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Distillation is the most widely used separation process in the chemical industry. It is also
known as fractional distillation or fractionation. It is normally used to separate liquid
mixtures into two or more vapor or liquid products with different compositions.
Distillation is an equilibrium stage operation. In each stage, a vapor phase is contacted with a
liquid phase and mass is from vapor to liquid and from liquid to vapor. The less volatile,
"heavy" or "high boiling", components concentrate in the liquid phase; the more volatile,
"light", components concentrate in the vapor. By using multiple stages in series with recycle,
separation can be accomplished.
Operating Principles:
The feed to a
distillation column
may be liquid, vapor,
or a liquid-vapor
mixture. It may enter
at any point in the
column, although the
optimal feed tray
location should be
determined and used.
More than one stream
may be fed to the
system, and more than
one product may be
drawn.
A column is divided
into a series of stages.
These correspond to a
cascade of equilibrium
stages. Liquid flows
down the column from
stage to stage and is
contacted by vapor
flowing upward.
Traditionally, most
columns have been
built from a set of
distinct "trays" or
"plates", so these
terms end up being
essentially interchangeable with "stages". Each tray in a distillation column is designed to
promote contact between the vapor and liquid on the stage. Distillation can be conducted in a
packed column (just as absorption can be done in a trayed column), but we will focus on
trayed columns for the present.
Stages may be numbered from top down or bottom up. When analyzing a stage, flows and
compositions take the number of the stage they leave. The text for this class calls the top tray
of the column "Tray 1" and numbers downward - - this is the convention we will use. MSH
also denote the streams between the column top and condenser with an "a" subscript and
those at the bottom with "b". Personally, I generally prefer to let "Tray 1" be the bottom tray
of the column, the reboiler "Tray 0" and number upward (so if you catch me doing this, don't
panic). I like this way of numbering because it tends to simplify computer based calculations.
The product leaving the top of the column is called the overhead product, the "overhead", the
"top product", the distillate, or "distillate product". Distillate product may be liquid or vapor
(or occasionally both) depending on the type of condenser used. Most of the time the
distillate flow rate is assigned the symbol D, and the composition xD or yD.
The product leaving the bottom of the column is called the bottom product or "bottoms", and
given the symbol B, with composition xB.
Vapor leaving the top of the column passes through a heat exchanger, the condenser, where it
is partially or totally condensed. The liquid which results is temporarily held in the
"accumulator" or reflux drum. A liquid stream is withdrawn from the drum and returned to
the top tray of the column as reflux (R or L) to promote separation.
The portion of the column above the feed tray is called the rectification section. In this
section, the vapor is enriched by contact with the reflux.
The portion of the column below the feed tray is called the stripping section. The liquid
portion of the feed serves as the reflux for this section.
The operating pressure of the column is typically controlled by adjusting heat removal in the
condenser.
The base of the column is typically used as a reservoir to hold liquid leaving the bottom tray.
A heat exchanger, the reboiler, is used to boil this liquid. The vapor which results, the
"boilup" (V) is returned to the column on one of the bottom three or four trays.
In normal operation, there are five "handles" that can be adjusted to manipulate the behavior
of a distillation column -- the feed flow, two product flows, the reflux flow, and the boilup
flow (or reboiler heat input).
A normal column has a temperature gradient and a pressure gradient from bottom to top.
Ideal Stages
When no azeotropes are present, both top and bottom products may be obtained in any
desired purity --- if enough stages are provided and enough reflux is available. In practice,
there are limits to the number of stages and to the amount of reflux, so not every separation
can be accomplished. Theoretical limits on performance are imposed by total reflux
(minimum stages) and minimum reflux (infinite number of ideal stages).
There are two main categories of condenser, differentiated by the extent of condensation.
In a partial
condenser,
the vapor is
only partially
liquefied. The liquid produced is returned to the column as
liquid, and a vapor product stream is removed. The
compositions of these three streams (V1, D, and R) are
different. Normally, D (composition yD) is in equilibrium
with R (composition xD).
Most reboilers are partial reboilers, that is they only vaporize part of the liquid in the column
base. Partial reboilers also provide an ideal separation stage.
