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Absorption 1

Absorption
Johann Schlauer, Lurgi GmbH, Frankfurt, Federal Republic of Germany (Chaps. 1 – 2)
Manfred Kriebel, Lurgi GmbH, Frankfurt, Federal Republic of Germany (Chaps. 3 – 5)

1. Equilibrium of Gas Solubility . . . . . 3 3.3. Absorption and Desorption Equip-


1.1. Introduction . . . . . . . . . . . . . . . . . 3 ment . . . . . . . . . . . . . . . . . . . . . . 23
1.2. Gas-Phase Fugacity . . . . . . . . . . . . 4 3.4. Columns with Mass-Transfer Plates . 23
1.3. Liquid-Phase Fugacity and Activity . 5 3.5. Columns with Random Packing . . . . 23
1.4. Physical Absorption . . . . . . . . . . . . 6 3.6. Columns with Structured Packing . . 24
1.5. Chemical Absorption . . . . . . . . . . . 8 3.7. Columns with Special Internals . . . . 24
1.6. Enthalpy and Absorption Equilibrium 13 4. Design of Absorption Equipment . . . 25
2. Mass Transfer . . . . . . . . . . . . . . . . 14 4.1. Physical Absorption in Plate Columns 25
2.1. Introduction . . . . . . . . . . . . . . . . . 14 4.2. Chemisorption in Packed Columns . . 28
2.2. Mass Transfer Coefficients . . . . . . . 15 4.3. Nonisothermal Absorption . . . . . . . 29
2.3. Effect of Solute Concentration . . . . . 16 5. Design of Desorption Equipment . . . 30
2.4. Correlation of Mass Transfer Coeffi- 5.1. Physical Desorption in Flash Columns 30
cients . . . . . . . . . . . . . . . . . . . . . 17 5.2. Physical Desorption in Stripper
2.5. Mass Transfer and Chemical Reaction 19 Columns . . . . . . . . . . . . . . . . . . . 31
2.6. Modeling of Mass Transfer with 5.3. Physical Desorption in Reboiler
Chemical Reaction . . . . . . . . . . . . 21 Columns . . . . . . . . . . . . . . . . . . . 33
3. Design of Absorption Systems . . . . . 21 5.4. Chemical Desorption in Reboiler
3.1. Methods of Absorption . . . . . . . . . . 21 Columns . . . . . . . . . . . . . . . . . . . 34
3.2. Methods of Desorption . . . . . . . . . . 22 6. References . . . . . . . . . . . . . . . . . . 35

Symbols DAL diffusion coefficient of reactant A in liq-


uid phase, m2 /s
a effective interfacial mass transfer area per
DAB gas-phase diffusion coefficient of solute
unit volume of tower or apparatus, m2 /m3
A in inert gas B, m2 /s
A absorption factor
DB diffusion coefficient of reactant B in liq-
A concentration of alkali or amine, kmol/m3
uid phase, m2 /s
B parameter
DL diffusion coefficient of inert solute in liq-
[B] bulk-liquid reactant concentration,
uid phase, m2 /s
kmol/m3
E enhancement factor
c concentration, kmol/m3
E A reaction activation energy, kJ/mol
cb solute concentration in bulk liquid,
E A absorption rate
kmol/m3
f fugacity, kPa
ci liquid solute concentration at gas – liquid
F reaction frequency factor, m3 kmol−1 s−1
interface, kmol/m3
F (. . .) function of . . .
ck liquid solute concentration (head),
∆G molar Gibbs energy, kJ/mol
kmol/m3
G E molar excess Gibbs energy, kJ/mol
cp specific heat capacity, kJ mol−1 K−1
G gas-phase flow rate, m3 /h
cs liquid solute concentration (sump),
GM gas-phase mass velocity, kg s−1 m−2
kmol/m3
h height of packed column, m
C dimensionless constant
∆H molar enthalpy, kJ/mol
d characteristic length appropriate to the
H Henry’s law constant, kPa
geometry of the system under consider-
Hci Henry’s law constant of solute i (molarity
ation, m
based), kPa m3 kmol−1
D desorption factor

c 2005 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim


10.1002/14356007.b03 08
2 Absorption

Hm
i Henry’s law constant of solute i (molality LM liquid-phase mass velocity, kg s−1 m−2
based), kPa kg mol−1 m mass, kg
Hc Henry’s law constant of carbon dioxide m slope of equilibrium curve (dy ∗/ dx)
in water, kPa m3 kmol−1 mi molality, mol/kg
Hi, L Henry’s law constant of solute i in solvent Mr molecular mass, kg/kmol
L, kPa ni moles of solute i, mol
Hs Henry’s law constant of hydrogen sulfide nth theoretical plate number
in water, kPa m3 kmol−1 n number of transfer units
Ha Hatta number NA mass transfer rate of solute A per unit in-
jM Chilton – Colburn j factor for mass trans- terfacial area, kmol s−1 m−2
fer N F number of transfer units in the liquid
k equilibrium constant, kmol m−3 bar−1 phase
k equilibrium constant, mol m−3 Pa−1 N G number of transfer units in the gas phase
kc rate constant of (pseudo) first-order reac- p total system pressure, kPa
tion, s−1 p (. . .) solute partial pressure in bulk gas, kPa
kg gas-phase mass transfer coefficient, m/s pr reference pressure, kPa
kG gas-phase mass transfer coefficient, p0A pure-component vapor pressure of solute
kmol s−1 m−2 A, kPa
k G a volumetric gas-phase mass transfer coef- pc critical pressure, kPa
ficient, kmol s−1 m−2 pi solute partial pressure, kPa
kl liquid-phase mass transfer coefficient, Pr Prandtl number (cp µ/k)
m/s Q enthalpy, kJ
k l liquid-phase mass transfer coefficient r volumetric reaction rate, kmol s−1 m−3
with reaction, m/s R gas constant, 8.314 J mol−1 K−1 ,
kL liquid-phase mass transfer coefficient, 8.314 m3 kPa kmol−1 K1
kmol s−1 m−2 Re Reynolds number (G M d/µG )
k L a volumetric liquid-phase mass transfer co- s volume of liquid on plate divided by total
efficient, kmol s−1 m−3 area of plate, cm
k 11 rate constant of a second-order reaction, Ss sulfur dioxide concentration,
m3 s−1 kmol−1 mol/100 mol H2 O
K vapor – liquid equilibrium K value Sc Schmidt number (µG /G DAB or
(dy ∗/dx) µL /L DL )
Ka dissociation constant of amine, kmol/m3 Sh Sherwood number (kG RTd/DAB p)
Kb dissociation constant of bicarbonate, St Stanton number (k G M G /G M or
kmol/m3 k L M L /L M )
Kc dissociation constant of carbamate, t temperature, ◦ C
kmol/m3 t time, s
K G overall gas-phase mass transfer coeffi- T temperature, K
cient, kmol s−1 m−2 Tc critical temperature, K
K G a overall volumetric gas-phase mass trans- u superficial gas velocity, cm/s
fer coefficient, kmol s−1 m−3 vGi molar volume of solute i in gas phase,
Kh dissociation constant of hydrogen sulfide, m3 /kmol
kmol/m3 vLi molar volume of solute i in liquid phase,
K k dissociation constant of carbonate, m3 /kmol
kmol/m3 vi0
molar volume of solute i in gas phase at
K L overall liquid-phase mass transfer coeffi- 0 ◦ C, 101.3 kPa, m3 /kmol
cient, kmol s−1 m−2 V volume of gas phase, m3
K L a overall volumetric liquid-phase mass Vi volume of solute i in gas phase, m3
transfer coefficient, kmol s−1 m−3 V 0i volume of solute i in gas phase at 0 ◦ C,
Ks dissociation constant of sulfide, kmol/m3 101.3 kPa, m3
Kw ion product of water, kmol2 /m6 V L volume of solute-free solvent, m3
L liquid-phase flow rate, m3 /h x mole fraction in liquid phase
Absorption 3

x∗ mole fraction in equilibrium with bulk m mean


mole fraction y r reduced condition
Xc moles of carbon dioxide in liquid per s sump
mole of alkali or amine
Xs moles of hydrogen sulfide in liquid per
mole of alkali or amine
y mole fraction of solute in gas phase
1. Equilibrium of Gas Solubility
y∗ mole fraction in equilibrium with bulk
1.1. Introduction
mole fraction x
z distance from interface, m Absorption is the uptake of gases by a solvent.
z compressibility factor Adsorption means accumulation on the surface
of a solid (→ Adsorption). The equilibrium of
Greek Symbols solubility describes the distribution of absorbed
materials between the vapor and liquid phases
α Bunsen solubility coefficient (VLE i.e., vapor – liquid equilibrium). Depend-
(old dimension, m3 m−3 atm−1 ) ing on its volatility, the solvent may appear in
β Ostwald solubility coefficient the vapor phase; this phenomenon will only be
(old dimension, m3 m−3 atm−1 ) mentioned tangentially (see Section 5.3 and 5.4).
γ activity coefficient The interaction of absorbed materials with
δ film thickness, m the solvent can be physical or chemical in na-
ε void fraction of packing available for gas ture (van der Waals forces, dissociation, neu-
flow tralization, oxidation). In physical absorption,
λ solubility coefficient the gas molecules are polarized but remain oth-
(SI-units), mol kg−1 kPa−1 erwise unchanged. In chemical absorption, they
µ viscosity, kg m−1 s−1 are also chemically converted. The type of inter-
ν specific solvent demand (L/G) action critically affects the solubility equilibria
 density, kg/m3 and the shape of the absorption isotherms.
σ relative supersaturation Chemical absorption entails greater changes
ϕ percentage of absorption in enthalpy than physical absorption, in which
Φ fugacity coefficient the enthalpy change is about equivalent to the
ω acentric factor enthalpy of condensation. Depending on which
interaction predominates, the terms physical or
Superscripts chemical solubility, and even physical or chem-
ical solvent, are used. The latter designation can
∗ equilibrium with the second phase be misleading because one and the same sol-
b bulk vent exhibits chemical solubility for some gases
G gas phase (e.g., carbon dioxide or hydrogen sulfide) and
i interface physical solubility for others (e.g., hydrogen or
L liquid phase methane).
0 pure component Solubility equilibria are governed by the gen-
eral thermodynamic condition that the entropy
Subscripts is at its maximum in a closed system. Thus, at
equilibrium the molar Gibbs energy G is
A, B components  
A, D absorption, desorption 
δ ni G /δni = 0 [T ,p= const.] (1)
c critical
i
g gas phase
G gas phase in all phases, and the fugacity is
h head
f G =f L and f G L
i =f i (2)
i component
l liquid phase in the gas and liquid phase. This chapter deals
L liquid phase first with the fugacity of the gas in the gas and
4 Absorption

liquid phase, as well as with the activity of the For gas mixtures, a weighted average is used for
liquid phase. The laws governing physical and the critical pressure pc and the critical tempera-
chemical solubility equilibria are then discussed. ture T c
 
pc = yi pc,i and Tc = yi Tc,i (8)
i i
1.2. Gas-Phase Fugacity
In the model considered most efficient at the mo-
The fugacity fi of component i in the gas phase ment, the fugacity is calculated from two terms
is defined by [3]:

dGi =RT dlnfi =viG dp (3) log (f /p) = [log (f /p)](0) +ω [log (f /p)](1) (9)

and a boundary condition where ω is the component-specific acentric fac-


tor. The logarithmic terms in square brackets
fi =yi p, atp→ 0 (4) have been published as a function of the reduced
temperature and the reduced pressure [1], [4].
Fugacity cannot be measured directly but is de- Unfortunately, this method can be used only for
termined from an equation of state that describes single-component gases; computer programs are
the gas mixture in question. required to calculate the fugacity in gas mix-
p   p
tures. A modification of the method has been
f VG 1 z −1 published along with the corresponding rules of
ln = − dp= dp (5)
p RT p p mixing [5]. For polar components, an additional
0 0
polar factor is introduced.
To solve this, either the molar volume vG of the Simulation programs calculate the fugacity
gas mixture from the equation of state or the by several methods. The user can select a suit-
compressibility factor z is substituted. The fu- able method but must be mindful of the areas of
gacity of component i is calculated from application to avoid gross errors.
 The virial equation offers a simple method of
lnfi /yi = lnf − yk (δlnf /δyk ) (6) calculation and is very popular. However, it is not
k=i suitable in the critical region or for liquids. Out-
In the partial derivation, all components except side the critical region, predicted compressibil-
the kth and ith are kept constant. Equations ity factors are reproduced with deviation <2 %
(5) and (6) have been solved and published for for pure components <3 % for weakly polar
many equations of state. Solutions for the van mixtures, and <5 % for highly polar mixtures.
der Waals equation, the virial equation with one This accuracy can be achieved in the following
or two constants, the cubic (Redlich – Kwong, region of application:
Soave and Peng – Robinson), and the com-
pr <Tr −0.65forTr <1 (10)
plex [Benedict – Webb – Rubin (BWR) and
BWR – Starling] equations of state will be found pr <1.05Tr −0.35forTr > 1 (11)
in [1].
The generalized method of calculation ac- For the critical data of gas mixtures weighted av-
cording to Hayden and O’Connell, based on erages according to Equation (8) are used for the
the virial equation, appears in [2]. All thermody- reduced pressure (pr = p/pc ) and for the reduced
namic data and many binary interaction param- temperature (T r = T /T c ). Among the cubic
eters required for the calculation are listed there equations of state, Soave and Peng – Robinson
for many gases. While the applicability of this are widely employed. They can also be used
method is limited, the calculations are not too sucessfully in the critical region, but binary in-
time-consuming. The method is not suitable for teraction parameters are required for gas mix-
the critical region, and its application is confined tures. Benedict – Webb – Rubin is suitable for
to the following pressures: hydrocarbons, and Lee – Kesler – Plöcker is rec-
ommended for broad ranges of pressure and tem-
p/pc ≤ 0.5T /Tc (7) perature (0 < pr < 10 and 0.3 < T r < 4) [4].
Absorption 5

In the commercial programs Process, Pro II, saturated vapor pressure of the pure component
and Aspen, one method is offered as default for i at temperature T and the fugacity coefficient
the fugacity calculation, and the user can select of this vapor ϕ0i = f /p is calculated according to
another. If the correct method is in doubt, the Equation (5). This symmetrical normalization
selected method must be checked against exper- can be used as long as the pure component i
imental data in the area of interest. forms a liquid, hence, in the temperature range
of its triple point up to the critical temperature.
At low to moderate pressure,
1.3. Liquid-Phase Fugacity and Activity
ϕ0i = 1, so that f 0i =p0i (16)
The fugacity of dissolved component i in the liq-
uid phase is given by and the Poynting factor → 1 so that Raoult’s law
follows from Equations (12) – (15):
p  
fL 0
i =γi xi f i exp viL /RT dp (12) pi =xi p0i (if xi → 1) (17)
pr
The standard fugacities of many liquids have
The exponential term represents the effect of been determined for the reference pressure pr = 0
gas-phase pressure and is called the Poynting and generalized by using the theorem of corre-
factor. Here, vi is the molar volume of compo- sponding states as a function of the reduced tem-
nent i in the liquid phase, and the integration perature T r and the acentric factor ω.
is carried out from the reference pressure pr to
the pressure of the system p. The activity coef- f 0i /pc,i =F (Tr,i ,ωi ) (18)
ficients γi are needed to correct the real liquid
phase; they are related to the molar excess Gibbs By extrapolation of Equation (18), the utility of
energy G E as follows: symmetric normalization has been expanded be-
 yond the critical temperature [2].
GE =RT xi lnγi (13)
i Infinitely Dilute Solutions. The activity co-
E efficients are chosen as
There are many G models for calculating the
activity coefficients γ i in the liquid phase. A key
γi = 1 if xi → 0 (19)
advance was made by Wilson in 1964, who in-
troduced the local concentration that led to the and the standard fugacity as
development of the powerful NRTL (nonran-
dom two liquid), ASOG (analytical solution of f 0i =Hi,L (20)
groups), UNIQUAC (universal quasi-chemical
equation) and UNIFAC (UNIQUAC functional Hi,L is Henry’s law constant of component i in
group activity coefficient) models [6–9]. the solvent L because, at low pressure, Equation
The following two conventions are preferred (12) becomes Henry’s law
for normalizing the activity coefficients γi and
the standard fugacity f 0i : pi =xi Hi,L (xi → 0) (21)

For gaseous component i in solvent L, the


Pure Liquid Component i. The activity co-
Henry’s law constant depends only on temper-
efficients γi are
ature and can be determined from the solubil-
γi = 1 if xi → 1 (14) ity equilibria (see Section 1.4). No temperature
limit exists to this so-called unsymmetric nor-
and the standard fugacity is malization because for gases, Henry’s law con-

stant can also be measured in the supercritical
f 0i =p0i ϕ0i exp pr −p0i v̄iL /RT (15) region. Henry’s law constant is determined from
solubility data. To do so, the ratio fi /xi is plot-
where ῡ Li is the average molar volume of the dis- ted vs. xi and extrapolated to x → 0. Henry’s law
solved component i in the liquid phase, p0i is the
6 Absorption

constant holds exactly only if the total pressure


p = p0L = vapor pressure of the solvent.
At higher pressure of the dissolved compo-
nent, Henry’s law constant is corrected sim-
ilar to the Poynting factor according to the
Krichevsky – Kasarnovski equation.



lnHi,L (p) = lnHi,L p0L +vi∞ p−p0L /RT (22)
At infinite dilution the molar volume v∞
i ,
is as-
sumed to be constant over the entire range of
pressure. The Krichevski – Illinskaya equation
applies to a larger range of concentration:



lnHi,L (p) = lnHi,L p0L +vi∞ p−p0L /RT +

2
+C xL −1 (23)
The constant C is fitted to the experimental data.
Figure 2. Solubility of hydrogen sulfide in N-methyl-
Henry’s law applies at low loading and is used pyrrolidone
frequently. Raoult’s law is used only rarely, for Data from [10]; lines calculated with UNIQUAC
example, in the region of condensation if loading a) t = 0 ◦ C; b) t = 10 ◦ C; c) t = 20 ◦ C; d) t = 30 ◦ C;
becomes extremely high. e) t = 40 ◦ C
Both laws are obeyed over the entire range The calculated lines show that measured val-
of concentration 0 < xi < 1 only by ideal solu- ues can be reproduced quite accurately once
tions. The deviation from Henry’s and Raoult’s both phases have been corrected in the following
laws in real solutions between the boundary val- manner.
ues is demonstrated in Figure 1 by the solubility The fugacity of the gas phase is determined
of carbon dioxide in methanol and in Figure 2 by from the virial equation, and the activity coef-
the solubility of hydrogen sulfide in N-methyl- ficients in the liquid phase are calculated with
pyrrolidone. The ratio pi /xi is shown in the fig- UNIQUAC; the temperature-dependent binary
ures as a function of the mole fraction xi for UNIQUAC parameters are then fitted to the mea-
several temperatures; in real solutions, consid- sured data (for details, see [2]).
erable deviations from ideality occur.

1.4. Physical Absorption

In physical absorption, the concentration of dis-


solved gases in the solvent increases in propor-
tion to the partial pressure of these gases; i.e., it
follows Henry’s law (Eq. 21).
Henry’s law constant H i, L has the same di-
mensions as the vapor pressure p0i and is nu-
merically equal to it in ideal solutions. In real
solutions, the numerical value of Henry’s law
constant depends on the solvent. While Henry’s
law constant has physical meaning even at super-
critical temperatures, the vapor pressure exists
only in the subcritical region. In the literature,
Henry’s law constant is often specified in differ-
ent units if the concentration of the dissolved gas
Figure 1. Solubility of carbon dioxide in methanol
Data from [14]; lines calculated with UNIQUAC is not expressed as the mole fraction xi . Some
a) t = −60 ◦ C; b) t = −40 ◦ C; c) t = −20 ◦ C; d) t = 0 ◦ C; examples are given in Table 1.
e) t = 25 ◦ C; f) t = 50 ◦ C; g) t = 75 ◦ C
Absorption 7

Table 1. Different expressing of Henry’s law constant constants depends on the loading or on the par-
tial pressure:
Constant Dimension Concentration

H i,L = pi /xi bar mole fraction Hi,L = factor/xL = factor+pi (26)


Hm i = pi /mi bar kg mol−1 molality 
H ci = pi /ci bar m3 kmol−1 molarity where xL = 1− xi = solventmolefraction.
i
Factors for converting the most common solu-
The following relations are used to recalcu- bility coefficients to Henry’s law constants are
late the various dimensions: 
listed in Table 3. At low gas loading, xi → 0,
 and x L → 1 or pi → 0, so that the conversion is
Hi,L /Him = 1000/ML + mj (24)
j independent of the concentration of dissolved
 gas.
Hi,L /Hic = /ML + cj (1−Mj /ML ) (25)
j Table 3. Factors for converting solubility coefficients to Henry’s law
constants
where M is the molar mass in g/mol; m is the mo- Solubility coefficient Factor ∗
lality in mol/kg; c is the molarity in kmol/m3 ;
and  is the density of the solution in kg/m3 . αi Bunsen 1.01325 v0i L /M L αi
βi Ostwald T v0 i L /269.58 M L βi
Indices represent the following: L solvent; i dis- λi SI 1000/ML λi
solved gaseous component; and j all dissolved
∗ Hi L is the Henry’s law constant of gas i in solvent L in bar; v0i
components. is the molar volume of gas i under standard conditions (0 ◦ C and
At low loading, the concentration-dependent 101.35 kPa) in m3 /kmol; L is the density of gas-free solvent in
kg/m3 ; and T is the temperature in K.
contribution can be neglected and the recalcu-
lation can be limited to merely the first term of
Equations (24) and (25). In the design of natural gas and petroleum
A lot of solubility data have been published refineries, the so-called K value
in the literature as solubility coefficients, defined
Ki =yi /xi (27)
as the ratio of the amount of gas dissolved at
the partial pressure pi = 1 to the amount of sol- is often used for the equilibrium of gas solubil-
vent. Many solubility coefficients differ in the ity. The K value is particularly useful for rep-
dimensions used to describe the amounts of gas resenting and calculating the solubility equilib-
and solvent or the pressure. Some examples are ria of hydrocarbons (e.g., methane or ethane) in
given in Table 2. petroleum or gasoline fractions. In these chemi-
Table 2. Examples of different solubility coefficients cally related materials the liquid phase behaves
ideally (Raoult’s law holds) so that the K values
Name Definition Dimension do not depend on the composition of the solvent
Bunsen αi = V 0 i /V L pi m3 m−3 atm−1 but only on the temperature and total pressure.
Ostwald βi = Vi /V L pi m3 m−3 atm−1 The Henry’s law constant of component i is cal-
SI λi = ni /mL pi mol kg−1 bar−1 culated from the K value and the pressure
∗ Conversion factor: 1 atm = 101.325 kPa = 1.013 bar.
Hi =Ki p (28)

In the Bunsen solubility coefficient, the gas For an ideal liquid phase, the K values and
volume is given at standard conditions (0 ◦ C and Henry’s law constants are independent of the
1 atm); in the Ostwald coefficient, at the measur- solvent so the index L is omitted. Solubility data
ing temperature. The value mL designates the of gases in liquids, as well as overviews of pub-
solvent mass. lished solubility equilibria, can be found in [1],
A review of the old solubility coefficients [2], [4], [11], and [12].
with appropriate conversion factors can be found The IUPAC Solubility Data Series publishes
in [11]. Because Henry’s law constants are de- critically selected measured values of gas solu-
fined in terms of mole fraction and the solubil- bilities [13]; 100 volumes are planned in all.
ity coefficients in terms of mass ratio, the con- Many of the published solubility equilibria
version of solubility coefficients to Henry’s law are stored in data banks [e.g., the Dortmund Data
8 Absorption

Bank (DDB), the Berlin Thermodynamic Data Carbon Dioxide in Alkali Carbonate – Bi-
Bank (BDBT)] or in Dechema Data Series; they carbonate. An absorption isotherm for car-
have been published in part or can be accessed bon dioxide in an aqueous solution of alkali
via commercial data markets. carbonate – bicarbonate was derived by Mac-
A data reduction by the G E model was il- Coy [17] as early as 1903 from the mass action
lustrated in Section 1.3 for the systems carbon law of the following reactions:
dioxide – methanol and hydrogen sulfide – N-
Reaction Equilibrium
methylpyrrolidone. The systems were corre- CO2 (g)  CO2 (l) p(CO2 ) = H c [CO2 ] (29)
lated by using the Peng – Robinson or the CO2 + H2 O  HCO− 3 +H
+
[CO2 ] K b = [HCO− +
3 ] [H ] (30)
Redlich – Kwong – Soave equation of state with HCO− 2−
3  CO3 + H
+
[HCO− 2−
3 ] K k = [CO3 ] [H ]
+
(31)
the temperature-dependent binary interaction
parameters determined by fitting experimental The formulas in square brackets denote the con-
data [14], [15], too. centration of the reaction partners; H c is Henry’s
To represent the solubility of gases in law constant for carbon dioxide in water; and
water, in concentrated aqueous solutions of K b and K k are the dissociation constants of
electrolytes, and in hydrocarbons, the hard- bicarbonate and carbonate, respectively. Thus,
sphere model and the Lennard – Jones poten- from Equations (29) – (31)
tial 6 – 12 are used with the dipole – dipole and 2
dipole – induced dipole contributions as the in- Hc Kk HCO−3
termolecular interactions [16]. An overview of p (CO2 ) = (32)
Kb CO2−
3
the older models appears in [11].
The concentration of alkali A (alkalinity) follows
from the condition of electroneutrality
1.5. Chemical Absorption
A= HCO− 2−
3 +2 CO3 (33)
Chemical absorption differs from physical ab-
sorption mainly in the higher enthalpy of ab- If a specific loading is introduced,
sorption and the nonlinearity of the absorption
isotherms. The high absorption enthalpy is due Xc = HCO−
3 /A (34)
to chemical reactions of the absorbed gases in the
solvents. This is also the reason for the greater from Equations (32) – (34) follows,
temperature dependence of chemical solubility
Hc Kk 2AXc2 1 2AXc2
(see Section 1.6). The enthalpy of chemical ab- p (CO2 ) = = · (35)
Kb (1−Xc ) k 1−Xc
sorption decreases much more rapidly with in-
creased loading than the enthalpy of physical The new equilibrium constant k combines all
absorption. Especially after consumption of the previous constants; like Henry’s law constant
chemical capacity (e.g., if amines in the solvent and the dissociation constant, it is temperature
are neutralized by the absorbed acid gases), the dependent. This temperature dependence is rep-
chemical enthalpy of absorption decreases pre- resented by the following empirical formula in
cipitously, approaching the physical absorption the temperature range from 0 to 190 ◦ C [11]:
enthalpy.
The chemical absorption isotherm is nonlin- logk= 4990/ (558+t) −6.265 (36)
ear and Henry’s law does not hold. At low load-
ing, the relation ∆p/∆(load) of the dissolved gas The constant k is calculated in kmol m−3 bar −1
increases with increasing loading. if the temperature t is in degrees Celsius. The ab-
Several isotherms have been proposed for sorption isotherm (Eq. 35) shows that the partial
quantitative representation of chemical solubil- pressure of carbon dioxide does not grow linear
ity equilibria; however, they do not have general at low loading but with the square of the loading
validity but describe only certain systems. The X c , if X c  1.
most important ones are listed in the following The solubility of CO2 in cold potassium car-
material. bonate can be calculated from the following
equation [18]:
Absorption 9

0.0338A1.29 Xc2 S s = [HSO− 2−


3 ] + [SO3 ] so that
p (CO2 ) = (37)
(150−t) λc (1−Xc ) [HSO− 2−
3 ] = (2 S s − A) and [SO3 ] = (A − S s ) (41)

which is valid for 0 < t < 40 C and for are used for the bisulfite and sulfite concentra-
1 < A < 2 kmol/m3 . The solubility of carbon di- tions, respectively. The partial pressure of sulfur
oxide in sodium carbonate can be calculated dioxide is then
from a similar formula [19]
0.1015A1.29 Xc2 p (SO2 ) = F (T ) (2 S s − A)2 /(A − S s ) (42)
p (CO2 ) = (38)
(185−t) λc (1−Xc )

which is valid for 18 < t < 65 ◦ C and for The temperature-dependent Henry’s law and
0.5 < A < 2 kmol/m3 . The solubility constant λc dissociation constants are collected in the func-
in Equations (37) and (38) is calculated as fol- tion F (T ). The following empirical formulas for
lows: F (T ) have been proposed for three bases [21],
[22]:
logλc = 169/ (94−t) −2.89 (39)
Sodium hydroxide log F (T ) = 1.644 − 1987/T
Methylamine log F (T ) = 2.515 − 2308/T
Ammonia log F (T ) = 2.990 − 2368/T
An empirical formula for CO2 pressure (atm)
over carbonate solution using the relationship
molarity ma = 2A is given by the equation of As- These formulas are valid for 308 < T < 363 K
tarita et al. (Eq. 40) [71]: and for the following alkalinities A in mol per
100 mol H2 O:
p (CO2 ) = 1.95 × 109 m0.4
a exp (−8160/T )
Sodium hydroxide 4.0 < A < 7.8
Xc2 / (1−Xc ) (40) Methylamine 7.3 < A < 22.0
Ammonia 5.8 < A < 22.4

In Equations (30) – (40), p(CO2 ) is the equi-


The partial pressure of sulfur dioxide is calcu-
librium pressure of carbon dioxide in bar, A
lated in bar if the loading S s is expressed in
is the concentration of alkali (alkalinity) in
moles per hundred moles of water.
kmol/m3 ; X c is the carbon dioxide loading
(X c = [HCO− ◦
3 ]/A), t is the temperature in C; and
λc is the solubility constant of carbon dioxide in Hydrogen Sulfide and Carbon Dioxide in
water in kmol m−3 bar−1 . Alkali Carbonate – Bicarbonate. By the ab-
In practice, the absorption of carbon dioxide sorption of hydrogen sulfide in aqueous solu-
by hot potassium carbonate solution (Hot-Pot tions of alkali carbonate – bicarbonate, the fol-
of Benfield) is applied widely. Sodium carbon- lowing reactions and equilibria are taken into
ate and cold potassium carbonate are no longer account:
used industrially. Reaction Equilibrium
H2 S(g)  H2 S(l) p(H2 S) = Hs [H2 S] (43)
The solubility equilibria of carbon dioxide H2 S  H+ + HS− Kh [H2 S] = [H+ ] [HS− ] (44)
in a potassium carbonate solution with addi-
tives (KH2 AsO3 , KH2 BO3 , K2 SeO3 , KHTeO4 ,
K2 HPO4 ), which serve as activators to acceler- H s is Henry’s law constant and K h is the
ate the rate of absorption of carbon dioxide, are dissociation constant of hydrogen sulfide. From
described in [20]. Equations (31), (43), and (44), the partial pres-
sure of hydrogen sulfide is
Sulfur Dioxide in Alkali Sulfite – Bisulfite. 
By using Equations (29) – (33), with SO2 , Hs Kk HS− HCO−3
p (H2 S) = (45)
HSO− 2− −
3 , and SO3 replacing CO2 , HCO3 , and Kh CO2−
3
CO2−3 a formally similar isotherm can be de-
rived for the absorption of sulfur dioxide [21], Analogous to Equation (34), the hydrogen sul-
[22]. The definition of loading, however, differs fide loading X s is defined as
from that in Equation (34),
10 Absorption

Xs = HS− /A (46) and 43) was taken into account. The mathemat-
ical description of the system is based on the
and, from electroneutrality, material balance of ammonia, carbon dioxide,
 and hydrogen sulfide, as well as on electroneu-
A= HS− + HCO− 2−
3 +2 CO3 (47)
trality. The equations can be solved by an ap-
By substitution in Equation (45), the partial proximation method, and the equilibria can thus
pressure of hydrogen sulfide is obtained: be calculated. A better representation of solu-
bility equilibria over a broad range of concen-
Hs Kk 2AXs Xc 1 2AXs Xc tration is achieved by introducing activity coef-
p (H2 S) = = (48)
Kh (1−Xs −Xc ) k (1−Xs −Xc ) ficients. Remarkable progress was made during
All previous constants are combined in the new the 1970 s in calculating activity coefficients of
constant k . The following empirical formula has electrolytes [28], [29].
been proposed [23] for its temperature depen- A calculation of activity coefficients by the
dence: semiempirical method of Bromley and Pitzer,
by using the TIDES program, successfully re-
logk = −5.81488 + 895.3/T (49) produces experimental solubility data of carbon
dioxide in concentrated ammonia solutions [30].
The constant k is calculated in moles per kilo- An additional program, DELTAS, is available
gram and pascal if the temperature T is ex- for calculating equilibria in a multicomponent
pressed in kelvin. Absorption isotherms (Eqs. 45 system containing ammonia, phenol, carbon di-
and 48, respectively) show that the partial pres- oxide, hydrogen sulfide, hydrogen cyanide, sul-
sure of hydrogen sulfide increases in direct pro- fur dioxide, and water; it was used for calculating
portion to its loading X s . However, during the solubility equilibria in sour water strippers (i.e.,
absorption of 1 mol of H2 S 1 mol H+ and 1 mol desorbers for the removal of hydrogen sulfide,
HS− are generated. By the reversal of Equation carbon dioxide, hydrogen cyanide, and ammo-
(31) 1 mol bicarbonate is formed by the reaction nia from waste water).
of 1 mol of H+ -ions while 1 mol of carbonate This model was checked experimentally by
is consumed, so that the partial pressure of H2 S measuring hydrogen sulfide – ammonia solubil-
increases more rapidly than the loading. ities at extremely high ammonia concentrations;
Many experimental solubility data of hydro- it reproduced the total pressure with less than
gen sulfide and carbon dioxide in aqueous potas- ± 10 % error up to about 30 mol/kg [31]. This er-
sium carbonate solution can be found in [24] and ror becomes larger with further increasing con-
[25]. The design of carbon dioxide and hydrogen centration.
sulfide absorption with hot potassium carbonate The fugacity of the vapor phase has been cal-
can be calculated with the aid of a published culated according to the Peng – Robinson equa-
simulation program written in FORTRAN [26]. tion of state, and the effect of water vapor
pressure on solubility equilibria at temperatures
Equilibria of Carbon Dioxide and Hydro- above 150 ◦ C is demonstrated in [32]. Commer-
gen Sulfide in Aqueous Ammonia. A model cial simulation programs also make use of other
of the solubility equilibria of carbon dioxide and models, e.g., the Chen model in Aspen Plus.
hydrogen sulfide in aqueous ammonia solution is The vapor – liquid equilibria of ammonia and
based on the following reactions and equilibria: hydrogen sulfide in aqueous solutions are given
deprotonization of ammonium ion and reaction by Newman [33] in the form of charts. They can
of carbamate ion with water [27]. be used for fast estimations without computer,
Reaction Equilibrium but a trial-and-error method is required.
NH+4  NH3 + H
+
K a [NH+ +
4 ] = [NH3 ] [H ] (50) Experimental data on the simultaneous solu-
NH2 COO + H2 O  NH3 + HCO−

3 bility of ammonia and carbon dioxide in concen-
Carbamate K c [NH2 COO− ] = [NH3 ] [HCO−
3 ] (51)
trated aqueous solutions containing dissolved
salts are reported by Maurer et al. [34]; for so-
as well as the equilibria for bicarbonate lutions containing sodium sulfate, see [35]. A
(Eq. 30), carbonate (Eq. 31), and hydrogen sul- data-correlation model treats the gas phase by
fide (Eq. 44). In addition, Henry’s law (Eqs. 29
Absorption 11

means of second virial coefficients, and the ac- In a simplified solubility model for a single
tivity coefficients in the liquid are calculated by a gas (CO2 or H2 S) reacting with an amine in sto-
modified Pitzer method for the excess Gibbs en- ichiometric ratios of 1 : 1 and 1 : 2, the effect of
ergy of an aqueous electrolyte solution. Selected amine concentration is described by an activity
binary and some ternary interaction parameters coefficient of the solvent [40]. Numerical val-
were fitted to the experimental data. ues of Henry’s law and reaction constants are
given for three nonaqueous solvents and their
Carbon Dioxide – Hydrogen Sulfide in mixtures.
Alkanolamine. A well-known method of Kent A formally similar model has been used for
and Eisenberg for representing solubility equi- two acid gases [41]. In this case, only a single
libria of carbon dioxide and hydrogen sulfide in reaction is considered per gas: the dissociation
aqueous alkanolamine solutions is based on nine of H2 S to HS− and H+ and the conversion of
reactions with their accompanying equilibrium carbon dioxide to carbamate. In both solubility
constants [36]: models, a system of equations must be solved
by an approximation method.
Reaction Equilibrium
RRNH+ +
K a [RRNH+ + To represent the solubility of carbon di-
2  H + RRNH 2 ] = [H ] [RRNH] (52)
RRNCOO− + H2 O  RRNH + HCO− 3 (53) oxide in MEA solutions explicitly [42], [43], an
− −
K c [RRNCOO ] = [RRNH] [HCO3 ] isotherm has been derived from the following
H2 O  H+ + OH− K w = [H+ ] [OH− ] (54) reaction

as well as Equations (29) – (31) and (40) – (41). CO2 + 2 RNH2  RNHCOO− + RNH+
3 (55)
Together with the mass balance of amine,
carbon dioxide, and hydrogen sulfide, as well From the equilibrium constant of this reaction
as electroneutrality in the solution, a system of and the amine balance, it folllows that
equations is obtained which can be solved by
p (CO2 ) =A [Xc / (1 − 2Xc )]2 exp (B) (56)
an approximation method. No explicit formula
for the isotherm of the entire system of equa- The dependence of parameters A and B on the
tions is known, but the equations can be solved temperature T and specific loading X c is repre-
by computer and the solubility equilibria cal- sented by empirical equations
culated. The numerical values needed to cal-
culate the temperature-dependent Henry’s law lnA= −3.70 − 4.83Xc (57)
constants and the dissociation constants of car-

2

bonate, bicarbonate and carbamate, sulfide and B = 9.71+8.18Xc −25.2Xc (3.0 − 1000/T ) (58)
hydrogen sulfide, as well as two alkanolamines
[monoethanolamine (MEA) and diethanolamine which can be used in the tempera-
(DEA)] , are given in [36]. ture range 0 – 140 ◦ C, at specific loadings
With the aid of this model, nomograms can X c < 0.45 mol/mol and MEA concentrations
also be calculated [37], by means of which the from 0.5 to 9.5 kmol/m3 . Another explicit
simultaneous solubility equilibria of carbon di- isotherm of carbon dioxide is derived in [44].
oxide and hydrogen sulfide in MEA or DEA can The derivation is based on the assumption that
be determined even without a powerful com- the carbonate concentration in an alkanolamine
puter. Significant deviations from the model, solution is so low it can be neglected in the mass
which occur at high loading, are corrected by balance. The solution of the equations for phys-
using empirical factors. ical solubility (Eq. 29), bicarbonate (Eq. 30),
Subprograms are available for calculating and carbamate (Eq. 53), and for the mass bal-
solubility equilibria by use of professional ance of amine and carbon dioxide as well as
simulation programs, for example, an “Amine electroneutrality (without H+ and OH− ),
Data Package” for PROCESS. Similar sub- 
A= [RRNH] + RRNCOO− + RRNH+
2 (59)
programs are offered for ASPEN, SOFTEC,
and ChemShare. The simulation programs 
AXc = RRNCOO− + HCO−
3 (60)
TSWEET and AMSIM (Amine Gas Treating
Plant Simulator) are also available [38], [39].
12 Absorption


