Principles of Absorption: Diameter of a packed absorption tower depends on the quantities of the gas and liquid handled their

r properties, and ratio of one stream to the other. Height of tower and hence total volume of packing depends on: 1. The magnitude of desired concentration changes 2. The rate of mass transfer per unit of packed volume In computing tower height: Consider: Material balances Enthalpy balance Estimates of driving force and mass transfer coefficient Material balances

La Xa

Va Xa

La + V + L + Va La Xa + Vy = Lx + Va Ya La + Vb = Lb + Va La Xa + Vb Yb + Lb Xb + Va Ya

Operating line: Y = (L/V)X + (Va Ya La Xa)V * Must lie above the EL in order for gas absorption to take place since this gives a positive driving force: Y-Y* for absorption X & Y represent the bulk compositions of L & G in contact with each other at any given section through the column. - assumed that the compositions at a given elevation are independent of position in the packing.

Vb Yb

Lb Xb

The absorption of a soluble component from gas mixtures makes V (total gas rate) decrease as the gas passes thru the column, and L (liquid flow) increases. - It makes OL slightly curved This complication can be circumvented by recognizing that the quantity of the solute free gas, which is essentially insoluble, is constant. Let V = molar flow rate of solute-free gas V = V (1-Y) *for dilute mixtures (containing less than 10% of soluble gas), the effect of changes in total flow is usually ignored and the design is based on the average flow rate. LIMITING GAS LIQUID RATIO OL equation: m = L/V important in the economics of absorption in a countercurrent column

Y Y* - driving force for mass transfer Y Y* vertical distance between OL and EL

Increasing L/V increases the driving force everywhere in the column except at the very top, and the absorption column does not need to be as tall. * However, using larger amount of liquid gives a more dilute liquid product, which makes it more difficult to recover the solute by desorption or stripping. Energy cost for stripping often a major part of the total cost of an absorption-stripping operation. *Optimum liquid rate for absorption is found by balancing the operating costs for both units against the fixed cost of the equipment. L = 1.1 1.5X the maximum rate (unless the liquid is to be discarded and not regenerated) Rate of Absorption - Expressed in 4 different ways using individual coefficients or overall coefficients based on the gas or liquid phases. Volumetric coefficient used because it is more difficult to determine the coefficient per unit area and because the purpose of the design calculations is generally to determine the total absorber volume. * rate of absorption per unit volume of packed column is given by any of the following equations where X & Y refer to the mole fraction of the component being absorbed. (18.7) r = ya (Y Yi) (18.8) r = xa (Xi X) (18.9) r = Kya (Y Y*) (18.10) r = Kxa (X* X) a = individual volumetric mass transfer coefficient (kg-mol/m3-h-unit mole fraction) Ka = overall volumetric mass transfer coefficient (kg-mol/m3-h-unit mole fraction) a = interfacial area/ unit volume of packed column *a hard to measure or predict - design calculations can be based on the volumetric coefficients. interface composition (Yi, Xi) (18.11) = * usually not necessary to know the interface compositions, but these values are used for calculations involving rich gases or when the equilibrium line is strongly curved. (17.57) = + * based on two film theory (many mass transfer theories)

Overall coefficients (from kya & kxa, using the local slope of the equilibrium curve m, as shown in (17.57) Kxa = (3-20) kxa **if kya and kxa are equal, m>1 liquid film resistance is controlling = + (18.12) & = resistance to mass transfer in the gas film & liquid film resp. = + (18.13) * in packed column kxa = 3 to 20 times (kya) Calculation of Tower Height *Gas-film coefficient are often used & Kya - choosing a gas-film coefficient does not require any assumption about the controlling resistance. Even if the liquid film controls, a design based on Kya is as simple and accurate as one based on Kya & kxa. * mass transfer in most cases is treated using the same type of equations, which feature a mass transfer coefficient, K = rate of mass transfer per unit area per unit concentration difference. fig. 18.12 S, cross section Differential volume in height dZ = SdZ Neglect V (molar flow rate)

