- Distillation Principles
- Distillation Modeling
- Distillation Operating Equations
- Distillation Calculations
- Distillation Enthalpy Balances
- Enthalpy-Concentration Methods
- Equipment & Column Sizing

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Distillation calculations can be performed graphically on an
enthalpy-concentration (Hx) diagram. This approach is sometimes called the
*Ponchon-Savarit Method*. Working on the Hx diagram is more general
than a McCabe-Thiele construction, because it takes direct account of the
thermal effects and does not require an assumption of equimolal overflow.

The very shape of the Hx diagram provides a clue as to the importance of the energy balances. If the dew point and bubble point lines are more or less straight and roughly parallel, it indicates that the latent heat of vaporization is basically constant with respect to composition. This is the prerequisite for assuming equimolar overflow, and so the energy balances may be neglected. If the saturation curves show significant changes in curvature or separation, it suggests that to assume equimolar overflow will introduce error.

Points for the feed and product can be located on the Hx diagram; for our purposes we'll call them the F, D, and B points. The coordinates are their composition and enthalpy. If the products are saturated liquid, as is the case for total condensers without subcooling and for partial reboilers, these points will lie on the bubble point curve on the Hx diagram.

The steady-state enthalpy balance for a distillation column is:

One of the tools of graphical solution is the notion of colinearity. This has been used before if you have used lever arm principles. For an adiabatic process, the feed and products will be colinear on an Hx diagram. Thus, it is useful to redefine our distillation system to be adiabatic, by bringing the condenser and reboiler inside the system boundary. Rearranging the enthalpy balance gives:

After this modification, the system is adiabatic, so a line can be drawn
through the feed point, F, and the points (x_{D}, h_{Dp}) and
(x_{B}, h_{Bp}). This line represents the system enthalpy
balance, and so is called the *overall enthalpy line*. Remember: for
a given separation only one of the reboiler and condenser duties is
independent. So, you will probably want to pick one duty and then construct
the line through the feed point to determine the other duty.

As before, the reflux ratio can be determined from the L/V ratio, and for this formulation is given by:

A calculation often begins by using the overhead product composition and
temperature to obtain h_{D}and H_{y1}. These in turn are
used with the reflux ratio to get h_{Dp}. Then the overall
enthalpy line is drawn from h_{Dp} through the feed point, and
the intersection with x_{B} gives h_{Bp}.

In the McCabe-Thiele procedure, operating curves were constructed to represent the component balances for the column and to relate the liquid composition on a stage to the composition of the entering vapor. These were then paired with the equilibrium curve, which relates the composition of liquid on a stage to the vapor leaving the stage.

A similar procedure can be followed on an Hx diagram, except instead of using component balances, enthalpy balances are used. The equilibrium data is represented by the equilibrium tie lines on the Hx diagram.

The operating lines are developed from enthalpy balances on the rectifying and
stripping sections (just as in the McCabe-Thiele approach operating equations
were developed from the equivalent component balances). The operating lines
will connect the point representing the liquid on a stage (with coordinates
x_{n}, h_{n}) to the point representing the adjusted enthalpy at
the appropriate end of the column. It will cross the saturated vapor line on
the Hx diagram at the point corresponding to the vapor leaving the stage
(coordinates y_{n+1}, H_{n+1}).

- Obtain enthalpy-composition diagram
- Fix the feed point F, and product points D and B using stream compositions and enthalpies
- Use the overhead product enthalpy and the reflux ratio to find the adjusted enthalpy of the overhead. Plot it as point D', on a vertical line with point D.
- Construct the overall enthalpy line from point D' through the feed point. It intersects a vertical line drawn through point B at point B'.
- Plot point V
_{1}. For a total condenser, the composition entering the condenser is the same as the overhead product, so this point will be vertically above point D on the saturated vapor curve. - Follow the tie line from point V
_{1}to the saturated liquid curve. This intersection will be point L_{1}. - Construct an operating line connecting points D' and L
_{1}. The intersection of the operating line with the saturated vapor curve will be point V_{2}. - Repeat the two preceding steps until one of the V or L points is
to the left of the overall enthalpy line. Once it is crossed,
construct operating lines using points L
_{i}and B'. - When x
_{i}is less than x_{B}, construction is finished.

