MASS TRANSFER,HEAT TRANSFER,FLUID MECHANICS, ENGINEERING THERMODYNAMICS, REACTION ENGINEERING, PLANT DESIGN
Sunday, August 2, 2009
Basic Mass Transfer Operations
Distillation:
Distillation is a method of separating mixtures based on differences in their volatilities in a boiling liquid mixture. Distillation is a unit operation, or a physical separation process, and not a chemical reaction
Applications:
Laboratory scale distillation:
1. Simple distillation
USES:(Limitations)
Distillation is a method of separating mixtures based on differences in their volatilities in a boiling liquid mixture. Distillation is a unit operation, or a physical separation process, and not a chemical reaction
- It is used to separate crude oil into more fractions.
- Air is distilled to separate its components—notably oxygen, nitrogen, and argon—for industrial use.
- To produce distilled beverages with a higher alcohol content.
Laboratory scale distillation:
1. Simple distillation
In simple distillation, all the hot vapors produced are immediately channeled into a condenser that cools and condenses the vapors. Therefore, the distillate will not be pure - its composition will be identical to the composition of the vapors at the given temperature and pressure, and can be computed from Raoult's law.
USES:(Limitations)
- Used only to separate liquids whose boiling points differ greatly (rule of thumb is 25 °C)
- To separate liquids from involatile solids or oils.
2.Fractional distillation
More theoretical plates lead to better separations. A spinning band distillation system uses a spinning band of Teflon or metal to force the rising vapors into close contact with the descending condensate, increasing the number of theoretical plates.
3.Steam distillation
steam distillation is a method for distilling compounds which are heat-sensitive. This process involves using bubbling steam through a heated mixture of the raw material. By Raoult's law, some of the target compound will vaporize (in accordance with its partial pressure). The vapor mixture is cooled and condensed, usually yielding a layer of oil and a layer of water.
Steam distillation of various aromatic herbs and flowers can result in two products; an essential oil as well as a watery herbal distillate. The essential oils are often used in perfumery and aromatherapy while the watery distillates have many applications in aromatherapy, food processing and skin care.
4.Vacuum distillation
5.Air-sensitive vacuum distillation
Some compounds have high boiling points as well as being air sensitive. A simple vacuum distillation system as exemplified above can be used, whereby the vacuum is replaced with an inert gas after the distillation is complete. However, this is a less satisfactory system if one desires to collect fractions under a reduced pressure. To do this a "pig" adaptor can be added to the end of the condenser, or for better results or for very air sensitive compounds a Perkin triangle apparatus can be used.
The Perkin triangle, has means via a series of glass or Teflon taps to allows fractions to be isolated from the rest of the still, without the main body of the distillation being removed from either the vacuum or heat source, and thus can remain in a state of reflux. To do this, the sample is first isolated from the vacuum by means of the taps, the vacuum over the sample is then replaced with an inert gas (such as nitrogen or argon) and can then be stoppered and removed. A fresh collection vessel can then be added to the system, evacuated and linked back into the distillation system via the taps to collect a second fraction, and so on, until all fractions have been collected.
Therefore, fractional distillation must be used in order to separate the components well by repeated vaporization-condensation cycles within a packed fractionating column. This separation, by successive distillations, is also referred to as rectification
As the solution to be purified is heated, its vapors rise to the fractionating column. As it rises, it cools, condensing on the condenser walls and the surfaces of the packing material. Here, the condensate continues to be heated by the rising hot vapors; it vaporizes once more. However, the composition of the fresh vapors are determined once again by Raoult's law. Each vaporization-condensation cycle (called a theoretical plate) will yield a purer solution of the more volatile component. In reality, each cycle at a given temperature does not occur at exactly the same position in the fractionating column; theoretical plate is thus a concept rather than an accurate description.
More theoretical plates lead to better separations. A spinning band distillation system uses a spinning band of Teflon or metal to force the rising vapors into close contact with the descending condensate, increasing the number of theoretical plates.
3.Steam distillation
steam distillation is a method for distilling compounds which are heat-sensitive. This process involves using bubbling steam through a heated mixture of the raw material. By Raoult's law, some of the target compound will vaporize (in accordance with its partial pressure). The vapor mixture is cooled and condensed, usually yielding a layer of oil and a layer of water.