Amount absorbed in section dZ = -Vdy Equals the absorption -Vdy = Kya (Y Y*) SdZ (18.14) r v Vol abs.rate rate x differential volume Rearrange for integration and group the constant factors ( = ) (to eliminate negative) (18.15) v = molar flowrate

Number of Transfer Units From 18.15; ZT =

(18.16) Represents the change in vapour concentration divided by the average driving force - Called the NUMBER of transfer units (NTU) Noy indicates that it is the overall driving force for the gas phase

has the unit of length:

= m (unit of length) Called the height of transfer unit (HTU), Hoy simple design method is to determine Noy from the xy diagram & multiply it by Hoy (obtained from literature or calculated from mass transfer correlations) ZT = HoyNoy (18.17) * NTU is like the number of ideal stages; Values are equal only if OL and EL are straight and parallel. (see fig. 18.13 p. 563) * for this case (18.19) for straight OL & EL, NTU is the change in concentration divided by the logarithmic mean driving force: (18.19)
( ( ) ( ) )

(based on the gas phase)

- a simplification made of eqn. 18.16 & 18.19 - important in the case of dilute concentrations - similar with the simplified heat-transfer design eqn. using log-mean driving forces Based on liquid phase: Number of liquid phase transfer units Nox Noy (unless the OL and EL are straight and parallel)

For absorption, OL is steeper than EL so: Noy> Nox( offset by the difference between Hoy & Hox, and column height can be determined using either approach) The OVERALL HEIGHT OF A TRANSFER UNIT can be defined as the height of a packed section required to accomplish a change in concentration equal to the average driving force in that section. 4 kinds of transfer unit (those based on individual or overall driving forces for gas and liquid phases)

Gas film: Liquid film: Overall gas:

Hy = Hx=

Ny = Ny =

(18.21) (18.22) (18.23) (18.24)

Hoy =

Noy = Nox =

Overall liquid: Hox =

Number of transfer units (overall) based on liquid phase Alternate form of transfer coefficients Gas-film coefficient - often based on a partial pressure driving force instead of a mole fraction difference - written as Kga of ga ; Substituting Hy = Hx =

; P = total pressure or Gm for and Hoy = Hox =

for (18.25) (18.26) Hoy =

Number of transfer units required - a measure of the difficulty of separation. If very high purity of the products are desired, larger number of transfer units is required. Height of a transfer unit - a measure of the separation effectiveness of the particular packing for the chemical species being processed. Small HTU - high rate of interphase mass transfer - surface area for transfer is large Single transfer unit - gives a change of composition of one of the phases equal to the average driving force producing the change. - its action can be compared to that of an equilibrium stage.
( ( ) ( ) )

To use the equation, knowledge of the following data is required: 1. value of kxa, kya, Kxa or Kya as a function of the flow rates of V and L and the transport properties of these 2 phases. 2. Relation between point compositions in either phase and the point driving force, (x - xi), (x x*), (yi y) or (y* - y) Equimolar counter diffusion - occurs in distillation since there is an equal rate of interchange of the more and less volatile constituent between phases * with the assumption of constant molar overflow * =
( )

Upon integration, the integral term gives a quantity defined by Chilton and Colburn known as NTU (number of transfer units) which as the measure of the ease or difficulty of separation

Diffusion through stationary phase - includes gas absorption, liquid extraction, adsorption and ion exchange. Unlike distillation, the assumption of constant V and L is not valid. Ex. In gas absorption, both phases will have variable flow rates as a result of the transfer of solute to or from the phases. - offset by recognizing that the quantity of solute-free gas, which is essentially insoluble is constant. Let V = molar flowrate of solute-free gas V = V (1-y) Thus: ( ) Vd( ) = V ( ) = V ( )=V ( ) ( ) ( )Sdz

From 18.6; (1) Design equation: Substitute V = ( ) ( V )

to the above equation;

Solve for tower height (Foust); ( )( )

In terms of L-phase, the design equation becomes:

