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    Chemical Engineering - Separations 5 Residue Curve Maps: ξ, such

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    Residue Curve Maps Chemical Engineering Separations 5 Lecture 8 - distillation Boundaries Introducing a dimensionless time, x. 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.

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    Chemical Engineering - Separations 5 Residue Curve Maps: ξ, such

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    chikukotwal
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    Residue Curve Maps Chemical Engineering Separations 5 Lecture 8 - distillation Boundaries Introducing a dimensionless time, x. 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.

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    Residue Curve Maps Chemical Engineering Separations 5 Lecture 8 - distillation Boundaries Introducing a dimensionless time, x. 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.

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    82 views4 pages

    Chemical Engineering - Separations 5 Residue Curve Maps: ξ, such

    Uploaded by

    chikukotwal
    Residue Curve Maps Chemical Engineering Separations 5 Lecture 8 - distillation Boundaries Introducing a dimensionless time, x. 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.

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    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

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