Steam distillation of various aromatic herbs and flowers can result in two products; an essential oil as well as a watery herbal distillate. The essential oils are often used in perfumery and aromatherapy while the watery distillates have many applications in aromatherapy, food processing and skin care.
4.Vacuum distillation
Some compounds have very high boiling points. To boil such compounds, it is often better to lower the pressure at which such compounds are boiled instead of increasing the temperature. Once the pressure is lowered to the vapor pressure of the compound (at the given temperature), boiling and the rest of the distillation process can commence. This technique is referred to as vacuum distillation and it is commonly found in the laboratory in the form of the rotary evaporator.
This technique is also very useful for compounds which boil beyond their decomposition temperature at atmospheric pressure and which would therefore be decomposed by any attempt to boil them under atmospheric pressure.
Molecular distillation is vacuum distillation below the pressure of 0.01 torr. 0.01 torr is one order of magnitude above high vacuum, where fluids are in the free molecular flow regime, i.e. the mean free path of molecules is comparable to the size of the equipment. The gaseous phase no longer exerts significant pressure on the substance to be evaporated, and consequently, rate of evaporation no longer depends on pressure. That is, because the continuum assumptions of fluid dynamics no longer apply, mass transport is governed by molecular dynamics rather than fluid dynamics. Thus, a short path between the hot surface and the cold surface is necessary, typically by suspending a hot plate covered with a film of feed next to a cold plate with a clear line of sight in between. Molecular distillation is used industrially for purification of oils.
5.Air-sensitive vacuum distillation
Some compounds have high boiling points as well as being air sensitive. A simple vacuum distillation system as exemplified above can be used, whereby the vacuum is replaced with an inert gas after the distillation is complete. However, this is a less satisfactory system if one desires to collect fractions under a reduced pressure. To do this a "pig" adaptor can be added to the end of the condenser, or for better results or for very air sensitive compounds a Perkin triangle apparatus can be used.
The Perkin triangle, has means via a series of glass or Teflon taps to allows fractions to be isolated from the rest of the still, without the main body of the distillation being removed from either the vacuum or heat source, and thus can remain in a state of reflux. To do this, the sample is first isolated from the vacuum by means of the taps, the vacuum over the sample is then replaced with an inert gas (such as nitrogen or argon) and can then be stoppered and removed. A fresh collection vessel can then be added to the system, evacuated and linked back into the distillation system via the taps to collect a second fraction, and so on, until all fractions have been collected.
Saturday, August 1, 2009
STUDY MATERIAL FOR ALL
Industry Equipments
- Distillation Columns
- Reactors
- Vessels
- Heat Exchangers
- Mass separation equipments
- Mechanical Separation equipment
- Mixing equipment
- Evaporating and drying Equipments
- Pums
- Compressors
- Steam Traps
General Topics
- Advanced Themodynamics
- Chemical process equipment selection
- Chemical Reaction Engineering
- Pressure safety design practices in Refineries
- Types of reactions and some compounds
- Steam and it's utilization
Ditillation operations
1. What is the driving force for mass transfer operation?
Ans: Chemical potential is the driving force for Mass Tranfer Operations
Distillation is a method of separating mixtures based on differences in their volatilities in a boiling liquid mixture. Distillation is a unit operation, or a physical separation process, and not a chemical reaction.
Relative volatility:
Ans: Chemical potential is the driving force for Mass Tranfer Operations
Distillation is a method of separating mixtures based on differences in their volatilities in a boiling liquid mixture. Distillation is a unit operation, or a physical separation process, and not a chemical reaction.
Relative volatility:
This can also be called as separation factor. This is the ratio of the concentration ration of 'A' and 'B' in one phase to that in the other and is a measure of separability.
y*/(1-y*) y*(1-x*)
α = --------------= ---------- (This is for Binary system only )
x*/(1-x*) x*(1-y*)
where A = More volatile component
B = Less volatile component
α = Relative volatility
x = Mole fraction of more volatility component 'A' in liquid phase
y*= equilibrium Mole fraction of more volatility component 'A' in vapor phase
If y* = x (Except at x=0 or 1), α =1.0 and no separation is possible. The larger the value of 'α' above unity the greater the degree of separability.