A model of vapor – liquid equilibria for aque-

RRNH+
2 = RRNCOO− + HCO−
3 (61) ous solutions of acid gases in alkanolamines in
which the activity coefficients are represented
leads to the following isotherm by the electrolyte NRTL equation was pub-
Hc Ka A Xc [Xc −F (Xc )] lished by Augsten et al. [61], [62]. The NRTL
p (CO2 ) = · (62)
Kb 1−Xc −F (Xc ) molecule – ion pair binary interaction parame-
The function F (X c ) can be replaced by ters are fitted to experimental data with the data-
1/2 regression system of the Aspen Plus process
F (Xc ) =Sa− Sa2 −Xc (1−Xc ) (63) simulator.
where Sa is a factor proposed by Sartori and A correlation of the solubility of CO2 and
Savage which is defined as H2 S in a mixed alkanolamine solutions by us-
ing the Pitzer electrolyte model and the Mar-
Sa= (1+Kc /A) /2 (64)
gules expansion for excess Gibbs energy was
Equation (62) shows the effect of carbamate for- published by Li and Mather [63], [64]. One
mation on the solubility isotherm. Carbamates binary molecule – molecule, as well as one bi-
can be formed only from primary and secondary nary and two ternary ion – moleule interaction
amines. Tertiary amines do not form carbamates, parameters, are fitted to experimental data.
and sterically hindered amines do so to only a A new absorption isotherm for the solubil-
minor extent. ity of acid gases in basic solutions was pub-
For the simultaneous solubility equilibria of lished in 1993 by Schlauer [65]. The chem-
carbon dioxide and hydrogen sulfide in aque- istry of the reactions is established by the ki-
ous MDEA solution, absorption isotherms have netics in Chapter 2.5. With the amine R2 NH as
been derived from the equilibria of bicarbonate the base B, R2 N+ HCO− 2 as the zwitterion, and
(Eq. 30), hydrogen sulfide (Eq. 44), and amine R2 NH+ 2 as the protonated base, the equilibria of
hydrolysis (Eq. 52), as well as from Henry’s law Equations (150) and (151) are given by Equa-
constant, electroneutrality, and amine balance tions (67) and (68).
[45].
Hc Ka A Xc (Xc +Xs ) K z [R2 NH][CO2 ] = [R2 N+ HCO−
2 ] (67)
p (CO2 ) = (65)
Kb 1−Xc −Xs
Hs Ka A Xs (Xc +Xs ) K d [R2 N+ HCO− − +
2 ][R2 NH] = [R2 NCOO ][R2 NH2 ] (68)
p (H2 S) = (66)
Kh (1−Xc −Xs )
with reaction constants K z and K d for the gen-
Otto et al. and Mather et al. have published eration of the zwitterion and its decomposition
extended experimental data on solubility equi- to the carbamate R2 NCOO− , respectively. Such
libria for carbon dioxide and hydrogen sulfide reactions generally describe stoichiometric ra-
in aqueous solutions of alkanolamine (see Ta- tios of acid gas to amine of 1:1 and 1:2.
ble 4).
Table 4. Solubility equilibria of carbon dioxide and hydrogen sulfide A = [R2 N+ HCO− −
2 ] + [R2 NH] + [R2 NCOO ]
in aqueous alkanolamine solutions + [R2 NH+
2 ] (69)
Amine ∗ Gas Reference
X c A = [CO2 ] + [R2 N+ HCO− −
2 ] + [R2 NCOO ] (70)
DEA H2 S + CO2 [46], [47]
DIPA H2 S, CO2 [48]
DIPA H2 S + CO2 [49] [R2 NCOO− ] = [R2 NH+
2 ] (71)
DGA H2 S, CO2 [50]
MEA H2 S + CO2 [51]
MDEA H2 S, CO2 [52], [55], [56] Eq. (29):
MEA + MDEA CO2 [57], [58]
DEA H2 S, CO2 [41], [54]
AMP H2 S, CO2 [59]
pc = H c [CO2 ]
AMP H2 S + CO2 [60]
TEA H2 S + CO2 [53] Equations (67) and (68), the mass balances of
the base (Eq. 69) and of the acid gas (Eq. 70), the
∗ AMP = 2-amino-2-methyl-1-propanol, DEA = diethanolamine,
DGA = diglycolamine, DIPA = diisopropanolamine, electroneutrality condition (Eq. 71), and Henry’s
MDEA = methyl diethanolamine, MEA = monoethanol amine, law (Eq. 29) can be solved analytically to give
and TEA = triethanolamine
Absorption 13

pc Experimental solubility data of the single gases


Xc = +
Hc A carbon dioxide and hydrogen sulfide in aqueous
pc Kz /Hc + (pc Kd Kz /Hc )1/2 solutions of MDEA were correlated by Maurer
+ (72) et al. [55] with a model already described for
1 + pc Kz /Hc + 2 (pc Kd Kz /Hc )1/2
aqueous solutions of ammonia. Selected binary
pc pc Cc + (pc Bc )1/2
Xc = + (73) parameters and one ternary interaction parame-
Hc A 1 + pc Cc + 2 (pc Bc )1/2 ter were fitted to the experimental data.
where

C c = K z /H c and Bc = K d K z /H c (74) 1.6. Enthalpy and Absorption


whereby the parameters H c , C c , and Bc are fit- Equilibrium
ted to the experimental data. The isotherm also
applies to the solubility of other sour gases in The temperature dependence of the fugacity fi of
alkaline solvents, for example, H2 S in aqueous a dissolved component i is related to the molar
MDEA (Fig. 3). The H2 S fugacity was calcu- enthalpy of absorption ∆H Abs
i of this compo-
lated from the experimental partial pressure by nent by the Clausius – Clapeyron equation
a truncated virial equation of state, and the sec-
δlnfi /δT = − ∆HiAbs /RT 2 ∆zi (76)
ond virial coefficients were calculated according
to Prausnitz et al. [2] where ∆zi is the difference between the com-
pressibility factors of the vapor and liquid phases
 
∆zi =ziG − ziL = viG − viL p/RT (77)

For zG L
i ≈ 1 in the vapor phase and z i  1 in the
liquid phase follows: ∆zi ≈ 1, fi ≈ pi ,

∆HiAbs =R [δlnpi /δ (1/T )]x (78)

Equation (78) is used to calculate the differ-


ential enthalpy of absorption at a loading xi
from known solubility equilibria. An average
enthalpy of absorption for a loading from xi (1)
to xi (2) is determined by the appropriate inte-
gration
x(2)

∆HiAbs = ∆HiAbs dxi / [xi (2) − xi (1)] (79)
x(1)

The enthalpy of absorption can be calculated by


using UNIQUAC [2] or UNIFAC [66]. The tem-
Figure 3. Comparison of predicted and experimental equi-
perature dependence of Henry’s law constant
librium data for H2 S in 1 M aqueous MDEA Hi, L is determined from Equations (21) and
(78):
The isotherm can be expanded to the simul-
taneous solubility of more sour gases (Eq. 75). δlnHi,L /δ (1/T ) =∆HiAbs /R (80)
 1/2
 The temperature dependence of Henry’s law
pi Ci + pi Bi / pj Bj constants can be estimated roughly by using the
pi j
Xi = +  1/2 (75) following formula [9]:
Hi A  
1+ pj Cj + 2 pj Bj
j j
14 Absorption

∞ 0
Hi,L =γi,L fi (81) temperature before it is brought to the absorber
head. The lowest temperature is obtained by adi-
where γ ∞
i, L is the activity coefficient of gas com- abatic expansion of the loaded solvent (possibly
ponent i in the solvent L at infinite dilution and under vacuum).
f 0i is the standard fugacity. The standard fugac- In processes involving chemical absorption,
ity is independent of the solvent, and its gener- reaction kinetics limit the use of low tempera-
alized temperature dependence is given by tures in an absorber. Although the partial pres-

sure of a dissolved component drops as the tem-
ln f 0i /pc,i = 7.224 − 7.534/Tr,i
−2.598lnTr,i (82)
perature decreases, this fact cannot be used to
advantage in an industrial absorber because the
for a range of temperatures 0.6 < T r,i < 16. The rates of chemical reaction are retarded by low
activity coefficient at infinite dilution γ ∞ i, L is temperatures to such an extent that mass trans-
specific for each pair (gas component i and sol- fer is hindered and a long residence time (i.e.,
vent L) but only weakly dependent on the tem- a larger absorber) is required. Reaction kinetics
perature. of chemical absorption and the use of kinetic
At low temperatures, Henry’s law constant effects are dealt with in Chapter 2.
increases with increasing temperature until a
maximum at T r, i = 2.8 is reached. At higher
temperatures Henry’s law constant decreases 2. Mass Transfer
slightly, i.e., the solubility again increases.
The enthalpy of absorption increases steadily A comprehensive treatment of mass transfer
with increasing temperature (i.e., it decreases phenomena is given elsewhere (→ Transport
in absolute value) and reaches zero at Phenomena).
T r, i = 2.8. At lower temperatures, heat is liber-
ated during absorption; at higher temperatures,
it is consumed. In chemical absorption the en- 2.1. Introduction
thalpy of absorption is strongly dependent on
loading [52]. Once the chemical capacity has This chapter deals with mass transfer during ab-
been saturated, the absorption enthalpy drops sorption occurring in a gas – liquid system not in
substantially. equilibrium. The nonequilibrium produces con-
The temperature dependence of the solubil- centration gradients at the interface and mass
ity equilibria and the enthalpy of absorption is of transfer across this boundary, which tends to
paramount importance in designing an absorp- equilibrate the system.
tion installation. In the absorber, the gas compo- During absorption or desorption, the ab-
nent to be washed out must be highly soluble. In sorbed component cannot spread spontaneously
the regenerator where the absorbed gas compo- over the total volume of a phase. In the gas phase,
nent from the solvent is removed, the solubility mass transfer during absorption is hindered by
must be as low as possible. The strong increase the gaseous components that are not absorbed
in solubility at low temperatures is utilized par- and remain as purified gas. During desorption,
ticularly in physical absorption processes, the it is hindered by the stripping gas or stripping
absorber being operated at as low a tempera- steam. In the liquid phase, mass transfer is hin-
ture as possible and the regenerator at a high dered by the solvent.
temperature. Because the enthalpy of absorp- Mass transfer of the absorbed components
tion becomes negative and, in absolute terms, near the interface occurs mainly by diffusion
always increases with decreasing temperature, and, in the bulk of the phase, mainly by turbu-
provision must be made to remove the liberated lence. At equilibrium, mass transfer across the
heat of absorption from the absorber to improve interface is equal in both directions so that no
the efficiency of the process. To do so, solvent is concentration gradient is established near the
removed from the absorber, cooled, expanded, phase boundary. This chapter deals only with
and then recirculated to the absorber. mass transfer that occurs before equilibrium has
To obtain as pure a treated gas as possible, been established between the two phases, not
the regenerated solvent is cooled to a very low with mass transfer at equilibrium.
Absorption 15

2.2. Mass Transfer Coefficients 4) The question of whether these values satisfy
the solubility equilbrium relation
Mass transfer across the interface of a compo-
nent to be absorbed is described quantitatively y1∗ =F (x1 ) (88)
by the mass transfer coefficients. The definition by meeting the following condition
of these coefficients is based on two assump-
tions: Abs [y1∗ −y1 ] <Abs y1 −y b /100 (89)

1) At the phase boundary the gas and liquid must be checked. If condition (89) is met, the
phases are at equilibrium. Significant devia- relative deviation is less than 1 %. If not, the
tions from equilibrium at the interface occur calculation is repeated beginning with step
only if mass transfer is extremely rapid. 1, but the new values x 1 and y1 in Equation
2) Mass transfer is proportional to the difference (87) are used in place of the mole fractions
between the concentration in the bulk of the x b and yb . Figure 4 shows that this approxi-
phase and the concentration at the interface. mation method converges rapidly, even if the
absorption equilibrium is strongly nonlinear.
In the stationary state, mass transfer is equal
on both sides of the interface so that
   
NA =kG y b −y i =kL xi −xb (83)

The mass transfer rate N A is the number of moles


of an absorbed component A being transferred
across a unit area of the interface per time unit;
yb and x b are the mole fractions of component A
in the bulk of the gas and liquid phases; yi and x i
are the mole fractions at the interface. The pro-
portionality constants k G and k L are the mass
transfer coefficients in the gas and liquid phase,
respectively. The mole fractions at the interface
can be calculated from known mass transfer co-
efficients and solubility equilibria by using the
following approximation method:
1) Mole fractions x∗ and y∗ are calculated
which are in equilibrium with mole fractions Figure 4. Prediction of the concentration at the interface:
yb and x b in the bulk of the other phases graphical demonstration of the approximation
  If the absorption equilibrium in the concen-
y ∗ =F xb and y b =F (x∗ ) (84)
tration region employed can be represented by a
straight line
where F (x b ) and F (x∗) are the solubility
equilibrium relationships. y=n+mx (n,m= const.) (90)
2) An intermediate value C is calculated
the mass transfer is also proportional to the dif-


kG y b −y ∗ ference between the concentration in the bulk of
C=
(85)
k L x∗ − xb one phase and the equilibrium value of the other
phase
3) As a first approximation, the equilibrium    
concentration at the interface is NA =KG y b −y ∗ =KL x∗ − xb (91)
 
y1 = C y b +y ∗ / (1+C) (86)
These proportionality constants K G and K L are
the overall mass transfer coefficients in the gas
  and liquid phase, respectively. For recalculation,
x1 =xb + y b −y1 kG /kL (87)
16 Absorption
1/KL = 1/kL +1/mkG (92) 2.3. Effect of Solute Concentration
1/KG = 1/kG +m/kL (93)
The relations given in Section 2.2 are valid only
KL =mKG (94) for low concentration of the absorbed compo-
nent A, as long as x A  1 and yA  1. At
The inverse of the mass transfer coefficients can higher concentration, the mass flow created by
be considered the resistance to mass transfer, and diffusion must be taken into account [68]. If two
the overall resistance consists of the resistance in components A and B in a gas film at the inter-
the gas and liquid phases. If the resistance is sub- face are considered, a concentration gradient is
stantially greater in one phase than in the other, formed in which
it is called a one-sided resistance. For one-sided
resistance in the gas phase, dyA
NA = −cDAB +yA (NA +NB ) (101)
dz
kL mkG xi →xb , y i →y ∗ (95)
Here, c is the overall concentration of compo-
If resistance in the liquid phase predominates, nents A and B in the gas phase, z the distance
analogously, from the interface, and DAB the diffusion con-
stant of component A in the binary gas mixture.
kL mkG xi →x∗ , y i →y b (96) In the steady state, the components diffuse in op-
The concentrations at the interface can only be posite directions so that only the adsorbed com-
between these extremes (cf. Fig. 4). ponent A flows through the gas film; the non-
adsorbed component B remains in the gas film.
xb ≤xi ≤x∗ andy ∗ ≤y i ≤ y b (97) Hence, N B = 0 and from Equation (101),
In industrial absorption devices, where the sur- cDAB dyA
NA = − (102)
face of the interface cannot be determined accu- 1−yA dz
rately, volume-related mass transfer coefficients
are used The mass transfer of component A increases in
proportion to the concentration gradient dyA /dz
KL a,KG a,kL a,andkG a (98) and to 1/(1 − yA ), hence with increasing con-
centration of yA . From the continuity of mass
where a is the unknown surface of the interface transfer,
per unit volume of the absorption device. For
 
