Operações Unitárias III

INSTITUTO SUPERIOR POLITÉCNICO DE TECNOLOGIAS E CIÊNCIAS

PROCESSOS DE ABSORÇÃO FÍSICA E QUÍMICA

Prof. Dr. António André Chivanga Barros

 Absorção
É uma operação de transferencia de massa baseada nos principios de
solubilidade de um soluto em um solvente líquido.

A absorção pode ser: a) Física; b) Fisico-Química.

A força motriz que rege esta operação é o gradiente de concentração.

Estas operações são realizadas em colunas de absorção com as mesmas

caracteristcas das colunas de destilação, mas sem os acessórios como o
condensador e o reboiler (refervedor).

2
 Absorção
As operações de absorção são isotérmicas com as temperaturas de
operação abaixo da temperatura de ebulição do solvente.

i. Lavagem de gases presentes em ambiente

confinado;
Principais ii. Purificação do GLP;

aplicações iii. Tratamento das emissões gasosas no sistema de

combustão;
iv. Tratamento do biogás produzido em um
biodigestor.

3
 Equipamentos utilizados

Por envolver soluções altamente diluidas, são comumente

utilizadas colunas com recheios (empacotados).
4
Funcionamento da Coluna de Absorção

O Liquido é o solvente que descende no interior

da coluna, absorvendo o soluto presente na fase
gasosa.

5
Principios de funcionamento

6
Principios de transferência de massa

7
 Typical Absorber
Effluent Air
Solvent (water) 70 ppm (molar) acetone
1943 kgmol / hr

Packed Tower

Feed (air + acetone)

703 kgmol / hr
Water Out + acetone 1.4 mol % acetone
 Mass Balance
Lo, Lm, xo, Xo
G1, Gm, y1, Y1

Tray 1

Tray N
LN, Lm, xN, XN
GN+1, Gm, yN+1, YN+1
 Conceito do estágio téorico

LN-1, Lm, xN-1, XN-1 GN, Gm, yN, YN

As correntes que
As correntes estão
abandonam o estágio
Stage N associadas ao balanço
estão em equilibrio
termodinamico entre si material

LN, Lm, xN, XN

GN+1, Gm, yN+1, YN+1
 Linha de operação de absorção
Solvent 200 80/4

4 CO2 Prato 1
200/4 80/8

Fluxos molares Prato 2

4 CO2
200/8 80/12

4 CO2 Prato 3

200/12 80/16

4 CO2 Prato 4

Solvente / CO2 200/16 80/20 N2 / CO2

Graphical Technique

Figure 6.8 Continuous steady-state

operation in a counter-current
contactor with equilibrium stages (a-
absorber, b–stripper) .
Graphical Technique

Figure 6.9 Operating lines for an

absorber
Graphical Technique
Kremser Method for Theoretical Trays
(Absorber)

Lo, x o G1,y1
Prato 1
Prato N

L N, x N GN+1, yN+1
Kremser Method for Theoretical Trays
(Stripper)
 y N 1  
  xo  m   1  1 
log    1    
  x N  y N 1   S  S 
  m   mG
N where : S 
log S L

Lo, x o G1,y1
Tray 1
Tray N

L N, x N GN+1, yN+1
Kremser Chart
Uma coluna de absorção com área da seção recta transversal de 0,52 m 2, contendo
Anéis Raschig de 2 ½”, é utilizada para a recuperação da amônia de uma corrente de
ar. A coluna opera a 20oC e 1 atm e recebe uma mistura de ar amônia (MM =
29g/mol) com 7,6 mol% de amônia, a uma vazão de 20 mol/h. O gás estabelece
contato com uma corrente de água com uma vazão de 35% maior que a mínima
necessária. Nas condições praticadas, considerando o recheio e o sistema ar-amônia
sob pressão atmosférica, a altura equivalente a um prato teórico é dada por (SETE
PONTOS):

H0G=0,453G0,152L-0,27, onde H0G é expresso em m e L e G em kg/(m2 h).

Para o caso referenciado, a relação de equilíbrio é dada por y=1,385x. Considere as

vazões de líquido e gás constantes ao longo da coluna de absorção e supondo que o
processo seja controlado pela resistência a transferência de massa na fase gasosa e
com uma recuperação da amônia de 97%, calcule a altura necessária para esta
operação, que ocorre em contracorrente. Determine o diâmetro da coluna e a área
da secção recta transversal.
 Example
Carbon Disulfide, CS2, used as a solvent in a chemical plant, is evaporated from the product in
a drier into an inert gas (essentially N 2) in order to avoid an explosion hazard. The vapor-N 2 mixture
is to be scrubbed with an absorbent oil, which will be subsequently steam stripped to recover the CS 2.
The CS2-N2 mixture has a partial pressure of CS 2 equal to 50 mm Hg at 24 C and is to be blown into
the absorber at essentially standard atmospheric pressure at the rate of 50,000 ft 3 / hr. The vapor
content of the gas is to be reduced to 0.5 %. The absorption oil has a molecular weight of 180.
The oil enters the absorber free of CS 2. The oil – CS2 solution follows Raoult’s Law. The vapor pressure
of CS2 at 24 C is 346 mm Hg.

Determine: The minimum liquid / gas ratio

For a liquid / gas ratio of 1.5 times the minimum, determine

the flow rate of oil in lb / hr

The required theoretical stages graphically and from

the Kremser method.
Packed Tower Design

Random Packing
 Structured Packing

Fair, J.R., Seibert, A.F., Behrens, M., Saraber, P.P., and Olujic, Z. “Structured
Packing Performance-Experimental Evaluation of Two Predictive Models ”,Ind. Eng.
Chem. Res. 39 (6), 1788-1796 (2000).
Structured Packing
Area = S
Mass Balance

 V dy  K y a y  y  *

Change in gas
dZ = Flux out of gas
composition
 Design Equations
L'  L (1  x) and V '  V (1  y )

 y  dy dy
d (V y )  V ' d    V '  V
1 y  (1  y ) 2 (1  y )

y1  V  dy Mass
Z   ' 
y 2  K aS  (1  y )( y  y * )
 y 

(1  y )  (1  y * ) cDAB ( y A1  y A 2 )
(1  y ) LM  NA 
  z 2  z1 (1  y A ) LM
ln (1  y ) * 
 (1  y )

HTUOG NTUOG Unidirectional diffusion

  Eqn. 3-35
y1
 V  (1  y ) LM dy
Z 
y2  K ' a (1  y ) S  (1  y )( y  y * )
 y LM 
 HTUOG Calculation

1 1 m
 
K y k y kx

Two resistance theory - need individual coefficients and

area from mass transfer model:

Onda, K., Takeuchi, H., Okumato, Y., “Mass Transfer Coefficients Between Gas
and Liquid Phases in Packed Columns,” Journal of Chemical Engineering of Japan,
1, 56 (1968).
 Onda Equations
0.70
 1   G 
k y    5.23  ScG 1/ 3 aP d P 2
 aP DAB   aP G 

1/ 3 2/3
   L 
k x  L   0.0051  ScL 1/ 2 aP d P 0.40
 g L   aw  L 

  0.75 0.1
 
 0.05 0.2  
     L  L 2
a  L 2
 
aw  aP 1  exp  1.45  c     2 P     
      aP  L    L g    L  aP   
 

c= 61 dyne /cm for ceramic packing

c= 75 dyne /cm for steel packing
c= 33 dyne /cm for plastic packing

Units on ky and kx are length per time

Effective Area (aw)
Structured Packing Wetted Area
NTUOG Calculation
(Absorber Example)

Vout = 62 lbmol/hr
Lin = 488 lbmol/hr 3.2 mol % NH3

35
NTUOG
95 % NH3 removal 30

25 0.40(1  y ) LM dy
Area    3.44
0.032 (1  y )( y  y * )
20

15

10
Vin = 100 lbmol/hr 5
40 mol % NH3

0.0 0.10 0.20 0.30 0.40

y
 NTUOG Calculation
(log mean approximation)

NTU OG 
 yin  yout 
 
 
  
 yin  yin*  yout  yout*
 
   
 y  y *


ln  in in
* 

 
  yout  yout  

Assumes dilute solution and plug flow of each phase

 Packed Column HETP Behavior
Mass Transfer Results
24.0 psia - C6/C7
25

RSR-#0.5
1" SS Pall Rings
IMTP-40
20

IMTP-40

15
HETP ( in )

1" SS Pall Rings

RSR-#0.5

10

0
0 0.2 0.4 0.6 0.8 1 1.2 1.4 1.6 1.8 2

f-Factor ( ft/s(lb/ft^3)^0.5 )
 Packed Absorber Example
Solvent (water)
Effluent Air (y1 = 0.004)
2.2 kmol / sec
xo = 0
Data:

yi = 40 xi Packed Tower
CSA = 1.5 m2
kx = 0.0176 kmol /m2 sec
ky = 0.0080 kmol / m2 sec

aw = 100 m2 / m3 Find: NOG, HOG, Z

Feed (air + SO2)

Water + SO2 Out 0.062 kmol / sec
(yN+1 = 0.016)
 10 Minute Problem
A packed absorption tower yields a concentration based. NTUOG of 10.
Determine the tower height given the following information (The concentrations
of the transferred component are dilute in both the liquid and gas).