Reboilers take several forms: they may be "thermosiphon" types that rely on the thermal
effects on density to draw liquid through the heat exchanger, "forced circulation" types that
use a pump to force liquid through, or even "stab-in" types that come through the side of the
column into the liquid reservoir.
In large, complex columns, sidestream reboilers can be used. These draw liquid off a tray,
heat it, and then return the vapor liquid mixture to the same or a similar trays.
Feed Condition
The thermal condition of the feed determines the column internal flows.
If the feed is below its bubble point, heat is needed to raise it to where it can be vaporized.
This heat must be obtained by condensing vapor rising through the column, so the liquid flow
moving down the column increases by the entire amount of the feed plus the condensed
material and the vapor flow upward is decreased.
If the feed enters as superheated vapor, it will vaporize some of the liquid to equalize the
enthalpy. In this case, the liquid flow down the column drops and the vapor flow up is
increased by the entire amount of the feed plus the vaporized material.
If the feed is saturated (liquid or vapor), no additional heat must be added or subtracted, and
the feed adds directly to the liquid or vapor flow.
• Subcooled Liquid
q>1
q=1+cpL(Tbp-Tf)/lambda
• Saturated Liquid (bubble point feed)
q=1
• Partially Vaporized
0<q<1
q is the fraction of the feed that is liquid. It can be found by doing a flash
calculation and then q=(L/F)=(1-V/F)
• Saturated Vapor (dew point feed)
q=0
• Superheated Vapor
q<0
q=(-cpV*(Tf-Tdp)/lambda)
Distillation II: Calculations
Before beginning most distillation calculations, a decision must be reached: does equimolal
overflow apply? If so, the operating equations are lines and you have one set of options --
notably the McCabe-Thiele method. If not, energy balances must be explicitly considered.
There are several ways of incorporating the energy effects. The Ponchon-Savarit method is a
graphical approach that does not require an assumption of equimolal overflow. Graphical
construction is done on the enthalpy composition diagram. Your text does not include this
method, but it may be useful.
In all cases, one can use a "stepping" approach. Starting from one end of the column, the
component, material, and energy balances can be solved simultaneously. After a stage is
determined, you step up (or down) to the next and calculate that stage. Depending on what
information is known, the form of the equilibrium relation, etc., this approach may require an
iterative solution.
McCabe-Thiele Method
The graphical McCabe-Thiele Method can be used to determine the number of ideal stages
and feed tray location. To do this, you make a plot showing the equilibrium curve, feed line,
and operating lines for the rectifying and stripping sections (all on the same axes), and then
find answers by graphical construction.
A standard (beginner) distillation problem provides you with xF, q, xD, xB, and RD; although
not necessarily directly. You may need to use the overall material balances to find some of
the compositions; to calculate the q factor from temperature and composition data; and/or
determine the reflux ratio based on the limiting minimum value. Once you have these values,
the solution procedure is:
If you don't want to draw, you can do the same thing, iteratively solving for the various
equation intersections. You'll need to be pretty careful with your "bookkeeping" if you try
this.
To apply Murphree tray efficiencies, construct an effective equilibrium curve between the
equilibrium and operating curves, and step using the effective curve to determine actual
separation stages. Remember that a partial reboiler or partial condenser is by definition an
ideal stage, so you use the ideal equilibrium curve (not the effective) for these stages.
The optimum feed tray is the triangle with one corner on the rectifying line and one on the
stripping line. Putting the feed anywhere else increases the number of stages needed to make
the separation. To visualize this, notice that the closer the operating line is to the equilibrium
curve, the smaller the stepping triangles become. Introducing the feed at the intersection of
the rectifying and stripping lines maximizes the size of the triangles and so leads to the fewest
steps.
When analyzing existing distillation systems, the actual feed entry point may not be at the
optimum (the tray where the operating lines intersect). In this case, the tray stepping should
switch from the rectifying line to the operating line at the actual feed tray location.
Limiting Cases
The design tradeoff between reflux and stages is the standard economic
optimization problem chemical engineers always face -- balancing capital costs
(the number of trays to be built) vs. the operating cost (the amount of reflux to
be recirculated). A good design will operate near a cost optimum reflux ratio.
Total Reflux
The total reflux condition represents operation with no product removal. All the overhead
vapor is condensed and returned as reflux. Consequently, the reflux ratio (L/D) is infinite.
This, in turn, makes the operating lines the 45 degree line (prove it to yourself by setting
D=0, and noticing that consequently L=V). With the operating lines on the diagonal, they are
as far as they can get from the equilibrium curve, so if the number of plates are stepped off
using the diagonal and the equilibrium curve, the number of theoretical stages will be a
minimum.
Often, columns are operated at total reflux during their initial startup, and product is not
withdrawn until a separation close to that desired is achieved.
The Fenske Equation is another method for determining the minimum number of trays
required for a given separation. It is an example of a "shortcut" distillation method. There are
a number of these approximate methods available to get initial estimates of distillation
requirements.
If the relative volatility varies through a column because of temperature effects, it is possible
to use a geometric mean value of the relative volatility (as is done for multicomponent
distillation) and the Fenske equation to get an approximate value for the number of stages.
Pinch Points
The intersection of an operating line and the equilibrium curve is called a pinch point. A
simple column will have two pinch points (because there are two operating lines). The points
change when the operating lines do. An existing column can "pinch" if its operating line is
too close to its equilibrium curve. This means that there are several stages doing very little
separation and wasting resources.
To cure a pinch, the most direct solution is to move the feed entry point. This is often an
expensive proposition. In such cases, the reflux and boilup ratios can be increased to change
the operating lines. This will increase operating costs and energy consumption, but may be
the only realistic option.
A pinch at the intersection of the feed line and the equilibrium curve indicates that the
column is operating at minimum reflux.
Minimum Reflux
The minimum reflux condition represents the theoretical opposite of total reflux -- an infinite
number of ideal separation stages. In this case, the intersection of the operating lines lies on
the equilibrium curve itself. Thus, the distance between the equilibrium curve and the
operating lines is at its minimum, the stepping triangles become very small, there is no gap
between the equilibrium curve and the intersection point, so you cannot step past the feed
point.
The minimum reflux rate can be determined mathematically from the endpoints of the
rectifying line at minimum reflux -- the overhead product composition point (xD,xD) and the
point of intersection of the feed line and equilibrium curve (x', y').
The derivation of this formula is given later. One important thing to realize: the
formula only applies when the feed line is the breakpoint for the operating curve
in the top portion of the column. If there are intermediate product draws
between the reflux and the feed, the formula does not apply. In this case, you
must calculate the liquid flow down the column at the pinch point, and then work
it back up the column to find the reflux flow at minimum reflux conditions.
If the equilibrium curve has an inflection point, it may not be possible to construct a line
between the overhead product point and the feed/equilibrium intersection without passing
outside the equilibrium envelope. Operating curves must always intersect within the
equilibrium envelope and cannot cross outside (in either half of the column). In this case,
minimum reflux occurs at a tangent pinch and the operating line is tangent to the equilibrium
curve. Calculations are based upon the intersection of the tangent operating line and the feed
point.
When designing columns, it is common to define the design reflux ratio as some multiple of
the theoretical minimum reflux. The cost optimum reflux ratio is typically in the 1.1 to 1.5
range depending on energy costs, condenser coolant, and materials of construction. The rule
of thumb reported most often suggests that a reflux ratio of about 1.2 times the minimum is a
good design value.
It may also be necessary to distinguish between returned reflux (the reflux stream flowing
from the accumulator to the column) and the effective reflux flowing down the column. This
is a concern if the reflux is subcooled. In this case, the effective reflux will consist of the
returned reflux plus whatever additional liquid is condensed when the cold liquid contacts
vapor on the reflux tray. It is probably best to use effective reflux in minumum reflux
calculations.
Some equations in this document are being displayed using MINSE, a browser independent approach to
displaying equations on the web. If the equations are not properly formatted by your brower, you need to
RENDER EQUATIONS (select this link) by invoking Ping's MINSE polymediator. This will run a special
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Minimum reflux corresponds to a pinch at the intersection of the feed line and the
equilibrium curve. From its formula, the rectifying line has slope'quot(R;D, R;D +1) and will
connect the intersection point (xint, yint) and (xD, xD). Consequently, we can express the slope
in terms of "rise over run", or'quot(x;D - y;int, x;D - x;int)
Clearly, this formula doesn't apply if there are more than two operating regions. In these
cases, it is probably smarter to calculate the reflux ratio from the ratio of the liquid and vapor
flow rates.
The heating and cooling loads in the condenser and reboiler can be calculated from
straighforward energy balances. The chief difficulty is in getting good values for the heats of
vaporization -- an enthalpy-concentration diagram is very useful!
For the reboiler, energy must be added equal to the sum of the sensible heat needed to raise
the liquid to its boiling point and the latent heat of vaporization. The steady-state energy
balance on the process side of the reboiler is then:
Q;B = V;B*(c;(mean)*(T;B-T;1)+?lambda?;(mean))
Q;B = V;B*?lambda?;(mean)
The heating medium requirements can be calculated from an energy balance on the heating
side of the reboiler. If saturated steam is the heating medium, then
Q;R = m;s*?lambda?;s
so that (neglecting thermal capacitance in the reboiler and heat losses) the
steam rate can be obtained from
Similarly, if a liquid heat transfer fluid (hot oil, etc.) is used, the equations
m;f*c;p*(T;(htfs)-T;(htfr))=V;B*?lambda?;(mean)
(htfs = heat transfer fluid supply, htfr = heat transfer fluid return) or
U*A*?Delta?T = V;B*?lambda?;(mean)
may be used.
(neglecting any subcooling of reflux), so that when cooling water is used in the
condenser
Q;C = m;w*c;w*(T;cwr-T;cws)
(cws = cooling water source, cwr = cooling water return) and since the specific
heat of water is 1.0 for common units
m;w = 'quot(V;1*?lambda?;(mean),T;cwr-T;cws)
When calculating cooling loads, you may need to adjust the vapor rate or
condenser duty to account for vapor condensed by direct contact with cold reflux
on the reflux return tray. Watch for this whenever the condenser temperature is
significantly below the expected tray temperature.
It is possible to imagine a case whereQ;B .approxeq Q;C ; that is, whenV;1 .approxeq V;B .
The case when the vapor rates at the top and bottom of the column are most likely to be the
same occurs when the feed is at its bubble point, andq=1 . In this situation, the condenser and
reboiler loads will be approximately equal.
Stage Efficiencies
Mass transfer limitations prevent the vapor leaving a tray from truly being in precise
equilibrium with the liquid on the tray; consequently, the assumption of ideal stages is only
an approximation.
An efficiency is used to represent the deviation from equilibrium. There are three types of
efficiencies we will consider:
1. Overall efficiency
2. Local efficiency
3. Murphree efficiency
An overall efficiency is the simplest choice. It is the ratio of the number of ideal stages to the
number of actual stages.
A single efficiency can thus be used for the entire column, but is only accurate
enough for prelimary design. Some improvement can be achieved by using
separate efficiencies for each section of the column. Accuracy is limited because
effectiveness of mass transfer is constrained by geometry and design of the
trays, flowrates and paths of all streams, compositions, etc. The problem is really
too complex to lump into a single parameter, so when overall efficiencies are
used they should be based on performance data from similar columns or
laboratory tests.
The local efficiency is the most accurate option, but also the most difficult to use. It is defined
at only a single point on a specific tray.
A Murphree efficiency is probably the most common choice, since it represents a workable
compromise between accuracy and ease of use. It has the same form as a local efficiency but
is based on tray average compositions.
Values between 0.6 and 0.75 are common for sieve trays. We know that the
liquid leaving a tray is not really the same as the tray average, so a Murphree
efficiency effectively assumes perfect mixing on the tray. In practice, we
normally measure the liquid composition and get the vapor composition from an
equilibrium calculation or diagram. In the case of multicomponent systems, the
efficiencies are different for each component.
The overall efficiency and the Murphree efficiency are not directly related. You cannot use
an average Murphree efficiency in place of an overall value.