recalculation, dNA d 1 dyA
= 0 then · =0 (103)
dz dz 1−yA dz
1/KL a= 1/kL a+1/mkG a (99)
After the first and second integration,
1/KG a= 1/kG a+m/kL a (100)
[1/ (1 − yA )] dyA /dz =C1 (104)
These relationships are especially useful in a
physical solubility equilibrium, where a dimen-
−ln (1 − yA ) =z C1 +C2 (105)
sionless Henry’s law constant Hi, L /p or the K
value can be substituted for m. The surface a de- The constants C 1 and C 2 can be calculated from
creases with decreasing liquid flow rate L and the boundary conditions that exist at the inter-
with increasing surface tension (Marangoni ef- face and at the boundary between the gas film
fect) because streams are formed and the surface and the bulk of the gas phase
of the packing is not completely wetted [74]. The
effective phase surface and the mass transfer co- i
yA =yA if z = 0 (106)
efficients has been measured in contact devices
[75] for gases with polar and nonpolar liquids as b
yA =yA if z =δG (107)
well as with highly viscous hydrocarbons.
Numerical values of mass transfer coeffi- where δG is the thickness of the gas film or the
cients K G a in packed columns for several in- distance from the interface where the concentra-
dustrially important absorption systems can be tion in the gas phase attains the value ybA . From
found in [67], [73] and [75]. Equations (104) – (107),
Absorption 17
 
i i plate, or the space between the bubble cap and
C2 = −ln 1−yA = −lnyB (108)
the plate. Turbulence in the gas phase is charac-
i
1 1−yA 1 yi terized by the Reynolds and Schmidt numbers:
C1 = ln b
= ln B
b
(109)
z 1−yA z yB
Re=GM d/µG (117)
and, finally, Equations (103), (104), and (105)
cDAB 1−yA i
cDAB yBi Sc=µG /G DAB (118)
NA = ln b
= ln b (110)
δG 1−yA δG yB The following relationship has been established
This equation describes the mass transfer at all from experimental mass transfer data in an ab-
concentrations of adsorbed component A. At a sorption unit:
lower concentration,
Sh=St·Re·Sc=f (Re,Sc) (119)
ln (1−yA ) ≈ −yA (yA → 0) (111)
This empirical relation can then be used to scale
and Equation (110) becomes up absorbers of the same type. The dimension-
less Stanton number is defined as
cDAB  b i

NA = yA −yA (112)
δG St=kG MG /GM (120)
By comparison with the definition of N A The following empirical formula has been pro-
(Eq. 83), posed for mass transfer in packed columns with
Raschig rings and Berl saddles [76]:
kG =cDAB /δG (113)

In an ideal gas phase, the concentration c is jM =St·Sc2/3 = 1.195Re−0.36 (121)

c=p/RT (114)
where jM is the j factor according to
Chilton – Colburn for the modified Reynolds
and the mass transfer coefficient is analogy among mass, heat, and impulse transfer.
Here, the Reynolds number is modified some-
kG =pDAB /δG RT (115) what to
which defines the thickness of the gas film δG ; it Re=GM d/µG (1−ε) (122)
is strongly dependent on turbulence in the gas
phase. Similar dependencies on concentration where d is the diameter of a sphere having the
apply in the liquid, but as a rule, the concen- same surface as a piece of packing and ε is the
tration of the absorbed component in the liquid void fraction of the packing available for gas
phase is low. flow.
In Equations (117) – (122), k G is the mass
transfer coefficient in kmol s−1 m−2 ; G M is the
2.4. Correlation of Mass Transfer specific gas flow rate in kg s−1 m−2 ; d is the
Coefficients characteristic length in m; µG is the viscosity of
the gas phase in kg s−1 m−1 , G is the density
Empirical relationships from dimensionless of the gas phase in kg/m3 ; DAB is the diffu-
analysis are used to correlate mass transfer co- sion constant of component A in m2 /s in inert
efficients in the gas phase. One criterion for the gas B; and
 M G is the molar mass of the gas
mass transfer coefficient in the gas phase is the phase = yi Mi in kg/kmol.
Sherwood number The following empirical formula can be used
for mass transfer in bubble-cap tray absorption
Sh=kG RT d/pDAB (116) columns [77]:
As characteristic length d is usually taken the  1/2
kg = 7 u1/2 DAB /s (123)
dimensions of the adsorption column packing,
the diameter of the gas channel in a perforated
18 Absorption

Here k g is the mass transfer coefficient in Sh=kl d/DAL (131)


cm/s; u is the gas velocity in cm/s; s is the liquid
Re=d2L nL L /µL (132)
level on the tray in cm; and DAB is the diffusion
coefficient in cm2 /s. Sc=µL /L DAL (133)
To convert from k g to k G (SI units),

kG =kg /100V (124)


where d L is the stirrer diameter in m; nL is the
rotation rate of the stirrer in s−1 ; d is the con-
or tainer diameter in m; and k l is the mass transfer
coefficient in m/s.
kG =kg p/100RT (125) The mass transfer coefficient k l is expressed
in meters per second and like Equation (83), is
where V is the molar volume of the gas phase in defined by the difference in concentrations
cubic meters per kilomole. Equation (125) ap-  
plies to an ideal gas phase. The mass transfer NA =kl ciA − cb
A (134)
coefficients k L in the liquid phase for Raschig
The concentrations of component A at the inter-
rings and Berl saddles can be calculated with the
face ciA and the bulk of the liquid phase cbA , are
following empirical formula [76]; similar corre-
expressed in kmol/m3 .
lations also apply to packed columns [78]:
To convert k l to k L (mass transfer coefficient
St= 25.1Re0.45 ·Sc0.5 (126)
referred to mole fraction)
kl =kL /ML L (135)
The Stanton, Reynolds, and Schmidt numbers in
the liquid are is used. In highly supersaturated solutions, bub-
ble formation occurs which increases the phase
St=kL ML /LM (127) surface and intensifies turbulence. Two regions
of spontaneous bubble formation of this type ex-
Re=LM d/µL (128) ist which differ in the intensity of bubble forma-
tion depending on the supersaturation σ:
Sc=µL /pL DAL (129)  
σ= cb ∗ ∗
A −cA /cA (136)

where k L is the mass transfer coefficient in where c∗A is the concentration in equilibrium
kmol s−1 m−2 ; M L the molar mass of liquid in with the gas phase (bulk). Bubble formation is
kg/kmol; d the characteristic length in m; DAL weak up to critical supersaturation σ c , and the
the diffusion constant of component A in the liq- volume-related mass transfer coefficient in the
uid phase in m2 /s; L the density of liquid phase bulk of the liquid phase is
in kg/m3 ; L M the specific liquid flow rate in klb a= 6.7710−6 Re0.5 ·σ 0.78 (137)
kg s−1 m−2 ; and µL the viscosity of the liquid
phase in kg s−1 m−1 . Once the critical supersaturation has been ex-
Additional correlations of mass and heat ceeded and σ > σ c , bubble formation becomes
transfer can be found in [79–84]. intense, and the mass transfer coefficient is
Another relation holds for the mass transfer klb a= 2.4510−6 Re0.98 ·σ 2.5 (138)
of carbon dioxide from a supersaturated aque-
ous solution in a container with a stirrer [85]. For the critical supersaturation σ c between weak
As long as no bubbles are formed, mass transfer and intense bubble formation, the range of va-
through the surface of the liquid can be described lidity is defined as follows:
by the following empirical formula:
σc = 1.81Re−0.25 (139)
Sh= 0.322Re0.7 ·Sc1/3 (130) 2190<Re<14000 (140)

In this case, the Sherwood, Reynolds, and 0.038<σ<0.80 (141)


Schmidt numbers are defined as follows
Absorption 19
 
2.5. Mass Transfer and Chemical k11 =F exp −E A /RT (145)
Reaction
where F is the frequency factor and E A the acti-
If the absorbed component reacts in the liq- vation energy of the reaction; numerical values
uid phase and is thus transformed chemically, of some second-order reactions are given in Ta-
its mass transfer in the liquid phase is acceler- ble 5.
ated. If this reaction is irreversible, the absorbed Table 5. Frequency factors and activation energies of several second-
component reacts until its concentration in the order reactions
liquid phase is practically zero. Thus, for ex-
Reaction ln F, EA , References
ample, in the absorption of carbon dioxide in m3 k mol−1 s−1 kJ/mol
aqueous potassium hydroxide solution, carbon-
ate (CO2− 3 ) and traces of bicarbonate (HCO3 )
− CO2 + OH− 31.43 55.42 [88], [89]
CO2 + H2 O 26.13 70.98 [89]
can be found in solution, but practically no car- CO2 + NH3 25.63 48.43 [89]
bon dioxide as long as an excess of alkali is CO2 + MEA 25.84 41.92 [90]
25.31 41.20 [91]
present. Mass transfer is then independent of CO2 + MIPA 26.43 43.84 [90]
loading and proportional to the concentration at CO2 + TEA 24.68 51.46 [91]
the interface ciA because the concentration in the CO2 + MDEA 16.83
18.63
37.21
42.48
[92]
[93]
bulk of the liquid phase cbA = 0. 29.80 71.71 [94]
For an irreversible first-order reaction, the NO + Co – TE 31.00 22.40 [95]
2−
O2 + SO3 30.8 58.1 [96]
mass transfer coefficient in the liquid phase de- (at pH 8.0; [Co2+ ] = 0.1 mmol/L as catalyst)
pends on the Hatta number [86]. According to
Danckwert’s surface renewal theory, the mass ∗ MIPA = monoisopropanolamine;
TE = tetraethylenepentamine; other abbreviations are defined in
transfer coefficient including a reaction of com- Table 4.
ponent A with reactant B is calculated according
to the following relation [87]: The reaction rate constant k 11 is calculated in
 1/2
1/2 m3 kmol−1 s−1 ; from equation (145) by using
kl = kl2 +DAL k11 cb
B =kl 1+Ha2 R = 0.008314 kJ mol−1 K−1 for the gas constant
=kl E (142) and expressing the temperature T in Kelvin. In
Table 5, Co – TE denotes a complex of cobalt
where Ha is a dimensionless Hatta number, E is (II) with tetraethylenepentamine, which forms
the enhancement factor, k 11 is the reaction rate a nitrosyl compound with nitric oxide. Numeri-
constant, and k l is the mass transfer coefficient cal values of the reaction rate constants of nitric
in the liquid phase without a reaction. oxide with similar cobalt and iron complexes in
 1/2 aqueous solution have also been published [95],
Ha= DAL k11 cb
B /kl (143) [97], and [98]. Brønsted has given a relation-

1/2 ship between the reaction rate constant k 11 of
E = 1+Ha2 (144)
carbon dioxide with alkanolamines and the dis-
For large Hatta numbers beginning with Ha > 3, sociation constand K a of these alkanolamines,
the enhancement factor E ≈ Ha. These param- which suggests a homogeneous base catalysis ,
eters describe the contribution of the reaction the following relation is recommended for pri-
to mass transfer if a chemical reaction occurs. mary and secondary alkanolamines [93]:
This equation can also be used for a pseudo-
first-order reaction, as long as an excess of B lnk11 = pKa +16.26 − 7188/T (146)
is present. For very rapid reactions, the Hatta This empirical formula applies from 293 to
number is large and mass transfer is controlled 303 K. For tertiary alkanolamines at 293 K,
increasingly by the mass transfer coefficient of
the gas phase. lnk11 = pKa −14.24 (147)
The reaction rate constants k 11 of the most
frequently encountered reactions are known, and is recommended [93]. Some industrially impor-
their temperature dependence is represented ac- tant reactions are of a higher order, e.g., the re-
cording to Arrhenius by action of carbon dioxide with the alkanolamines
20 Absorption

DEA or DIPA, shown in Figures 5 and 6. For


higher order reactions,

r=kmn [A]m [B]n (148)

the Hatta number according to Higbie is

Ha=kl−1 ·
  m−1  n 1/2
2DAL kmn ciA cb
B / (m+1) (149)

These reactions probably occur according to the


following mechanism [88], [100]. Carbon di-
oxide forms a zwitterion with an alkanolamine
which, in a subsequent reaction, donates a pro-
ton to a base and is converted to the carbamate:

(150)

(151)

Figure 6. Rate constant for the reaction of carbon dioxide


with diisopropanolamine – effect of amine concentration
Temperature = 298 K.
o Data from [101]; × Data from [93]

In the second reaction (Eq. 151) the proton


can be accepted by various bases for example,
OH− (→ H2 O), water (→ H3 O+ ), or an amine
(→ amine H+ ). After the concentration of the
zwitterion [R2 NHCO2 ] is eliminated mathemat-
ically, from the kinetics of Equations (150) and
(151),
d [CO2 ] k11 [CO2 ] [R2 NH]
r= =  (152)
dt 1+k−1 / kB [B]

If the increase in concentration of bases, [B] , is


proportional to the amine concentration

[B] = KB [R2 NH] (153)

and the denominator of Equation (152) is



1  k−1 / kB [B] (154)

the reaction tends toward third order and the re-


Figure 5. Rate constant for the reaction of carbon dioxide
with diethanolamine – effect of amine concentration
action rate is proportional to the square of the
Temperature = 298 K. amine concentration
+ Data from [91]; o Data from [101]; × Data and calculation  
[99]: kc = A/(1/1410 + 1/1200 A) r≈ kB k11 KB /k−1 [CO2 ] [R2 NH]2 (155)
Absorption 21

