Residue Curve Maps Chemical Engineering Separations 5

Lecture 8 Residue Flow Maps and Distillation Boundaries John Christy

V y

For a batch still dt = Vy where x and y are composition vectors dx dM Expanding M dt = dt x Vy = V (x y ) and noting we obtain M dx = x y dM = V
dt V dt

dMx

Residue Curve Maps

Introducing a dimensionless time, , such that d = V dt
M

Below is a plot of x versus for six different initial compositions of ethanol - isopropanol In all cases x decreases with time. I.e. ethanol boils off until only isopropanol is left in the still pot. All trajectories on the phase line move towards x=0 with time

Residue Curve Maps - Binary

gives

dx = xy d

(1) ,
d = dM 1 dt = d ln M dt M

Note since

dM =V dt

and initial conditions =0 and M=M0 at t=0

(t ) = ln

M0 M (t )

Residue Curve Maps - Binary

For pentane-dichloromethane at 1bar a minimum boiling azeotrope (30.6C) is found at 52% pentane. 34.9C The final component left in the still pot will 30.6C now depend on which side of the azeotrope the feed composition lies
38.9C

Residue Curve Maps - Binary

Below is a plot of x versus for six different initial compositions of pentane-dichloromethane For x<0.52 initially, all compositions tend towards x=0 as time proceeds For x>0.52 initially, all compositions tend towards x=1 as time proceeds

Residue Curve Maps - Binary

Representing the concentrations (x) along a line, we have
Isopropanol Ethanol

Residue Curve Maps - Ternary

Consider ideal system: methanol ethanol npropanol at 1atm Integration of eqn (1) for different feeds leads to the residue curve map on the right first methanol-rich vapour boils off, then ethanol

For the ideal binary separation, and

dichloromethane 38.9C azeotrope 30.6C pentane 34.9C

The composition always moves towards the less volatile (higher boiling) component as the distillation proceeds

Residue Curve Maps - Ternary

All residue curves start with methanol - this is an unstable node n-propanol acts as a sink and is called a stable node ethanol acts as sink along methanolethanol line and source along ethanol-propanol line - saddle point

Residue Curve Maps - Properties

1 Residue curve through any point is tangent to vapour-liquid tie-line through point 2 Residue curves do not cross or intersect 3 Boiling temp always increases along curve 4 steady state solutions occur at all pure components and azeotropes 5 steady state solutions are stable nodes, unstable nodes or saddle points 6 residue curves at nodes are tangent to edge with relative volatility closest to unity

Residue Curve Maps - azeotropes

For ideal system only one type of residue curve map For single minimum boiling azeotrope 3 maps are possible

Residue Curve Maps - azeotropes

Azeotrope is unstable node (lowest boiling), heavy pure component is stable node (high BP) light and intermediate comps are saddles

Residue Curve Maps - azeotropes

Azeotrope is unstable node (lowest boiling), heavy pure component is stable node (high BP) light and intermediate comps are saddles This is basis of extractive distillation. Known as extractive map

Residue Curve Maps - azeotropes

Light comp is unstable node (lowest boiling), heavy pure component and intermediate are stable nodes (high BP) azeotrope is saddle Line between light comp and azeotrope is distillation boundary feed above boundary yields intermediate, below, heavy comp.

Residue Curve Maps - Properties

7 Each distillation region must contain one unstable node, one stable node and at least one saddle 8 There must be a saddle on at least one end of every distillation boundary

Residue Curve Maps - Examples

Residue Curve Maps - Examples

Distillation Boundaries
80.1 Benzene

Mixture A in still, acetone boils off, so that liquid composition moves towards azeotrope Mixture B - liquid composition moves towards azeotrope Mixture C - liquid composition moves towards benzene
D

Mixture D - liquid composition moves towards benzene

C A B Azeotrope 64.4 Chloroform 61.2

Examples with more than one azeotrope

Acetone 56.2

Distillation Boundaries
80.1 Benzene

Distillation trajectories
For batch still
dx = xy d

Similarly with B, chloroform boils off first, followed by azeotrope, to leave benzene

as

dx = x y dh


x (h = 0 ) = x D r 1 xn + xD r +1 r +1
      

Staged column
A Acetone 56.2 Azeotrope 64.4 B Chloroform 61.2

y n +1 =

as

y n +1 = x n

x0 = x D

an integrated form of the differential eqn

Distillation trajectories
Through use of K values, noting that at equilibrium y = K x , we can either integrate with respect to h for packed columns or substitute y = K x in the expression for staged columns (giving Kx = x ). This leads to the form of composition trajectory obtained above for residues in batch distillation. The curves are identical to residue curves for packed columns and almost the same for staged columns (both at total reflux)
i i i

Distillation trajectories
Comparison solid lines, residue curves; dashed lines, staged column distillation lines

i , n +1

i i ,n +1

i i , n +1

i ,n

Distillation Boundaries
80.1 Benzene

Distillation Boundaries
80.1 Benzene Distillation Boundary

x F1

x F2

If we choose a range of feed positions, we discover that there is a Distillation Boundary distillation boundary, with all feeds to the left of this boundary producing acetone-rich mixtures overhead and benzene bottoms, whereas to the right of the boundary, chloroform-rich mixtures are obtained overhead
Azeotrope 64.4 Chloroform 61.2

x F1

x F2

Acetone 56.2

Acetone 56.2

A B Azeotrope 64.4

Chloroform 61.2



Mixture A in still, initially acetone boils off, so that liquid composition moves towards azeotrope. Once binary azeotrope ratio of acetone to chloroform is almost achieved, azeotrope boils off so that liquid left is enriched in benzene

For continuous still under total reflux

Packed column
dx r +1 x =x y+ D dh r r