Data: Tower diameter = 5 ft.

Gas density = 0.20 lb/ ft3
Gas superficial velocity = 3 ft / sec
Kog = 0.01 m /sec
m = 2.0
P = 1 atm, T = 80 F
ae = 200 m2 /m3
 Packed Tower Hydraulics
(random packing)

1) Leva plot technique

2) Stichlmair model
 Pressure Drop Behavior
Pressure Drop Results
24.0 psia - C6/C7
10

RSR-#0.5
1" SS Pall Rings
IMTP-40
1" SS Pall Rings

1
DP/Z ( in H2O/ft )

RSR-#0.5

0.1 IMTP-40

0.01
0.1 1 10
f-Factor ( ft/s(lb/ft^3)^0.5 )
 Pressure Drop (Leva) Plot

Figure 6.35 (a) Generalized pressure drop correlation for packed columns.
(b) Correction for liquid density. (c) Correction for liquid viscosity.
Packing Factors
 Stichlmair Model

2  C 
  h   3

 1   1   
       PIrr 
2
Pirr 
(1   )
 
h  ho 1  20 
     Z  g  
 
PDry    L

4.65
 h
1  
 

Stichlmair, J., Bravo, J.L., Fair, J.R., “General Model for

Prediction of Pressure Drop and Capacity of Countercurrent Gas/Liquid
Packed Columns,” Gas Separations and Purification, 3:19-28 (1989)
 Stichlmair Model
 C1 C2

2 Re g 1
2 Re g 2
V a
ho  0.555 Fr 1/ 3
FrL  L
C
g
L 4.65
fo

C1 C d pVg  g 61   
fo   21  C3 Re g  dp 
Re g Re 2 g a
g

3 1    Z  2
PDry  f o  4.65   g   Vg
4     dP 
 Stichlmair Model (flood point)
PIrr
 Infinite pressure drop at the flood point
PDry

2c
2 40   ho
 PIrr   3  186 ho
    0
 Z L g  flood    
2 2
 PIrr   PIrr 
1    ho 1  20      ho 1  20   
 Z  g
 L  flood   Z  g
 L  flood 
Stichlmair Constants
 Example
A tower packed with 1 in. Ceramic Intalox saddles is to be built to
treat 25,000 ft3/ hr of entering gas. The ammonia content of the
entering gas is 2 percent by volume. Ammonia-free water is used as
the absorbent. The temperature is 68 F and the pressure is 1 atm.
The ratio of the gas flow to the liquid flow is 1 lb of gas per lb of
liquid.
The tower diameter is 1.67 ft.

Using both the Leva plot and the Stichlmair correlation determine the
total tower pressure drop if the tower packed height is 20 feet.
 10 Minute Problem
An air-water test is being run on a 10 foot bed of 1
inch (25 mm) metal Pall rings. The air rate is 350 ft3 /
min and the liquid rate is 15 GPM / ft2. The tower is
16.8 inches in diameter, the operating pressure is 1
atm and the temperature is 80 F. What is the total
column pressure drop?
 Carbon Capture and Sequestration
Power N2 H2O

CO2 + N2 + H2O
Boiler / Generator CO2 Recovery CO2

Trace
Components
Coal Air (O2 + N2)

Underground Formation
 Absorption with Chemical Reaction
Flue Gas Out CO2

Absorber Stripper 100–120 °C

40–65 °C Heat X

Flue Gas In
5 % O2
Reboiler
12 % CO2
83 % N2
Rich Amine Lean Amine
Commercial Process Configuration
Mass Transfer with Fast Reaction
CO2 + 2MEA = MEACOO- + MEAH+
Mass Transfer with Fast Chemical Reaction (CO2
+ MEA)

DCO 2 k Rxn [CMEA ]interface

N CO 2  ( PCO 2,interface  PCO
*
2 , bulk )
H CO 2

MEA (monoethanolamine)