Numerical values for the rate constants and ener- r=kc [A] , where kc =k1n [B]n (161)
gies of activation of reactions of carbon dioxide All three models lead to similar results [103]. No
with aqueous and alcoholic solutions of DEA, analytical solution of the differential equations
MEA, and DIPA are given in [93], [101], and is known for reversible reactions: other models
[102]. or numerical methods are used to solve differ-
ential equations.
To represent the absorption kinetics of carbon
2.6. Modeling of Mass Transfer with dioxide and hydrogen sulfide in aqueous solu-
Chemical Reaction tions of DIPA and MDEA the two-film theory
with two layers is used [104]. The assumption
An analytical solution of the differential equa- is that the reaction is an irreversible first-order
tions for mass transfer with a reaction of the ab- reaction and that the concentration profiles are
sorbed component in the liquid phase is known linear [105]. If the boundary values from Danck-
only for a (pseudo) first-order reaction. This re- wert’s model are used for the concentration gra-
action must be either irreversible or coupled with dient of both layers, the differential equations
a rapid secondary reaction of the products so that can be replaced by nonlinear algebraic equations
re-formation of the absorbed components need and solved numerically. This model was used by
not be considered. Formulas derived for the fol- Shell Oil in the design of commercial installa-
lowing three models are known. tions for the selective absorption of hydrogen
sulfide from gases containing carbon dioxide.
1) Penetration Theory (Danckwerts, Higbie): With the aid of a computation model based on

  the penetration theory, the differential equations
kl =kl Ha 1 + 1/8Ha2 erf 2Ha/π 1/2 for mass transfer, including complex reversible

reactions in the liquid phase, can be solved
+2Haexp −4Ha2 /π (156)
numerically [106]. The concentration gradients
2) Two-Film Theory (Sherwood and Pigford): are calculated by using a grid, the differential
equations being replaced by a system of linear
kl =kl Ha/tanhHa (157) equations. Further computational models can be
found in [107] and [108].
3) Surface-Renewal Theory (Danckwerts): A professional simulation program dealing

1/2 with kinetics and absorption is available under
kl =kl 1+Ha2 (158) the name Aspen plus, which offers the method
Ratefrac.
Here, Ha is the Hatta number (DAL k c /k 2l )1/2 ,
k l
is the mass transfer coefficient with chemi-
cal reaction in the liquid phase in m/s; k l is the 3. Design of Absorption Systems
mass transfer coefficient in the liquid phase (with
no reaction) in m/s; k c is the reaction rate con- 3.1. Methods of Absorption
stant of the (pseudo) first-order reaction in s−1 ,
and DAL is the diffusion coefficient of absorbed The use of physical absorption processes is pre-
component A in liquid phase L in m2 /s. ferred whenever
A reaction of higher order 1) feed gases are present in large amounts at
high pressure and the amount of the compo-
A + nB → Product (159) nent to be absorbed is relatively large;
and its reaction rate r 2) the purified gas (the fraction of gas that is not
absorbed) must be of high purity;
r=k1n [A] [B]n (160)
3) one or more selectively absorbed compo-
nents are to be obtained in enriched or pure
can be considered pseudo-first order with respect form, possibly still at elevated pressure;
to A as long as the reaction partner B is not con- 4) the absorbent is also the product of a subse-
sumed to any great extent. Until then, quent synthesis, e.g., methanol (→ Gas Pro-
duction).
22 Absorption

On the other hand, absorption processes with 3.2. Methods of Desorption


simultaneous chemical reaction (chemisorption)
are always preferred when Desorption (→ Gas Production) is the reverse
process of absorption in which the absorbate is
1) the components to be separated from feed again removed from the solvent. Desorption is
gases are present in small concentrations and achieved with the following methods:
at low partial pressures;
2) the purity requirements of the purified gas are 1) Flashing the solvent to lower the partial pres-
not too high; sure of the dissolved components, to vacuum
3) the components to be separated from feed if necessary;
gases are strongly acidic and undergo a ther- 2) Reboiling the solvent, to generate stripping
mally reversible reaction with the chemical vapor by evaporation of part of the solvent;
component of the absorbent; 3) Stripping with an (extraneous) inert gas;
4) low-cost waste heat is available for thermally 4) A combination of methods 1 to 3.
regenerating the absorbent.
Organic solvents can also be dried during des-
Absorption equipment for both types of ab- orption, when the water vapor absorbed with the
sorption generally consists of a column with in- feed gas is again given off. This leads to a dry
ternals for heat and material exchange (plate or clean gas with reduced vapor dew point.
packing) in which the feed gas is brought into Desorption occurs by the same basic mech-
countercurrent contact with the regenerated ab- anism as absorption. Each reduction in par-
sorbent. tial pressure of the absorbed component over
The purified gas is taken off the head of this the loaded solvent produces a desorption effect.
column. The absorbent loaded with the removed Wide use is made of desorption by pressure re-
component, the absorbate, leaves the bottom of duction because the energy requirements are low
the column and is regenerated by desorption. and cover energy can even be recovered. In the
The basic scheme thus consists of an absorp- second regeneration step after depressurization,
tion and a desorption stage with the absorbent stripping with inert gas is often more economic
cycling between them as it takes up and again than thermal regeneration.
gives off the absorbate (Fig. 7). The desired purity of the gas determines the
final cost of desorption. The necessary differ-
ence between the partial pressure of the absorbed

Figure 7. Schematic of absorption installation with desorption for regeneration


a) Absorber; b) Depressurization (flash) stage; c) Desorber (regenerator); d) Pump; e) Reducing valve; f) Cooler
Absorption 23

key componentover the regenerated solution (1) and its very small pressure drop. High flexibil-
and in the purified gas (2) serves as a criterion ity is achieved by the movable plate inside the
for determining the dimensions of the absorption fixed cap, whose lifting motion is always syn-
and desorption equipment. chronized with the gas loading. In more recent
designs the valve tray is perforated so that an
even wider loading range can be achieved [131].
3.3. Absorption and Desorption The Cross-Stream Plate (Montz), a valve
Equipment plate without moving parts, is intended for espe-
cially high gas loading. The rectangular valves
Because reactions and conversions between are arranged so that the gas streams intersect
gaseous and liquid phases are substantially with neighboring streams and head-on collisions
slower than those between equal states of aggre- of opposing streams are thus prevented. In this
gation, relatively large reaction volumes are re- manner, the otherwise inevitable upward en-
quired in gas absorption installations. Mechani- trainment of liquid is avoided [131].
cal accessories which create the largest possible Sieve plates are suitable for high gas load-
phase interface serve to improve mass exchange ings. They are needed to prevent liquid weep-
in sorption equipment. Relatively large gas and ing through the plate (→ Distillation and Rec-
liquid velocities produce high turbulences as the tification, Chap. 8.2.). Good mass transfer oc-
hydraulic flooding point is approached. curs due to the bubble layer formation on the
Appropriate internals direct the liquid and plate. The sieve plate can also be designed to
gas streams and increase the contact area have several downcomers. Except for special
between the two phases, thereby substan- low-temperature separation plants, it has thus far
tially improving mass transfer. Various de- not been widely used in absorption technology.
signs have proved suitable, especially absorp- The Kittel Polygonal Plate (Stahl) is espe-
tion plates, randomly poured packings and struc- cially suited for high liquid loadings. The down-
tured packings (→ Distillation and Rectifica- comers can be positioned inside or outside the
tion, Chap. 8.3.). plate. Some types have an internal tube in the
The internals must be designed to withstand center of the plate which is used to transport liq-
high hydraulic loads, produce minimum pres- uid or gas [132].
sure loss and achieve good mass transfer with The Performkontact Plate (CLG) is also a
high separation efficiency. Various types of in- cross-flow plate with downcomers for high liq-
ternals are described in [126–133]. uid loading. Its active surface consists of ex-
panded metal arranged so that the gas slots in
the mesh are at an acute angle to the flow direc-
3.4. Columns with Mass-Transfer Plates tion of liquid flows [133], [134].

Columns with mass-transfer plates have proved


to be as suitable in absorption as in distillation 3.5. Columns with Random Packing
(→ Distillation and Rectification, Chap. 8.1.3.).
In comparison with most other internals, they are Packings can take high liquid loads and have
distinguished by high hydraulic flexibility, espe- a low pressure drop. In addition to the well-
cially under extremely low load. Common char- known and well-tested Raschig rings, Pall rings,
acteristics of the most diverse designs of such Berl saddles and Intalox packings [135–139]
plates are overflow weirs and downcomers for (→ Distillation and Rectification, Chap. 8.3.)
hydrostatic holdup of the liquid. Another type new developments contribute to further reduc-
are dynamic plates without downcomers, hold- tion of the pressure drop occurring with in-
ing up the liquid by the kinetic energy of the creased mass transfer. Thus, for example, Cas-
rising gases. cade mini rings (Mass Transfer, Inc.) are used in
Valve plates (ballast plates) are widely used a wide range of applications and excel by virtue
[130]. The Varioflex Plate (Stahl) has proved it- of high performance [140].
self in practice. It is distinguished particularly
by its lower hydraulic loading limit of 20 %
24 Absorption

Intalox metal saddles also have special ad- 3.7. Columns with Special Internals
vantages [141–144]. Super-intalox (R) pack-
ings of plastic and ceramic materials (Norton) Atomizing absorbents in spraying devices, e.g.,
are used often in practice and are distinguished through nozzles, produces a suspension of finely
by high capacities and good separation perfor- divided drops in a stream of gas. Such absorption
mance [145]. Compared to steel packings, ther- methods are suitable for highly soluble compo-
moplastic packings are not only lighter but fre- nents if resistance to mass transfer occurs pri-
quently also more cost-effective. In contrast to marily in the gas phase. The ratio of absorbent
ceramic packings, they do not exhibit abrasion. to gas can then often be very small and contact
Stabilizing additives ensure that their tempera- times can be short.
ture resistance is relatively high. Wetting of plas- Scrubbers with several series of nozzles and
tic packings can be improved substantially by short contact times are successfully employed
hydrophilic surface treatment which eliminates for these tasks. The size of the droplets and the
this disadvantage compared with metal packings residence time for a given gas throughput can
[146]. be adjusted appropriately by a suitable choice
The new VSP packing (Vereinigte Füllkörper of nozzles shapes [118].
Fabriken) also shows high performance. This Cyclone scrubbers can be used whenever a
packing has better properties than the classical single absorption stage is sufficient. The liquid
Pall rings and may also be somewhat more cost- drops are injected, entrained by the high-velocity
effective [148], [149]. gas, loaded with absorbate and separated at the
wall.
This group also includes Venturi scrubbers
3.6. Columns with Structured Packing (→ Dust Separation, Chap. 4.2.) in which the
liquid is separated from the gas at the outlet. In
Structured packings for columns have come into addition to their original application for separat-
increasing use. Their efficiency often consider- ing such particles as dust, mist, or aerosols, they
ably exceeds that of conventional random pack- are increasingly used in absorption technology
ings. (e.g., of sulfur dioxide in flue gas scrubbers) or
Thus, packings of metal, synthetic wo- in chemisorption (e.g., of hydrogen sulfide in
ven fabrics and ceramics such as Mellapack oxidative scrubbers).
(metal) and Kerpak (ceramics) have been used However, Venturi scrubbers normally reach
(Sulzer) (→ Distillation and Rectification). Ex- only moderate absorption efficiencies of about
isting columns can be retrofitted with such pack- 95 % and their pressure drop of 2.0 – 5.0 kPa is
ings to increase their capacity [150], [151]. relatively high.
Special requirements tailored to specific sep- Absorption equipment with rotating internals
aration problems can be met with Pyrapack to disperse the solvent (e.g., “High Gee”) has so
packings G and F [152], [153]. The elements are far not been widely accepted. Practical applica-
fabricated from expanded metal (CLG). Type F tions were limited to special cases [155], [156].
packing has a greater specific surface and thus Spraying devices generally require too much en-
achieves a high specific separation performance. ergy to be cost-effective.
Variant G is coarser and is mainly used for high Film scrubbers are used for absorption par-
gas and liquid loading. ticularly when large absorption enthalpies have
Increased packing surfaces in connection to be removed at the same time, e.g., for the
with additional turbulences in the liquid film are absorption of hydrogen chloride in water. Tube
achieved with Rombapak (Kühni) by means of walls on which the absorbent trickles down can
finely grooved surfaces. The distribution of liq- easily be cooled with water on the other side. In
uid is significantly improved, and a separation the case of an “adiabatic absorber” the reaction
performance of 3.5 – 4 separation stages per me- enthalpy, e.g., from hydrogen chloride absorp-
ter of packing height is achieved [154]. tion, is also removed by water evaporating from
the upper end of the tube [114].
The absorption efficiency can be improved by
installing “mechanical stirrers” which increase
Absorption 25

the path of the gas bubbles and mix the liquid


more thoroughly. Stirrer vessels are normally
employed for systems in which the resistance
to mass transfer occurs in the liquid phase. This
may be the case for aeration basins of oxidative
scrubbers or open wastewater treatment basins
if oxygen has to be injected into the liquid.

4. Design of Absorption Equipment


Graphical and analytical methods are used to
design absorption equipment [157]. Usually, a
material and heat balance is drawn up first. The
absorbed component in each case should prefer-
ably be referred to the pure absorbent at a prede-
termined temperature (e.g., 20 ◦ C). In this way,
stationary mass flows are defined.