)(

Graphical Integration by Baker based upon the use of an arithmetic average of the driving forces and the assumption that over the length of 1 transfer unit, both operating line and equilibrium line are essentially linear. [Ex. 16.1] (Foust) A gas stream containing a valuable hydrocarbon (MW=44) is to be scrubbed with a nonvolatile oil (MW=300) in a tower packed with 1-in Raschig rings. The entering gas analyzes 20 mole % HC and 95% of this HC is to be recovered. The inert gas MW is 29. The gas stream enters the column at 5,000lb/hr.ft2 and HC-free oil enters the top of the column at 10, 000lb/hr.ft 2. Determine the NOG for this operation. OIL MW = 300 10, 000lb/hr.ft2
Gas Absorption Column Va Ya

Lb Xb *95% recovered

Gas Stream 20% mole HC 5,000lb/hr.ft2 HC (MW = 44) Gas (MW = 29)

Reqd: NOG Solution: *Because gas absorption involves diffusion through stationary components, appropriate expression for NTU is: ( ) ( )( ) (This equation is valid since it is substantially free of any assumption.) Basis: 1 lbmole of entering gas (0.2 mol HC; 0.8 mol inert gas) Average MW = Y1M1 + Y2M2 = 0.20(44) + 0.8(29) = 32 lb/lbmole Molar flow rate: Vb = (5,000lb/hr.ft2)(1 lbmole/32lb) = 156.25lbmole/hr-ft2 Gas in = Gas out = (156.25)(0.8) = 125 La = 33.33 HC in Va = (156.25)(0.20)(0.05) = 1.5625 Xa = 0 Va = 1.5625 + 125 = 126.5625 Ya =

Va = 126.5625 Ya = 0.01235

= 0.01235

For the oil: La = 10,000/300 = 33.33 lbmole/hr-ft2 Xa = 0 HC in Lb = 156.25(0.20)(0.95) = 29.6875 Lb = 29.6875 + 33.33 = 63.0175 Xb = 4
L x V y

Lb = 63.0175 Xb = 4

Vb = 156.25 Yb = 0.2

Y= (1-Y)lm =
( ( ) ( ) )

It is quite evident that the phase flow rates are not constant through the column so that the use of Eq. 16. 16 is needed: ( ) Vd( ) = V ( ) = V To plot the operating line, a material balance is written from the tower bottom to any point within the tower: Vbyb + Lx = Vy +Lbxb (a) In terms of non-diffusing component ( yb) ( y) V = V (1-yb) (b) L = L (1-xb) (c)
( xb) ( x)

Therefore, (

( )

( )

This equation is valid throughout the column, and simply by knowing V, L, x b, yb and any point (x,y), intermediate between the terminal points may be obtained. V = (156.25)(0.80) = 125 L = 33.33 ( ) ( ) ( ) ( ) Therefore, equation of the operating line is: ( ( ) ) ( ) ( ( ) ( ) ( ( ) ) ( ) ( )

Data for the operating line are calculated from (f) and tabulated: x 0 0.0307 0.1325 y 0.0125 0.02 0.05 Data for the equilibrium line: x 0.1 y 0.01 Plot:
EL OL 0.25

0.271 0.10

0.383 0.15

0.472 0.20

0.2 0.023

0.3 0.06

0.4 0.125

y (mole fraction HC)

0.2 0.15 0.1 0.05 0 0 0.1 0.2 0.3 0.4 0.5

- OL and EL are both curved, which causes serious error if t e log mean driving force (YL) is employed. - HC concentration in the gas stream is relatively high throughout most of the column. The assumption that (1-y) is equal to (1-y)lm is not completely sound, so eq. 16.7 works best.

x (mole fraction HC)

( (

( )

Yb* = 0.173 Yb* = mXb Ya* = 0.0124 Ya* = mXa ( ) ( ( ) Trapezoidal Rule -area of trapezoid by Y2 and Xi = (Y2 Yi) ( )
( ) ( )

( )

( )

) (

*True for four equal segments but can be generalized to any number. *Tends to overestimate the area under the curve for functions of the shape shown, a shape often encountered in the integration of 2 expressions for transfer units. -dividing the integral into larger number of segments increases the accuracy of numerical integration. Graphical Integration by Baker (accurate if both OL & EL are slightly curved; 4+ stages) Noy based on YL based upon the assumption of both phases being dilute, but in this example, the liquid phase is concentrated as it leaves.