometric wave front through the adsorbent bed is given
by:
(𝑽⁄𝜺)
𝒖𝒘 =
𝟏 − 𝜺 𝒅𝒒
𝟏 + 𝝆𝑷 ( 𝜺 )
𝒅𝒄

The 𝝆𝑷 term is the density of the adsorbent particles and has been added
because of the units of the Toth isotherm.

For chromatographic separations – it is assumed that pure component

adsorption isotherm can be used for the following reasons:
 The injected mixture is diluted by the carrier fluid.
 The components in the mixture will be separated effectively making the
adsorption/desorption process one for the pure gas.

The Toth isotherm is written in terms of pressure. For each component in the
mixture this is the partial pressure. For an ideal mixture, partial pressure is
𝒚𝒊 𝑷.

a) The concentration and partial pressure for an ideal gas mixture are
linked by the following equation:
𝒚𝒊 𝑷
𝒄𝒊 =
𝑹𝑻

Replacing P in the Toth isotherm with 𝒄𝒊 :

𝒎𝑹𝑻𝒄𝒊
𝒒𝒊 =
(𝒃 + (𝑹𝑻𝒄𝒊 )𝒕 )𝟏/𝒕

Differentiating with respect to 𝒄𝒊 :

𝒅𝒒𝒊 𝒃𝒎𝑹𝑻
= 𝒕+𝟏
𝒅𝒄𝒊
[𝒃 + (𝒄𝒊 𝑹𝑻)𝒕 ] 𝒕

The stoichiometric wave front speeds can now be calculated – but note that P
in the equation are in kPa, therefore:
𝒅𝒒𝒊 𝟎. 𝟎𝟎𝟏 × 𝒃𝒎𝑹𝑻
= 𝒕+𝟏
𝒅𝒄𝒊
[𝒃 + (𝟎. 𝟎𝟎𝟏 × 𝒄𝒊 𝑹𝑻)𝒕 ] 𝒕
Results can be seen in Table 7a.

Table 7a. Calculated stoichiometric wave front speeds

𝒅𝒒𝒊
Compound ci (mol m-3) (m3 kg-1) uW,i (m s-1)
𝒅 𝒄𝒊
methane 4.087 0.0293 0.0034
ethene 6.130 0.0679 0.0015
ethane 6.130 0.1872 0.0005
propene 8.173 0.1169 0.0009
propane 6.130 0.0714 0.0014
butane 6.130 0.0836 0.0012
pentane 4.087 0.0604 0.0017

b) The position of the leading edge of each component peak is given by:
𝑳𝒍𝒆𝒂𝒅𝒊𝒏𝒈,𝒊 = 𝒖𝒘,𝒊 × 𝒕

The trailing edge of each component peak travels at the same speed as the
leading edge, but 1 second behind due to duration of the injection pulse.
𝑳𝒕𝒓𝒂𝒊𝒍𝒊𝒏𝒈,𝒊 = 𝒖𝒘,𝒊 × (𝒕 − 𝟏)

Time is 5.5 minutes:

𝒕 = 𝟓. 𝟓 × 𝟔𝟎 = 𝟑𝟑𝟎 𝒔

The position of the hydrocarbon peaks after 5.5 minutes can be seen in Table
7b.

Table 7b. Position of the hydrocarbon peaks after 5.5 minutes

Compound uW (m s-1) Lleading,i (mm) Ltrailing,i (mm)

methane 0.0034 1124 1121
ethene 0.0015 489 487
ethane 0.0005 178 177
propene 0.0009 285 284
propane 0.0014 465 463
butane 0.0012 398 396
pentane 0.0017 549 548