4.1. Physical Absorption in Plate


Columns Figure 8. Absorption by a solvent in an absorption column

For component i to be absorbed, the material G1 1−y1


· = constant,
balance for the absorber with cross-section a – a L 1−y2
(see Fig. 8) is, for the lower section: the balance or operating line of the absorber is
G1 ·y1 +L·c=G·y+L·c1 (162) y − y2
c=c2 +const. (166)
1−y
for the upper section:
If the operating line and the equilibrium line are
G·y+L·c2 =G2 ·y2 +L·c (163)
plotted on a concentration-loading diagram the
curves shown in Figure 9 are obtained. For con-
with: stant streams of liquid and gas, the balance line
is a straight line. The equilibrium line is obtained
G (1−y) =G1 (1−y1 ) =G2 (1−y2 ) (164) by the method described in Chapter 2.
where G1 is the flow rate of gas entering the
absorber; G2 the flow rate of gas leaving the
absorber; y1 the gas phase mole fraction of ab-
sorbate entering the absorber; y2 the gas phase
mole fraction of absorbate leaving the absorber
at the heat; L the flow rate of the solvent; c1 the
concentration of absorbate leaving the absorber
at the bottom; and c2 the residual load of ab-
sorbate in the regenerated solvent entering the
absorber.
Solving for c, the concentration after loading,
gives:
G1 1−y1 y − y2
c=c2 + · · (165) Figure 9. Loading diagram for determining theoretical
L 1−y2 1−y
number of separation stages for isothermal absorption
with
26 Absorption

The equilibrium line in Figure 9 is plotted The minimum amount of absorbent required
for a constant temperature, which is permissi- is obtained from the slope of the operating line
ble only for isothermal absorption. With the aid for an infinite number of theoretical separation
of a set of steps drawn between the equilibrium stages. It is given by the ratio of absorbent to the
line and the operating line from y1 to y2 , the total gas rate:
number of theoretical separation stages can be
Lmin y2 − y1 ∆y
determined. The number of theoretical separa- = =
tion stages depends on the absorbent flow rate G c2 − c1 ∆c
G
L . The less absorbent enters the absorber, the L min = (168)
αi ·Pg
smaller will be the slope of the operating line
and the more stages are needed for a given sep- where αi is the solubility coefficient of compo-
aration problem. If the operating line and the nent i and
equilibrium line intersect, the number of sepa-
ration stages is infinite. To increase the slope of ci =αi ·pi =αi ·yi ·Pg (169)
the operating line it is necessary to increase the
absorbent flow rate. To determine the true amount of absorbent,
A theoretical separation stage is character- L min is multiplied by an absorption factor A
ized by: for the excess of solvent

1) perfect phase equilibrium between gas and L=A·Lmin (170)


absorbent,
2) complete mixing of the liquid on the plate The absorption factor A must always be cho-
of the separation stage, the concentration of sen such that the operating line is steeper than
liquid above the plate being constant, and the equilibrium line, i.e., it must be greater than
3) flow of gas to the next plate without entrained 1. If the equilibrium line is a straight line, the
absorbent droplets. absorption factor is the ratio of the slope of the
operating line to that of the equilibrium line. For
Practically, phase equilibrium is never a mixture of gases, the theoretical stage num-
reached completely with the plates in commer- ber can be determined graphically for each indi-
cial installations. Also, droplets are frequently vidual component to be absorbed. When this is
entrained with the gas and a concentration gra- done, different numbers of required theoretical
dient occurs above the plate. The combined ef- stages are usually obtained. In such a case, A is
fect of these “imperfections” is reflected by the calculated by using the critical component for
degree of plate efficiency. the absorption process (key component).
Although different values are obtained, de- Next, the rest content of each individual com-
pending on the principle of plate construction ponent at the head of the absorber is determined
and the pairing of materials, the degree of ef- with this selected absorption factor A and the ap-
ficiency in absorption technology is generally propriate equilibrium line, starting with the load-
about 18 – 25 % for poorly soluble compo- ing at the bottom. If the purity requirements for a
nents and 30 – 40 % for readily soluble com- component are not met, the operating line and/or
ponents. This is clearly below the degrees of the absorption factor A have to be changed.
efficiency attainable in distillation technology The design of columns for the absorption
(→ Distillation and Rectification). of multiple components can be calculated by
Once the number of theoretical separation a number of methods, largely supported by
stages is known, the practical number of plates computers. Plate-to-plate calculations have been
has to be defined for each theoretical stage, using successfully carried out with variable gas and
this degree of efficiency. The practical number liquid streams and with variable absorption and
of absorption plates required is extremely im- desorption factors [158–161].
portant for the economy of an absorption pro- Concepts which have been introduced to
cess. Therefore, an optimum balance must be good advantage in absorption technology are the
achieved between excess of absorbent and min- absorption rate E A and the absorption coeffi-
imum number of plates in the column. cient ϕA (see Figs. 10 and 11, next two pages).
Absorption 27

Figure 10. Degree of absorption or desorption as functions of the absorption and desorption factors A and D, respectively, and
of the theoretical plate number nth according to Equation (177)

The (percent) absorption coefficient ϕA of a defined as the ratio of the slopes between the op-
component i from a gas which can be attained erating line and the equilibrium curve, can also
in case of incomplete regeneration is defined as be written as
y2 − y2∗ yh −yh∗ y1 − y2 ys −yh
ϕA = = (171) A= = (176)
y1 − y2∗ ys −yh∗ y1∗ −y2∗ ys∗ −yh∗
Substituting the relation
Combining the relations for the absorption rate
c∗h
yh∗ = (172) (Eq. 174) and the absorption factor (176) for ar-
α∗i ·Pg bitrary numbers of theoretical stages nth yields
for the equilibrium content of the gas phase [158]
y∗h = y∗2 and designating the slope of the equi-
librium line as Anth +1 −A
EA = (177)
Anth +1 −1
1
=m (173) Equation (177) is plotted in Figure 10 for var-
α∗i ·Pg
ious theoretical stage numbers between 1 and
the absorption rate E A is obtained as 20. The limiting tangent of this family of curves
y1 − y2 ys −yh is the line for infinitely large theoretical stage
EA = = (174)
y1 − m·C2∗ ys −m·c∗h numbers.
With the aid of Figure 10, the required theo-
If the amount of component i in the absorber
retical plate numbers can be determined both for
head approaches the equilibrium value, than
absorption, by using the absorption factor A, and

y2i =y2i ∗
or yhi =yhi (175) for desorption, by using the desorption factor D,
if
the absorption rate E A = 1, i.e., the maximum
possible amount of component i has been ab- 1) gas and liquid loading in the column are con-
sorbed from the gas. The absorption factor A, stant,
28 Absorption

factor D can be used to determine the theoretical


stage number nth of the desorber.
By relating the difference between actual and
equilibrium concentration in the absorber head
for the gas phase (y2 – y2 ∗) and for the liquid
phase (c2 − c∗2 ) to the change in concentration
at the bottom of the absorber for the gas phase
(y1 − y∗1 ) and for the liquid phase (c1 − c∗1 ), the
following relation is obtained for the absorption
coefficient:
y2 − y2∗ y2 − m·c∗2
ϕA = =
y1 − y2∗ y1 − m·c∗2
or
yh −yh∗ yh −m·c∗h
ϕA = = (179)
ys −yh∗ ys −m·c∗h

Analogously, for desorption


1
c1 − c∗1 c1 − ·y ∗
m 1
ϕD = = 1
c2 − c∗1 c2 − ·y ∗
m 1
or
1
cs −c∗s cs − m ·ys∗
ϕD = ∗
= 1
(180)
ch −cs ch − m ·ys∗

This correlation is illustrated graphically in Fig-


ure 11 using ϕA and ϕD respectively as ordinate
and the theoretical stage number nth as abscissa
and the absorption or desorption factor A, D as
parameter. The assumptions already mentioned
for Figure 10 apply also to this diagram.

4.2. Chemisorption in Packed Columns


Figure 11. Absorption and desorption coefficient ϕA and
ϕD as a function of the theoretical stage number nth de- Chemisorption normally uses columns with
pending on the absorption and desorption factor A and D packings or similar internals. Mass transfer oc-
(Eq. 179, 180)
curs along the trickling film of the packing and
2) absorption or desorption is isothermal, calculating the required column height becomes
3) the absorbate is present at low concentra- difficult. Hence, packed columns are often cal-
tions, and culated according ot the concept of theoreti-
4) the solubility coefficient αi is constant. cal separation steps. However, experimental data
are required as a rule to get the true number of
Equation (178) shows the dependence of the theoretical separation stages per meter of pack-
theoretical stage number nth on the absorption ing height for given packings and material sys-
factor A: tems.
∗   Colburn [162] introduced a method in
y1 −y2 A−1 1
ln ∗
y2 −y2
· A
+A which the region of separation is subdivided into
nth = (178)
lnA a number of consecutive mass exchange units,
the so-called number of transfer units (NTU).
Here, y∗2 is the equilibrium concentration of the
The sum of the transfer units is called N tot . The
gas phase pertaining to the liquid with residual
transfer unit N must be related either to the gas
loading c2 in the absorber head. Analogous to the
phase or to the liquid phase, N G or N F , respec-
absorption factor A, the desorption or stripping
tively.
Absorption 29

The transfer unit N is a pure thermodynamic


quantity representing the driving force of the
equilibrium process. It is a measure of the devi-
ation from thermodynamic equilibrium and de-
pends on mass transfer.
A simple relation for determining the sum of
the transfer units in the gaseous phase N G,tot is
obtained by analogy to the corresponding rela-
tion (178) for plate columns. For absorption
∗  
y1 −y2 A−1 1
A·ln ∗
y2 −y2 A
+A
NG,tot =
(A − 1)
or
∗  
ys −yh A−1 1
A·ln ∗
yh −yh A
+A
NG,tot = (181)
(A − 1)

A corresponding relation can be derived for des-


orption as a function of loading c.
Figure 12 shows the absorption coefficient
ϕA or the desorption coefficient ϕD , respec-
tively, plotted as a function of N G,tot . The ab-
sorption and desorption rates are defined analo-
gous to those for plate columns (Fig. 10). Other
calculation methods for determining transfer
units will be found in the literature [163].
In addition to the number of required (the-
oretical) transfer units N tot , another practical
equivalence value corresponding to the transfer
unit N G,tot = 1 is needed for the calculation of
packed columns. This is the height of transfer
unit (HTU) which can be referred to either the
gas or the liquid phase. The practical total pack-
ing height h of a packed column is then Figure 12. Absorption and desorption coefficient ϕA and
ϕD as a function of the number of transfer units N G ,tot
h=hG,tot ·NG,tot =hF,tot ·NF,tot (182) with absorption and desorption factor A and D as parameters
(Eq. 181)

concentrations will the thermal effect be so


The transfer units hG,tot or hF,tot are best
small that the absorption can be regarded as be-
determined on actual working columns. If such
ing virtually isothermal. If the key component
practical data are not available, packed columns
is present in larger amounts, the solvent will
can also be calculated by a number of methods
be heated by taking up enthalpy of absorption
found in the literature [157].
because physical processes of absorption are
Nevertheless, despite the increasing accuracy
as a rule exothermic. Part of the enthalpy of
of these often highly complex calculations, it has
absorption is then transferred to the gas.
always been necessary to subject them to a prac-
In chemisorption, this effect is produced by
tical test.
the enthalpy of the reaction which, as a rule,
entails greater heat effect. This temperature in-
crease has such a strong effect on the equilibria
4.3. Nonisothermal Absorption along the height of the column that it must be
taken into account in the calculation.
Only if the component to be absorbed from the
gas mixture (key component) is present in low
30 Absorption

The enthalpy of absorption is approximately 5. Design of Desorption Equipment


equal to the enthalpy of condensation only for [164–169]
components of the gas present in sub-critical
concentrations. For super-critical components it 5.1. Physical Desorption in Flash
must be calculated from known equilibrium val-
ues (see Section 1.6).
Columns
In nonideal mixtures, the enthalpy of mix-
When the total pressure of physical solvents con-
ing (excess enthalpy) appears in addition to the
taining dissolved gases is reduced, the gases des-
enthalpy of condensation. The total enthalpy of
orb until a new equilibrium is established. This
absorption consists of the enthalpy of condensa-
is by far the most economical method for regen-
tion and the differential enthalpy of solution.
erating loaded solvents.
The enthalpy of absorption depends on the
This pressure reduction occurs predomi-
concentration but often only slightly on tem-
nantly isenthalpic, i.e., without performing
perature. To determine the equilibrium line for
work, by way of butterfly valves. If the quan-
nonisothermal absorption, a temperature profile
tities of solvent are large and the pressure differ-
along the column must be given or calculated.
ential great, using flash turbines, that perform
In the simplest case, a linear relation with the
work (Francis or Pelton turbines, or even a re-
loading of the solvent is assumed:
verse running pump) is recommendable.
∆c To calculate the amount of gas that has to
=const. (183)
∆t be flashed per stage in order to reach a speci-
fied pressure it may generally be assumed that
To determine the equilibrium line for
the rate of desorbed gas is in equilibrium with
constructing the McCabe – Thiele diagram
the regenerated solvent. A flash stage thus cor-
(→ Distillation and Rectification,, Chap. 3.1.1.),
responds to a theoretical separation stage.
the equilibria at different temperatures must be
The new equilibrium at the reduced pressure
known.
is again calculated via the material and enthalpy
For given loadings and known average en-
balance for the dissolved component i, with the
thalpies of solution and specific heats, the tem-
nomenclature used in Figure 14.
peratures of the solvent at the various equilibria
can then be determined from the material and L·c4 =L·c3 +y4 ·G4
heat balances for adiabatic absorption. A char-
L· (c4 −c3 ) =y4 ·G4 (184)
acteristic of the equilibrium line is then obtained
as shown in Figure 13. where c4 is the concentration of component i in
the absorbent entering the flash column, c3 is
the concentration of i in the absorbent leaving
the column, G4 is the flow rate of flash gas, and
y4 is the mole fraction of component i in the flash
gas with
G
γ= (relativegasvolume) (185)
L
then
c4 − c3 c4 c3
y4 = = − (186)
γ γ γ

