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Introduction
This course is, in general, concerned with the processes effecting the separation in the outline of a chemical process shown below.
One example of a separation process, liquid-liquid extraction, may be used to seperate propionic acid from a mixture with kerosine as follows:
phases/streams in thermodynamic equilibrium, each phase/stream being removed from the stage without entraining any of the other phase / stream.
Binary Distillation
Distillation is a process involving an equilibrium between two phases - liquid and vapour. For a pure compound, in particular a pure ionic compound, a sharp boiling point usually exists. For a mixture, however, a phase equilibrium exists over a range of temperature, as shown below.
The first bubble of vapour formed when a liquid (subcooled) is heated is formed at the bubble curve. The first drop of liquid formed when a vapour (superheated) is cooled is formed at the dew curve. x = mole fraction m.v.c. in liquid y = mole fraction m.v.c. in vapour
The temperature - composition diagram is used for isobaric conditions. For isothermal (constant temperature) conditions a pressure - composition diagram is used.
Pmvc = partial pressure of more volatile component Plvc = partial pressure of less volatile component
Azeotropes
Type A
(e.g. Acetone - CS2, Chloroform - methanol)
Fig 9:
Fig 10:
Fig 11:
Type B
(e.g. Acetone-Chloroform)
Fig 12:
Fig 13:
Fig 14:
Fig 15:
Fig 16:
Flash Distillation
Flash distillation is a process typically used to effect seperation of crude oil. The process involves heating a feed stream and then allowing it to expand into a vessel maintained at low pressure. Partial vaporisation then occurs, and a phase equilibrium is (ideally) reached.
A material balance gives: F = L + V ...1 An m.v.c. balance gives: FZF = Lxe + Vye ...2 Now from 2,
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Vye = FZF - Lxe ye = (FZF / V) - (Lxe/V) y = c + mx Putting xe = ZF gives ye = ZF[ (F / V) - (L/V) ] but from 1, (F / V) = (L / V) + 1, so (F / V) - (L / V) = 1 thus ye = ZF when xe = ZF (this is not surprising considering the fact that with a feed of composition ZF and a liquid bottom product of composition ZF the top product cannot be of any composition other than ZF). For the constant pressure at which the flash vessel is operated, a y against x diagram may be plotted and the material balance line (which is straight) is seen to pass through ZF, ZF and xe, ye (corresponding to the temperature Te).
Fig 18:
The above diagrams represent classical simple laboratory distillation, attributed to Rayleigh, 1903. Heat is applied to vapourise some of the solution. The vapour is condensed and found to contain a high m.v.c. composition (depending on amount vapourised). Now in a small time increment dt, vapour of m.v.c. composition y is given off. The amount of vapour given off is V kmol. Assuming x and y are equilibrium values throughout the process, In time increment dt, dV = -dS m.v.c. balance ydV = -d(Sx) = -Sdx - xdS -ydS = -Sdx - xdS xdS - ydS = -Sdx (x - y) dS = -Sdx
Fig 20:
The last equation above is known as Rayleighs Equation, where S1 = total kmol solution to start with S2 = total kmol solution left in bottoms x1 = starting m.v.c. composition in liquid x2 = finishing m.v.c. composition in liquid
Fig 21:
Continuous Fractionation
The system typically adopted for continuous fractionation is shown below.
where, F = Feed flow rate (kmols/hr) xf = m.v.c. composition of feed (mole fraction or mol percentage) V = Vapour flow rate (kmols/hr) L = Reflux flow rate (kmols/hr) D = Top Product flow rate (kmols/hr) xD = m.v.c. composition of top vapour stream, top product, and reflux (mole fraction or mol percentage) V" = Reboiler exit stream flow rate (kmols/hr) W = Bottom-product flow rate (kmols/hr) xW = m.v.c. composition of bottom product and feed to reboiler (mole fraction or mol percentage)
A single stage of the continuous fractionation column is now considered for comparison.
Consider a fractionating column of N plates, where the condenser and reboiler are counted as 'plates'. A typical 'nth' plate has the streams shown below associated with it:
But XN+1 = XD VN-1YN-1 + LN+1XD = VNYN + LNXN M.v.c. balance for plates n to N (where n,N in rectifying section)
(The balance is for the solid red line area) Vn-1Yn-1 + LN+1XN+1 = VNYN + LnXn But XN+1 = XD Vn-1Yn-1 + LN+1XD = VNYN + LnXn M.v.c. balance as above incorporating condenser. (balance as above + dotted red line area) Vn-1Yn-1 = LnXn + DXD
3. Equal or close heats of vaporisation In general, values of V and L very from stage to stage, and an enthalpy balance over each stage is required to calculate L,V. With constant molal overflow assumption, Ln-1 = Ln = Ln+1 = ... etc. Vn-1 = Vn = Vn+1 = ... etc. M.v.c. balance for plate n to condenser continued. Vn-1Yn-1 = LnXn + DXD Assuming constant molal overflow, Note: V=Vapour from top of column L = reflux D = top-product
Dividing through by V gives Yn-1 = (L/V)Xn + (D/V)XD Y = m X + c This material balance equation is called the Upper Operating Line. Note that (L/V) and (D/V) are constants. This linear relationship links the compositions of passing streams between stages.
McCabe-Thiele
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On an x-y diagram, the operating line is a straight line of gradient (L/V) and passes through XD, XD
Fig 31:
Fig 32:
Fig 33:
Fig 34:
Fig 35:
L', V' may be different from L, V m.v.c. balance L' xm = V' Ym-1 + W Xw Ym-1 = (L' / V') Xm - (W/V') Xw This material balance is a straight line passing through the point (Xw,Xw) The intersection of the upper and lower operating lines is determined by the feed.
3. Two-Phase Feed
Fig 39:
q q q q q q q q
Plot equilibrium line Draw 45o line Locate Distillate (XD,XD) Draw Upper Operating Line (gradient R / (R + 1)) between (XD,XD) and (D,XD/(R + 1) ) Locate bottom product (XW,XW) Locate (XF,XF) Draw "q-line" with gradient q / (q - 1) Draw lower operating line (from q-line / upper operating line intersection to (XW,XW) )
Fig 40:
The q-line
For a two phase feed (assumed in equilibrium) F hF = LF hL + VF hv where, hF = specific enthalpy of feed hL = specific enthalpy of saturated liquid hv = specific enthalpy of saturated vapour Generalize by defining q: q = Enthalpy change req to vaporise 1 mole of feed (change it to saturated vapour) / molar enthalpy of vaporisation = (hv - hF) / (hv - hL) Increasing Superheated Vapour q<0 Specific q=0 Enthalpy hv Saturated Vapour 2-phase feed hL Saturated Liquid Sub-cooled Liquid qhv - qhL = hv - hF
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hF = hv - qhv + qhL = (1-q)hv + qhL FhF = FqhL + F(1-q)hv c.f. FhF = LFhL + VFhV LF = qF and VF = (1 - q)F (q / (q - 1)) = - LF / VF Now V = V' + VF = V' + (1 - q)F and L = L' - LF = L' - qF
Fig 41:
Fig 42:
Total Reflux
Fig 43:
Minimum Reflux
Fig 44:
Fig 45:
Fig 46:
Relative Volatility
Volatility = y / x Relative Volatility, AB = ( yA / xA ) / ( yB / xB )
Fig 47: