Distillation Principles
Distillation Principles
Distillation Principles
Definition of distillation, Types of columns, Simple Distillation methods (Flash, batch, Steam), Basic distillation Equipment and operation, Column internal, Reboilers, Distillation principles, Vapor `liquid equilibria, Distillation column design, Effect of the number of trays or stages, Factors affecting distillation column operation, Introduction to multi-component Distillation
Definition of Distillation
A process in which a liquid or vapour mixture of two or more substances is separated into its component fractions of desired purity, by the application and removal of heat.
Distillation is based on the fact that the vapour of a boiling mixture will be richer in the components that have lower boiling points. Therefore, when this vapour is cooled and condensed, the condensate will contain more volatile components. At the same time, the original mixture will contain more of the less volatile material. Distillation columns are designed to achieve this separation efficiently.
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Although many people have a fair idea what distillation means, the important aspects that seem to be missed from the manufacturing point of view are that: distillation is the most common separation technique it consumes enormous amounts of energy, both in terms of cooling and heating requirements it can contribute to more than 50% of plant operating costs
The best way to reduce operating costs of existing units, is to improve their efficiency and operation via process optimization and control. To achieve this improvement, a thorough understanding of distillation principles and how distillation systems are designed is essential.
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The purpose of this introduction is to expose you to the terminology used in distillation practice and to give a very basic introduction to:
Types of columns Simple distillation methods (Flash, batch and Steam distillation) Basic distillation equipment and operation Column internals Reboilers Distillation principles Vapor liquid equilibria Distillation column design Effect of the number of trays or stages Factors affecting distillation column operation Introduction to multi-component distillation
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Continuous Columns In contrast, continuous columns process a continuous feed stream. No interruptions occur unless there is a problem with the column or surrounding process units. They are capable of handling high throughputs and are the most common of the two types. We shall concentrate only on this class of columns.
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The nature of the feed that they are processing, 9 binary column - feed contains only two components
9 multi-component column - feed contains more than two components The number of product streams they have 9 multi-product column - column has more than two product streams Where the extra feed exits when it is used to help with the separation, 9 extractive distillation - where the extra feed appears in the bottom product stream 9 azeotropic distillation - where the extra feed appears at the top product stream The type of column internals 9 tray column - where trays of various designs are used to hold up the liquid to provide better contact between vapor and liquid, hence better separation 9 packed column - where instead of trays, 'packings' are used to enhance contact between vapor and liquid
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y = f(x)
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When the sum of the separate vapor pressures equals the total pressure, the mixture boils and where pA is vapor pressure of pure water pA + pB = P pB is vapor pressure of pure B
Vapor composition:
yA = pA/P
yB = pA/P
As long as the two liquid phases are present, the mixture will boil at the same temperature, giving a vapor of constant composition. Note: as long as liquid water is present, the high-boiling component B vaporizes at a temperature well below its normal boiling point without vacuum. The vapors of water (A) and high-boiling component (B) are usually condensed in a condenser and the resulting two immiscible liquid phases are separated. Disadvantage: large amounts of heat must be used to simultaneously evaporate the water with the high-boiling compound Used in the food industry for the removal of volatile taints and flavors from edible fats and oils.
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The vertical shell houses the column internals and together with the condenser and reboiler, constitute a distillation column. A schematic of a typical distillation unit with a single feed and two product streams is shown below:
The liquid mixture that is to be processed is known as the feed and this is introduced usually somewhere near the middle of the column to a tray known as the feed tray. The feed tray divides the column into a top (enriching or rectification) section and a bottom (stripping) section. The feed flows down the column where it is collected at the bottom in the reboiler.
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Thus, there are internal flows of vapour and liquid within the column as well as external flows of feeds and product streams, into and out of the column.
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COLUMN INTERNALS
The terms "trays" and "plates" are used interchangeably. There are many types of tray designs, but the most common ones are:
Bubble cap trays A bubble cap tray has riser or chimney fitted over each hole, and a cap that covers the riser. The cap is mounted so that there is a space between riser and cap to allow the passage of vapor. Vapor rises through the chimney and is directed downward by the cap, finally discharging through slots in the cap, and finally bubbling through the liquid on the tray.
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Valve trays In valve trays, perforations are covered by liftable caps. Vapor flows lifts the caps, thus self creating a flow area for the passage of vapor. The lifting cap directs the vapor to flow horizontally into the liquid, thus providing better mixing than is possible in sieve trays Sieve trays Sieve trays are simply metal plates with holes in them. Vapor passes straight upward through the liquid on the plate. The arrangement, number and size of the holes are design parameters.
Because of their efficiency, wide operating range, ease of maintenance and cost factors, sieve and valve trays have replaced the once highly thought of bubble cap trays in many applications.
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Each tray has 2 conduits, one on each side, called downcomers. Liquid falls through the downcomers by gravity from one tray to the one below it. The flow across each plate is shown in the above diagram on the right. A weir on the tray ensures that there is always some liquid (holdup) on the tray and is designed such that the the holdup is at a suitable height, e.g. such that the bubble caps are covered by liquid. Being lighter, vapor flows up the column and is forced to pass through the liquid, via the openings on each tray. The area allowed for the passage of vapor on each tray is called the active tray area. The picture on the left is a photograph of a section of a pilot scale column equiped with bubble capped trays. The tops of the 4 bubble caps on the tray can just be seen. The down- comer in this case is a pipe, and is shown on the right. The frothing of the liquid on the active tray area is due to both passage of vapour from the tray below as well as boiling.
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As the hotter vapor passes through the liquid on the tray above, it transfers heat to the liquid. In doing so, some of the vapor condenses adding to the liquid on the tray. The condensate, however, is richer in the less volatile components than is in the vapor. Additionally, because of the heat input from the vapor, the liquid on the tray boils, generating more vapor. This vapor, which moves up to the next tray in the column, is richer in the more volatile components. This continuous contacting between vapor and liquid occurs on each tray in the column and brings about the separation between low boiling point components and those with higher boiling points.
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Tray Designs
A tray essentially acts as a mini-column, each accomplishing a fraction of the separation task. From this we can deduce that the more trays there are, the better the degree of separation and that overall separation efficiency will depend significantly on the design of the tray. Trays are designed to maximize vapor-liquid contact by considering the: liquid distribution and vapor distribution. This is because better vapor-liquid contact means better separation at each tray, translating to better column performance. Less trays will be required to achieve the same degree of separation. Attendant benefits include less energy usage and lower construction costs. There is a clear trend to improve separations by supplementing the use of trays by additions of packings.
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Packings
Packings are passive devices that are designed to increase the interfacial area for vapor-liquid contact. The following pictures show 3 different types of packings.
These strangely shaped pieces are supposed to impart good vapor-liquid contact when a particular type is placed together in numbers, without causing excessive pressure-drop across a packed section. This is important because a high pressure drop would mean that more energy is required to drive the vapor up the distillation column.
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COLUMN REBOILERS
There are a number of designs of reboilers. It is beyond the scope of this set of introductory notes to delve into their design principles. However, they can be regarded as heat-exchangers that are required to transfer enough energy to bring the liquid at the bottom of the column to boiling boint. The following are examples of typical reboiler types.
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A novel development in reboiler design is the self-cleaning shell-andtube heat exchangers by Klarex Technology for applications where heat exchange surfaces are prone to fouling by the process fluid. Particles are introduced into the process stream and these produce a scouring action on the heat exchange surfaces. An example is shown in the diagram on the left.
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DISTILLATION PRINCIPLES
Separation of components from a liquid mixture via distillation depends on the differences in boiling points of the individual components. Also, depending on the concentrations of the components present, the liquid mixture will have different boiling point characteristics. Therefore, distillation processes depends on the vapor pressure characteristics of liquid mixtures.
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The boiling point of A is that at which the mole fraction of A is 1. The boiling point of B is that at which the mole fraction of A is 0. In this example, A is the more volatile component and therefore has a lower boiling point than B. The upper curve in the diagram is called the dew-point curve while the lower one is called the bubble-point curve.
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Dew-point: is the temperature at which the saturated vapor starts to condense. Bubble-point: is the temperature at which the liquid starts to boil.
The region above the dew-point curve shows the equilibrium composition of the superheated vapor while the region below the bubble-point curve shows the equilibrium composition of the subcooled liquid.
For example, when a subcooled liquid with mole fraction of A=0.4 (point A) is heated, its concentration remains constant until it reaches the bubble-point (point B), when it starts to boil. The vapors evolved during the boiling has the equilibrium composition given by point C, approximately 0.8 mole fraction A. This is approximately 50% richer in A than the original liquid. This difference between liquid and vapor compositions is the basis for distillation operations.
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Relative Volatility
Relative volatility: is a measure of the differences in volatility between 2 components, and hence their boiling points. It indicates how easy or difficult a particular separation will be. The relative volatility of component i with respect to component j is defined as
yi = mole fraction of component i in the vapour xi = mole fraction of component i in the liquid
Thus if the relative volatility between 2 components is very close to one, it is an indication that they have very similar vapor pressure characteristics. This means that they have very similar boiling points and therefore, it will be difficult to separate the two components via distillation.
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The previous particular VLE plot shows a binary mixture that has a uniform vapor-liquid equilibrium that is relatively easy to separate. The next two VLE plots below on the other hand, shows non-ideal systems which will present more difficult separations.
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The most intriguing VLE curves are generated by azeotropic systems. An azeotrope is a liquid mixture which when vaporised, produces the same composition as the liquid. The two VLE plots below, show two different azeotropic systems, one with a minimum boiling point and one with a maximum boiling point. In both plots, the equilibrium curves cross the diagonal lines, and this are azeotropic points where the azeotropes occur. In other words azeotropic systems give rise to VLE plots where the equilibrium curves crosses the diagonals.
Note the shapes of the respective equilibrium lines in relation to the diagonal lines that bisect the VLE plots.
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Both plots are however, obtained from homogenous azeotropic systems. An azeotrope that contains one liquid phase in contact with vapour is called a homogenous azeotrope. A homogenous azeotrope cannot be separated by conventional distillation. However, vacumn distillation may be used as the lower pressures can shift the azeotropic point.Alternatively, an additional substance may added to shift the azeotropic point to a more favourable position. When this additional component appears in appreciable amounts at the top of the column, the operation is called azeotropic distillation. When the additional component appears mostly at the bottom of the column, the operation is called extractive distillation
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The VLE curve on the left is also generated by an azeotropic system, in this case a heterogenous azeotrope. Heterogenous azeotropes can be identified by the flat portion on the equilibrium diagram.
They may be separated in 2 distillation columns since these substances usually form two liquid phases with widely differing compositions. The phases may be separated using settling tanks under appropriate conditions. Next, we will look at how VLE plots/data are used to design distillation columns.
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The design procedure is simple. Given the VLE diagram of the binary mixture, operating lines are drawn first. Operating lines define the mass balance relationships between the liquid and vapor phases in the column. There is one operating line for the bottom (stripping) section of the column, and on for the top (rectification or enriching) section of the column. Use of the constant molar overflow assumption also ensures the operating lines are straight lines.
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R is the ratio of reflux flow (L) to distillate flow (D) and is called the reflux ratio and is a measure of how much of the material going up the top of the column is returned back to the column as reflux.
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Ls is the liquid rate down the stripping section of the column, while Vs is the vapor rate up the stripping section of the column. Thus the slope of the operating line for the stripping section is a ratio between the liquid and vapor flows in that part of the column.
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A magnified section of the operating line for the stripping section is shown in relation to the corresponding n'th stage in the column. L's are the liquid flows while V's are the vapor flows. x and y denote liquid and vapor compositions and the subscripts denote the origin of the flows or compositions. That is 'n-1' will mean from the stage below stage 'n' while 'n+1' will mean from the stage above stage 'n'. The liquid in stage 'n' and the vapor above it are in equilibrium, therefore, xn and yn lie on the equilibrium line. Since the vapor is carried to the tray above without changing composition, this is depicted as a horizontal line on the VLE plot. Its intersection with the operating line will give the composition of the liquid on tray 'n+1' as the operating line defines the material balance on the trays. The composition of the vapor above the 'n+1' tray is obtained from the intersection of the vertical line from this point to the equilibrium line.
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Doing the graphical construction repeatedly will give rise to a number of 'corner' sections, and each section will be equivalent to a stage of the distillation. This is the basis of sizing distillation columns using the McCabeThiele graphical design methodology as shown in the following example.
sections, the graphical construction described above was applied. This particular example shows that 7 theoretical stages are required to achieve the desired separation. The required number of trays (as opposed to stages) is one less than the number of stages since the graphical construction includes the contribution of the reboiler in carrying out the separation.
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Typical values for tray efficiency ranges from 0.5 to 0.7 and depends on a number of factors, such as the type of trays being used, and internal liquid and vapor flow conditions. Sometimes, additional trays are added (up to 10%) to accomodate the possibility that the column may be under-designed.
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q = 0 (saturated vapor) q = 1 (saturated liquid) 0 < q < 1 (mix of liquid and vapor) q > 1 (subcooled liquid) q < 0 (superheated vapour)
9 The q-lines for the various feed conditions are shown in the diagram on the left.
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It can be deduced from the previous section on distillation column design that the number of trays will influence the degree of separation. This is illustrated by the following example.
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9 Consider as a base case, a 10 stage column. The feed is a binary mixture that has a composition of 0.5 mole fraction in terms of the more volatile component, and introduced at stage 5. The steady-state terminal compositions of about 0.65 at the top (stage 1) and 0.1 at the bottom (stage 10) are shown below: Composition Profile: 10 stages, feed at stage 5
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Suppose we decrease the number of stages to 8, and keep the feed at the middle stage, i.e. stage 4. The resulting composition profile is:
Composition Profile: 8 stages, feed at stage 4 9 We can see that the top composition has decreased while the bottom composition has increased. That is, the separation is poorer.
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Now, if we increase the number of stages to 12, and again introduce the feed at mid-column, i.e. stage 6, the composition profile we get is:
Composition Profile: 12 stages, feed at stage 6 9 Again, the composition has changed. This time the distillate is much richer in the more volatile component, while the bottoms has less, indicating better separation. Thus, increasing the number of stages will improve separation.
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Suppose we have a 20 stage column, again separating a binary mixture that has a composition of 0.5 mole fraction in terms of the more volatile component. The terminal compositions obtained when the feed is introduced at stages 5, 10 and 15 (at fixed reflux and reboil rates) are shown in the following plots.
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As the feed stage is moved lower down the column, the top composition becomes less rich in the more volatile component while the bottoms contains more of the more volatile component. However, the changes in top composition is not as marked as the bottoms composition.
The preceding examples illustrate what can happen if the position of the feed tray is shifted for this particular system. They should not be used to generalize to other distillation systems, as the effects are not straightforward.
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Feed Conditions
The state of the feed mixture and feed composition affects the operating lines and hence the number of stages required for separation. It also affects the location of feed tray. During operation, if the deviations from design specifications are excessive, then the column may no longer be able handle the separation task. To overcome the problems associated with the feed, some column are designed to have multiple feed points when the feed is expected to containing varying amounts of components.
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Reflux Conditions
As the reflux ratio is increased, the gradient of operating line for the rectification section moves towards a maximum value of 1. Physically, what this means is that more and more liquid that is rich in the more volatile components are being recycled back into the column. Separation then becomes better and thus less trays are needed to achieve the same degree of separation. Minimum trays are required under total reflux conditions, i.e. there is no withdrawal of distillate.
9 On the other hand, as reflux is decreased, the operating line for the rectification section moves towards the equilibrium line. The pinch between operating and equilibrium lines becomes more pronounced and more and more trays are required.This is easy to verify using the McCabeThiele method.
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9 The limiting condition occurs at minimum reflux ration, when an infinite number of trays will be required to effect separation. Most columns are designed to operate between 1.2 to 1.5 times the minimum reflux ratio because this is approximately the region of minimum operating costs (more reflux means higher reboiler duty).
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Foaming refers to the expansion of liquid due to passage of vapour or gas. Although it provides high interfacial liquid-vapour contact, excessive foaming often leads to liquid buildup on trays. In some cases, foaming may be so bad that the foam mixes with liquid on the tray above. Whether foaming will occur depends primarily on physical properties of the liquid mixtures, but is sometimes due to tray designs and condition. Whatever the cause, separation efficiency is always reduced.
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Entrainment
Entrainment refers to the liquid carried by vapor up to the tray above and is again caused by high vapor flow rates. It is detrimental because tray efficiency is reduced: lower volatile material is carried to a plate holding liquid of higher volatility. It could also contaminate high purity distillate. Excessive entrainment can lead to flooding.
Weeping/Dumping
This phenomenon is caused by low vapor flow. The pressure exerted by the vapour is insufficient to hold up the liquid on the tray. Therefore, liquid starts to leak through perforations. Excessive weeping will lead to dumping. That is the liquid on all trays will crash (dump) through to the base of the column (via a domino effect) and the column will have to be re-started. Weeping is indicated by a sharp pressure drop in the column and reduced separation efficiency.
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Flooding
Flooding is brought about by excessive vapor flow, causing liquid to be entrained in the vapor up the column. The increased pressure from excessive vapor also backs up the liquid in the downcomer, causing an increase in liquid holdup on the plate above. Depending on the degree of flooding, the maximum capacity of the column may be severely reduced. Flooding is detected by sharp increases in column differential pressure and significant decrease in separation efficiency.
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Column Diameter Most of the above factors that affect column operation is due to vapor flow conditions: either excessive or too low. Vapor flow velocity is dependent on column diameter. Weeping determines the minimum vapor flow required while flooding determines the maximum vapor flow allowed, hence column capacity. Thus, if the column diameter is not sized properly, the column will not perform well. Not only will operational problems occur, the desired separation duties may not be achieved.
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Weather Conditions
Most distillation columns are open to the atmosphere. Although many of the columns are insulated, changing weather conditions can still affect column operation. Thus the reboiler must be appropriately sized to ensure that enough vapor can be generated during cold and windy spells and that it can be turned down sufficiently during hot seasons. The same applies to condensers.
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Other Factors
These are some of the more important factors that can cause poor distillation column performance. Other factors include changing operating conditions and throughputs, brought about by changes in upstream conditions and changes in the demand for the products. All these factors, including the associated control system, should be considered at the design stages because once a column is built and installed, nothing much can be done to rectify the situation without incurring significant costs. The control of distillation columns is a field in its own right, but that's another story.
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Multi, n-component:
n-1 columns are required
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Design Calculations
Procedure is similar to binary, requiring material, energy and equilibrium equations: - Then computations of stage-to-stage are performed to solve the system of equations at each tray Involves trial and error calculations and digital computers are generally used Two methods are normally used: 1. Desired separation is specified and NT is determined for a given reflux ratio. Trial and error procedure is used to determine the composition of distillate and bottom products. 2. NT enriching and NT stripping and reflux ratio are specified. Separation of the components is calculated using assumed liquid and vapor flows and temperatures
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This corresponds to total reflux and Nmin is determined by Fenske equation which was derived for binary system. When applied to heavy key (H) and light key (L), it becomes: log[( x L, D D / x H , D D)( x H , B B / x L, B B) Nm = log( L,av ) Light key: the more volatile component to be separated Heavy key: the least volatile component to be separated Light component: components that are lighter than the light key Heavy component: components that are less volatile than the heavy key xL,D: mole fraction of light key in distillate xH,D: mole fraction of heavy key in distillate xL,B: mole fraction of light key in bottom xH,B: mole fraction of heavy key in bottom
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Relative volatility
Using component C as the base component in the mixture, e.g., A, B, C, D: yi / xi Ki i = = yC / xC KC K: Equilibrium K-value
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Ne: number of plates above feed Ns: number of plates below the feed plate
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Other Approaches
Use of computer packages to perform more accurate calculations: - Aspen plus - HYSYS - Design II - PROTO
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