The absorption equilibrium after flashing is:

c3 =α∗i ·p∗3 (187)


Figure 13. Equilibrium curve for nonisothermal absorption
superimposed on equilibrium curves at constant tempera-
tures T 1 to T 5
Absorption 31

QL,4 =QG,4 +QL,3 +QD (190)

where QD is the enthalpy of desorption,


or L · cp, m · t 4 = G4 · cp, m · t 4 + L · cp, m · t 3 + QD
The flash temperature t 4 can be eliminated by
combination with Equation (185) to obtain
QD
CP,m ·t4 − L
t4 =t3 = (191)
v·CP,m,G +CP,m,L

Equation (180) provides a relation between the


flash temperature t 4 = t 3 and the flow rate of flash
gas G4 at a given flash pressure. For physical
systems, the enthalpy of desorption QD is gener-
ally not very temperature-dependent. Equations
(188) and (191) are conveniently solved by itera-
tion on computers. In doing so, the time required
for the calculation can be reduced by using suit-
able initial values from experience with known
material systems.
If the solvent is desorbed by flashing to atmo-
spheric pressure, the partial pressure of the key
component that can be attained is about 0.11 to
0.12 MPa. With direct recycling to the absorber,
this permits only moderate gas purities so that
this method is adequate only for bulk removal
Figure 14. Isenthalpic depressurization of a loaded solvent of gaseous components or as a prestage for fine
in a flash column regeneration. Another flash stage operating un-
By combining equations (186) and (187), the der vacuum may be provided in order to further
concentration of component i in the flashed gas reduce this partial pressure. Further reduction
is: of the partial pressure can be achieved also by
bringing the absorbent into contact with an in-
c3 α∗ (t4 ) ·P4∗ ert gas. This is more economical even in most
y4 = − i (188)
γ γ cases. Also a combination of vacuum regenera-
tion and stripping with inert gas is frequently a
Strictly speaking, this relationship is valid good method.
only for ideal gas behavior, as is usually the case
at reduced flash pressure. At higher total pres-
sure the real gas behavior must be taken into ac- 5.2. Physical Desorption in Stripper
count by introducing fugacity coefficients (see Columns
Chap. 1).
Equation (177) serves for iterative flash cal- Desorption of a loaded absorbent by stripping
culations. The flash temperature t 3 and the flash with an inert gas has the advantage that the ab-
concentration y4 must initially be estimated for sorbent usually does not have to be heated or
each component in a first pass. Here, the gas vol- evacuated. This method of regeneration can be
ume referred to L must be chosen such that the used also at elevated temperatures, thereby re-
boundary condition ducing the amount of stripping gas required.
To design such a stripper column, the oper-
Σyi = 1 (189) ating line is again determined from a balance
in addition to the equilibrium line. The material
is met for all desorbed components. For the en-
balance for the stripper column is calculated in
thalpy balance about the flash stage
the cross-section a – a according to Figure 15
32 Absorption
 
G5 y
c5 =c5 + (196)
L 1−y

Plotting the operating line determined according


to Equation (184) on a concentration-loading di-
agram leads to the curve shown in Figure 16.

Figure 16. Loading diagram for determining the theoreti-


Figure 15. Desorption of a loaded solvent by stripping in a cal number of separation stages for isothermal desorption
stripper column by stripping with inert gas

for a given component i, by following the same For constant liquid and gas streams, the bal-
principle as for absorption (Chap. 4). ance or operating line for desorption, as for ab-
For the lower part sorption, is a straight line. However, the operat-
ing line for desorption is below the equilibrium
L·c+G5 ·y5 =L·c5 +G·y (192) line. By using the same method employed in ab-
sorption, the number of theoretical separation
and for the upper part
stages required for nonisothermal desorption in
L·c6 +G·y=L·c+G6 ·y6 (193) a stripper column is obtained by drawing a se-
ries of steps between yh and ys . The theoreti-
where G5 is the flow rate of strip gas entering the cal number of separation stages for isothermal
stripper column, G 6 is the flow rate of gas leav- desorption can also be determined according to
ing the stripper column, y5 is the mole fraction [158].
of desorbed component i in the stripping gas, y6 From the ratio of the slopes between the op-
is the mole fraction of i in the gas leaving the erating and the equilibrium line, the stripping
stripper column, c5 is the concentration of i in factor D can be determined as shown in Sec-
the absorbent leaving the stripper column, and tion 4.1. Its relation to the absorption factor is
c6 is the concentration of i in the absorbent en-
tering the column. The stripping gas balance in 1
A= (197)
the lower part is D
The isothermal desorption conditions repre-
G (1−y) =G5 (1−y5 ) (194)
sented in Figure 16 apply, strictly speaking, only
For each loading c, the operating line of the des- to the low-loading common when stripping with
orber is obtained as a function of the mole frac- inert gas. At high loading and without the use of
tion y of the key component in the stripping gas an inert stripping fluid, desorption proceeds like
  distillation if the stripping vapor is generated by
y5 ·G5 y·G5 1−y5
c=c5 − + · (195) boiling and evaporation of the solvent.
L L 1−y
If a pure inert stripping gas is used that does not
contain fractions of the component to be des-
orbed y5 = 0 and equation (195) simplifies to
Absorption 33

5.3. Physical Desorption in Reboiler


Columns
Here, nonisothermal desorption occurs by boil-
ing the solvent at the bottom of the column. Tem-
perature increases from the solvent inlet to the
bottom of the column where it reaches the boil-
ing point of the solvent. The component to be
driven off, as a rule, boils at a lower tempera-
ture than the solvent. The rising vapor stream,
consisting mostly of solvent, acts as a stripping
fluid, supported, if necessary, by simultaneously
desorbed inert gases.
Thermodynamically, this type of desorp-
tion is a distillation or rectification process
(→ Distillation and Rectification). It is the most
Figure 17. Loading diagram for determining the theoretical
energy-consuming method for the regeneration number of separation stages in nonisothermal desorption by
of a loaded solvent. reboiling
To desorb dissolved hydrocarbons, for exam-
ple, superheated (live) steam is often blown di- As in distillation, the reboiler column may
rectly into the bottom of the column, producing consist of a distilling and a concentration sec-
an additional stripping effect that lowers the par- tion. The solvent loaded with load C M is fed to
tial pressure similar to vacuum regeneration. the head of the column. In this case, the reboiler
If the solvent has a high boiling point (a so- column consists only of a distillation section, the
called high-boiler), boiling under vacuum is of- operating line being the distillation line R – G.
ten required to attain high degrees of regener- Only when the vapor pressures psi of the com-
ation. If compared to stripping with inert gas, ponents to be distilled and of the solvent psL are
this method has the advantage that the compo- very close, i.e., when β is relatively small, will a
nent to be desorbed, usually hydrogen sulfide, concentrating section G – P be needed. This sec-
is not unnecessarily diluted and is easier to re- tion will then be placed above the solvent inlet.
cover in subsequent process steps (e.g., Claus With the solvents used today, this is generally
units → Sulfur). not necessary.
The design of reboiler columns follows the The theoretical number of separation stages
same principles as in distillation (→ Distillation in desorption is determined graphically by con-
and Rectification). Here, too, the use of equilib- structing a sequence of steps between head and
rium constants with Ki for the key component bottom. The vapor rate to be produced by the
to be driven off and KL for the solvent is advan- reboiler in the column bottom is defined by the
tageous. slope of the operating line. The minimum vapor
For a binary mixture, the following equations rate for concentrations between c5 = cs and cM is
apply to the key component i to be desorbed and given by the slope of the distillation line R – G.
the solvent L (see also Chapter 1): The gaseous mixture leaving the uppermost
plate of the column still contains a considerable
yi yi yL yL
Ki = = ;KL = = amount of solvent vapor which is condensed in
xi c i xL c L
an overhead condenser. The condensate is gen-
Ki yi cL yi (1−ci )
= · = (198) erally used as reflux.
KL ci yL ci (1−yi )
s
In addition to the production of stripping
P
Ki KL = is =β (199) steam, the heat requirements of the reboiler col-
PL
umn consist of the fraction needed to raise the
β ·ci
yi = (200) temperature of the solvent if the latter is not sup-
1 + (β − 1) ·ci
plied to the column at boiling temperature. If
In an equilibrium diagram, Equation (189) is a any low-boiling component, which desorb eas-
hyperbola (Fig. 17).
34 Absorption

ily, are present in the solvent in addition to the in temperature, the conditions during chemical
key component, the heat requirements are even desorption are reflected by the loading diagram
higher. In this case, their enthalpy of desorption (Fig. 18). The theoretical number of separation
must be taken into account. stages is established as previously described by
Any higher boiling components in the sol- a sequence of steps.
vent (e.g., hydrocarbons) are (1) either left in the The partial pressure of the component to be
solvent, because they desorb with difficulty, or expelled is reduced by reboiling the solvent or
(2) considerably increase the steam required for by directly injecting live steam into the bottom
regeneration if they have to be distilled. In addi- of the regenerating column.
tion to the material balances, enthalpy balances While the stripping vapor rises to the column
are also calculated for the reboiler column in the head, if condenses partly, providing the desorp-
usual way to finally determine the performance tion enthalpy for the components to be expelled.
of the reboiler. If the temperature of the spent chemical solvent
The spent solvent leaving the absorber is of- is lower than the boiling temperature in the re-
ten cooled further in the subsequent flash regen- generator bottom, the heat required for heating it
eration stage. To minimize the energy required to the boiling point in order to produce stripping
for the production of stripping steam, the sol- vapor must be supplied as well.
vent is heated in heat exchangers in counterflow The steam demand of the reboiler is derived
to the hot solvent leaving the reboiler column. from an accurate regenerator heat balance.
The design of these heat exchangers has to al- Sufficient stripping vapor must remain at the
low particularly for the inevitable degassing of regenerator head to sufficiently reduce the par-
easily desorbable gases. Otherwise, a so-called tial pressure of the component to be expelled
“back pressure” has to be applied to the solvent relative to the total pressure. The resulting slope
by means of an additional pump to avoid de- of the operating line is generally such that ther-
gassing of dissolved components. mal chemical desorption requires a low number
of theoretical plates, as shown in Figure 18.

5.4. Chemical Desorption in Reboiler


Columns
Because of the parabolic form of the equilibrium
curves in chemisorption, only a relatively small
amount of gas can be desorbed from chemical
absorbents by flashing. Regeneration occurs by
increasing the temperature and reducing the par-
tial pressure in a regenerator. Stripping vapor is
normally generated by reboiling the solvent with
steam.
Nevertheless, a physical flash stage fre-
quently precedes this thermal regenerator, par-
ticularly if the absorption pressure is extremely
high and a large fraction of valuable gases such
as carbon monoxide, hydrogen and hydrocar-
bons, is coabsorbed in the water content of the
solvent.
Chemically loaded absorbents are thermally
regenerated in counterflow columns in the same
way that is used for stripping regeneration of
physical solvents (see Section 5.3).
Assuming that desorption in the regenerat-
ing column is isothermal, and neglecting the fact Figure 18. Loading diagram for the isothermal desorption
of a chemically loaded solvent by reboiling
that the reduction in pressure leads to an increase
Absorption 35

Due to the inflection of the equilibrium curve, 2. J. M. Prausnitz, T. F. Andersen, E. A. Grens,


the difference in partial pressure in the regenera- C. A. Eckert, R. Hsieh, J. P. O’Connell:
tor bottom is considerably less than in the head. Computer Calculations for Multicomponent
As the stripping vapor rate Gh at the column Vapor-Liquid Equilibria, Prentice Hall,
head is required to make up for the difference be- Englewood Cliffs, N.J. 1980.
tween the total pressure pg and the partial pres- 3. B. I. Lee, M. G. Kesler: “A Generalized
sure of the key component p1 as illustrated by Thermodynamic Correlation Based on
point 1 in Fig. 18, the required stripping vapor Tree-Parameter Corresponding States,” AIChE
J. 21 (1975) 510 – 527.
rate Gh at the column head can be described by
4. S. Westmeier, W. H. Hanthal, G. Hecht, R.
L· (ch −cs ) · (Pg −p1 ) Kümmel, D. Lempe, F. Rösler, M. Rotter, I.
Gh = (201) Westmeier, W. Wettengel: “Stoffwerte,
p1
Verfahrenstechnische Berechnungsmethoden,”
The stripping vapor rate for the column bot- Part 7, VCH Verlagsgesellschaft, Weinheim,
tom can then be derived from the regenerator New York 1986.
heat balance according to Equation (190). If the 5. U. Plöcker, H. Knapp, J. M. Prausnitz:
residual partial pressure of the expelled compo- “Calculation of High-Pressure Vapour-Liquid
nent above the regenerated solvent is limited by Equilibria from a Corresponding States
the vapor requirement of the regenerator, the gas Correlation with Emphasis on Asymmetric
purity increases with higher pressure in the ab- Mixtures,” Ind. Eng. Chem. Process Des. Dev.
sorber. Chemical regeneration systems provide 17 (1978) 324 – 332.
6. H. Renon, J. M. Prausnitz: “Local
for heat exchange between the spent and the re-
Compositions in Thermodynamic Excess
generated solvent in order to reduce the demand
Functions for Liquid Mixtures,” AIChe J. 14
for stripping vapor. (1968) 135 – 144.
Also in chemical desorption systems the 7. J. Gmehling, B. Kolbe; Angewandte
stripping effect can be supported by an inert gas. Chemische Thermodynamik für Chemiker,
If a dry inert gas is used, it takes up steam until Verfahrenstechniker and Chemieingenieure,
it is saturated. The cooling effect in the regener- Thieme Verlag, Stuttgart 1988.
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