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)
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
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)
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)
Table 1. Different expressing of Henry’s law constant constants depends on the loading or on the par-
tial pressure:
Constant Dimension Concentration
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
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
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
For zG L
i ≈ 1 in the vapor phase and z i 1 in the
liquid phase follows: ∆zi ≈ 1, fi ≈ pi ,
∞ 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)
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
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)
Ha=kl−1 ·
m−1 n 1/2
2DAL kmn ciA cb
B / (m+1) (149)
(150)
(151)
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
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].
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 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
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
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
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.
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Absorption 37