At total reflux, operating lines are vertical (infinite slope). This can be used to determine the minimum number of stages. Not that operating curves are not required to do this -- only the endpoint compositions.

While doing constructions on the *yx* diagram, a "pinch" was
defined as the intersection point between the equilibrium curve and the
operating curve. On an *Hx* diagram, there isn't an equilibrium
curve -- it has expanded to a region, and each point from the xy
equilibrium curve is represented by a tie line. The "pinch point" also expands,
resulting in a single line where the operating and tie lines overlap.

Minimum reflux still corresponds to a pinch at the feed conditions, so to determine the minimum reflux a line must be constructed so that the overall enthalpy line coincides with the tie line that runs through the feed point.

A feed containing 40 mole percent *n-*hexane and 60 percent
*n-*octane is fed to a distillation column. A reflux ratio of 1.2 is
maintained. The overhead product is 95 percent hexane and the bottoms 10
percent hexane. Find the number of theoretical stages and the optimum feed
stage. Assume that a total condenser is used. The column is to operate at 1
atm.

**Step 1: ** Equilibrium data is collected.

VLE Data, Mole Fraction Hexane, 1 atm | |||||||
---|---|---|---|---|---|---|---|

x (liquid) | 0.0 | 0.1 | 0.3 | 0.5 | 0.55 | 0.7 | 1.0 |

y (vapor) | 0.0 | 0.36 | 0.70 | 0.85 | 0.90 | 0.95 | 1.0 |

Enthalpy-Concentration Data | ||
---|---|---|

Mole Fraction Hexane | Enthalpy cal/gmol | |

Sat. Liquid | Sat. Vapor | |

0.0 | 7000 | 15,700 |

0.1 | 6300 | 15,400 |

0.3 | 5000 | 14,700 |

0.5 | 4100 | 13,900 |

0.7 | 3400 | 12,900 |

0.9 | 3100 | 11,600 |

1.0 | 3000 | 10,000 |

**Step 2: ** Plot the feed and product points. All three will lie on the saturated liquid
line, B at x_{B}=0.1, F at x_{F}=0.4, and D at
x_{D}=0.95.

**Step 3: ** From the data tables (or from the Hx diagram) find the enthalpy of the
distillate, h_{D}=3050 cal/gmol. Because a total condenser is used,
the vapor leaving the top stage will have concentration y_{1}=0.95.
Consequently, it will have enthalpy H_{D}=10,800. These values and the
reflux ratio can be used to find the enthalpy coordinate for the D' point,
H_{Dp}.

**Step 4: ** The overall enthalpy line is then drawn from D', through F. Its
intersection with the line x=0.1 is the point B'.

**Step 5: ** Because of the total condenser, the V_{1} point will lie on the
saturated vapor curve at x=x_{D}.

**Step 6: ** Follow the tie line that passes through the V_{1} point back to the
saturated liquid curve. The intersection is the point L_{1} (liquid on
tray 1). If tie lines are not available, they may be constructed using the xy
diagram.

**Step 7: ** Construct an operating line through both the L_{1} point and the D'
point. Its intersection with the saturated vapor curve will be the point
V_{2}.

**Step 8: ** Continue the construction, alternating between tie lines and and operating
lines until you have moved to the left of the overall enthalpy line at point
L_{3}.

Consequently, there are 5 ideal stages required for this separation -- with a partial reboiler, that means 4 ideal trays. The optimum feed tray is number 3.

Another example may be downloaded as a Mathcad 5.0+ file.

- McCabe, W.L., and J.C. Smith, P. Harriott, Unit Operations of Chemical Engineering, 3rd Edition, McGraw-Hill, 1976. pp. 571-579.
- Treybal, R.E., Mass-Transfer Operations, 3rd Edition (Reissue), McGraw-Hill, 1987.

R.M. Price

Original: 3/19/97

Modified: 1/27/98, 2/14/2003

Copyright 1997, 1998, 2003 by R.M. Price -- All Rights Reserved