To use a local or Murphree efficiency with a graphical method, the true equilibrium curve is
replaced with an effective equilibrium curve located between the true curve and the operating
curves. The effective curve is used to count stages. Note, however, that the efficiency doesn't
apply to the reboiler, so the true equilibrium curve should be used for the last stage of the
stripping section.
To construct an effective equilibrium curve is not difficult. The effective curve is given by:
y;eff = y + ?eta?;M*(y;eq - y)
where y represents the operating curve. A plot of yeff will produce an interior
line on the equilbrium diagram construction.
Distillation III: Equipment and Column Sizing
In order to have stable operation in a distillation column, the vapor and liquid flows must be
managed. Requirements are:
• vapor should flow only through the open regions of the tray between the
downcomers
• liquid should flow only through the downcomers
• liquid should not weep through tray perforations
• liquid should not be carried up the column entrained in the vapor
• vapor should not be carried down the column in the liquid
• vapor should not bubble up through the downcomers
These requirements can be met if the column is properly sized and the tray
layouts correctly determined.
Tray layout and column internal design is quite specialized, so final designs are usually done
by specialists; however, it is common for preliminary designs to be done by ordinarily
superhuman process engineers. These notes are intended to give you an overview of how this
can be done, so that it won't be a complete mystery when you have to do it for your design
project.
Basically in order to get a preliminary sizing for you column, you need to obtain values for
Typically, the liquid flow between trays is governed by a weir on each tray. The flow
depends on the length of the weir and how high the liquid level on the tray is above the weir.
The Francis weir equation is one example of how the flow off a tray may be modeled.
Tray Efficiency
The O'Connell correlation is based on data collected from actual columns. It is based on
bubble cap trays and is conservative for sieve and valve trays. It correlates the overall
efficiency of the column with the product of the feed viscosity and the relative volatility of
the key component in the mixture. These properties should be determined at the arithmetic
mean of the column top and bottom temperatures. A fit of the data has been determined:
This, or a similar data set, can be used to get preliminary estimates of efficiency
numbers.
Column Diameter
Column diameter is found based on the constraints imposed by flooding. The number of ideal
stages isn't needed to find the diameter -- only the vapor and liquid loads. You do need the
number of actual stages to get the column height.
Before beginning a diameter calculation, you want to know the vapor and liquid rates
throughout the column. You then do a diameter calculation for each point where the loading
might be an extreme: the top and bottom trays; above and below feeds, sidedraws, or heat
addition or removal; and any other places where you suspect peak loads.
Once you've calculated these diameters, you select one to use for the column, then check it to
make sure it will work. Some columns will have two sections with different diameters --
consider this possibility if you end up with regions where the estimated diameter varies by
20% or more, but realize it will be more expensive than a column that is the same all the way
up.
One issue that ought to be considered is the validity of your design numbers. If you are
following the "traditional" approach, you've probably designed your column for reflux rates
in the range of 1.1 to 1.2 times the minimum. This may not give you a column that can handle
"upsets" well, so you may want to design for a capacity slightly greater than that -- increasing
the flows by about 20% might be wise.
Flooding
Downcomer flooding occurs when liquid backs up on a tray because the downcomer area is
two small. This is not usually a problem. More worrisome is entrainment flooding, caused by
too much liquid being carried up the column by the vapor stream.
A number of correlations and techniques exist for calculating the flooding velocity; from this,
the active area of the column is calculated so that the actual velocity can be kept to no more
than 80-85% of flood; values down to 60% are sometimes used.
A force balance can be made on droplets entrained by the vapor stream (which can lead to
entrainment flooding). This balance yields an expression relating the vapor and liquid
densities and a capacity factor (C, with velocity units) to the flooding velocity:
Capacity Factors
The capacity factor can be determined from theory (it depends on droplet diameter, drag
coefficient, etc.), but is usually obtained from correlations based on experimental data from
distillation tray tests. Depending on the correlation used, C may include the effects of surface
tension, tendency to foam, and other parameters.
A common correlation is one proposed by Fair in the late 50s - early 60s. The version for
sieve trays is available in a wide range of sources (including Figure 21.28 of MSH). The
correlation takes the form of a plot of a capacity factor (which must be corrected for surface
tension) vs. a functional group based on the liquid to vapor mass ratio:
Enter the plot from the bottom with this number, and then read the capacity
factor from the left. This capacity factor applies to nonfoaming systems and trays
meeting certain hole and weir size restrictions. It will need to be corrected for
surface tension:
Other correlations for the capacity factor are also available. Several are based on more recent
information, and may well be more accurate than the Fair plot; however, they also tend to be
less broadly known and often require more a priori information on the system. You should
use a correlation that is acceptable for your problem.
Diameter
Once you have the capacity factor, you can readily solve for the flooding velocity:
(this solution is for the Fair correlation, and adds the surface tension correction).
We know that flow=velocity*area, so we can calculate the flow area from the known vapor
flow rate and the desired velocity (a fraction of flood). This area needs to be increased to
account for the downcomer area which is unavailable for mass transfer. The resulting tray
area can then be used to calculate the column diameter. So, with everything lumped together,
we have:
The only "new" term is the ratio of downcomer area to tray area. This should
probably never be less than 0.1, and probably seldom will be greater than 0.2.
Trays probably aren't a good idea for columns less than about 1.5 ft in diameter (you can't
work on them) -- these are normally packed. Packing is less desirable for large diameter
columns (over about 5 ft in diameter).
Pressure Drop
There is a pressure gradient through the column -- otherwise the vapor wouldn't flow. This
gradient is normally expressed in terms of a pressure drop per tray, usually on the order of
0.10 psi.
The best source of pressure drop information is to measure the actual drop between trays, but
this isn't always feasible at the beginning of a design. Detailed calculations are possible, but
these depend so much on the actual tray specifications that final values are usually obtained
from experts, but approximate methods can be used to get values to put in your design basis.
There are two main components to the pressure drop: the "dry tray" drop caused by
restrictions to vapor flow imposed by the holes and slots in the trays and the head of the
liquid that the vapor must flow through.
The dry tray head loss can be related to an orifice flow equation:
This equation determines the dry tray drop in inches of fluid (your text has a
similar equation in SI units). The constant 0.186 takes care of the units and is
appropriate for sieve trays. The orifice size coefficient Co depends on the tray
configuration and will usually fall between 0.65 and 0.85. The hole velocity can
be obtained by dividing the vapor flow rate by the total hole area of the tray.
Liquid Losses
The liquid head pressure drop includes the effects of surface tension and of the frothing on
the tray. It is typically represented as the product of an aeration factor and the height of liquid
on the tray:
Correlations are available for the aeration factor (beta); a value of 0.6 is good for
a wide variety of situations.
The height of liquid on the tray is the sum of the weir height and the height of liquid over the
weir. The total height can be calculated directly from the volume of liquid on the tray and its
active area. Another approach is to back the height out of a version of the Francis weir
equation (which relates flow off a tray to liquid height and weir length). One version, for a
straight weir, in units of inches and gal/min is:
Realize that these equations depend on the size and shape of the weir.
Column Height
The height of a trayed column is calculated by multiplying the number of (actual) stages by
the tray separation. Tray spacing can be determined as a cost optimum, but is usually set by
mechanical factors. The most common tray spacing in 24 inches -- it allows enough space to
work on the trays whenever the column is big enough around (>5 ft diameter) that workers
must crawl inside. Smaller diameter columns may be able to get by with 18 inch tray
spacings.
In addition to the space occupied by the trays, height is needed at the top and bottom of the
column. Space at the top -- typically an additional 5 to 10 ft -- is needed to allow for
disengaging space.
The bottom of the tower must be tall enough to serve as a liquid reservoir. Depending on your
boss's feelings about keeping inventory in the column, you will probably design the base for
about 5 minutes of holdup, so that the total material entering the base can be contained for at
least 5 minutes before reaching the bottom tray.
The total of height added to the top and bottom will usually amount to about 15% or so added
to that required by the trays.
You rarely will see a real tower that is more than about 175 ft. tall. Tall, skinny towers are not
a good idea, so watch the height/diameter ratio. You generally want to keep it less than 20 or
30. If your tower ends up exceeding these values, you probably want to look at a redesign,
maybe by reducing the tray spacing, or splitting the tower into two parts.