Multi component systems:
For multicomponent systems equilibrium data described by means of distribution coefficient 'm'
For component 'j'
y*j
mj = ----
xj
Where in general mj depends upon temperature, pressure and composition of the mixture. The relative volatility
y*i/xi
'α'ij = ----
y*j/xj
xj
Where in general mj depends upon temperature, pressure and composition of the mixture. The relative volatility
y*i/xi
'α'ij = ----
y*j/xj
Ideal solutions:
Four significant characteristics of ideal solutions
1. The average intermolecular forces of attraction and repulsion in the solution are unchanged on mixing the solution
2. The volume of the solution varies linearly with composition.
3.There is neither absorption nor evolution of heat in mixing the constituents.
For gases dissolving in liquids this criterion should not include the heat of condensation of the gas to the liquid state
4. the total vapor pressure of the solution varies linearly with composition expressed as mole fraction
Applications of distillation:
The application of distillation can roughly be divided in four groups: laboratory scale, industrial distillation, distillation of herbs for perfumery and medicinals (herbal distillate), and food processing. The latter two are distinctively different from the former two in that in the processing of beverages, the distillation is not used as a true purification method but more to transfer all volatiles from the source materials to the distillate.
The main difference between laboratory scale distillation and industrial distillation is that laboratory scale distillation is often performed batch-wise, whereas industrial distillation often occurs continuously. In batch distillation, the composition of the source material, the vapors of the distilling compounds and the distillate change during the distillation. In batch distillation, a still is charged (supplied) with a batch of feed mixture, which is then separated into its component fractions which are collected sequentially from most volatile to less volatile, with the bottoms (remaining least or non-volatile fraction) removed at the end. The still can then be recharged and the process repeated.
In continuous distillation, the source materials, vapors, and distillate are kept at a constant composition by carefully replenishing the source material and removing fractions from both vapor and liquid in the system. This results in a better control of the separation process.
Idealized distillation model:
The boiling point of a liquid is the temperature at which the vapor pressure of the liquid equals the pressure in the liquid, enabling bubbles to form without being crushed. A special case is the normal boiling point, where the vapor pressure of the liquid equals the ambient atmospheric pressure.
It is a common misconception that in a liquid mixture at a given pressure, each component boils at the boiling point corresponding to the given pressure and the vapors of each component will collect separately and purely. This, however, does not occur even in an idealized system. Idealized models of distillation are essentially governed by Raoult's law and Dalton's law, and assume that vapor-liquid equilibria are attained.
Raoult's law assumes that a component contributes to the total vapor pressure of the mixture in proportion to its percentage of the mixture and its vapor pressure when pure, or succinctly: partial pressure equals mole fraction multiplied by vapor pressure when pure. If one component changes another component's vapor pressure, or if the volatility of a component is dependent on its percentage in the mixture, the law will fail.
Dalton's law states that the total vapor pressure is the sum of the vapor pressures of each individual component in the mixture. When a multi-component liquid is heated, the vapor pressure of each component will rise, thus causing the total vapor pressure to rise. When the total vapor pressure reaches the pressure surrounding the liquid, boiling occurs and liquid turns to gas throughout the bulk of the liquid. Note that a mixture with a given composition has one boiling point at a given pressure, when the components are mutually soluble.
An implication of one boiling point is that lighter components never cleanly "boil first". At boiling point, all volatile components boil, but for a component, its percentage in the vapor is the same as its percentage of the total vapor pressure. Lighter components have a higher partial pressure and thus are concentrated in the vapor, but heavier volatile components also have a (smaller) partial pressure and necessarily evaporate also, albeit being less concentrated in the vapor. Indeed, batch distillation and fractionation succeed by varying the composition of the mixture. In batch distillation, the batch evaporates, which changes its composition; in fractionation, liquid higher in the fractionation column contains more lights and boils at lower temperatures.
The idealized model is accurate in the case of chemically similar liquids, such as benzene and toluene. In other cases, severe deviations from Raoult's law and Dalton's law are observed, most famously in the mixture of ethanol and water. These compounds, when heated together, form an azeotrope, which is a composition with a boiling point higher or lower than the boiling point of each separate liquid. Virtually all liquids, when mixed and heated, will display azeotropic behaviour. Although there are computational methods that can be used to estimate the behavior of a mixture of arbitrary components, the only way to obtain accurate vapor-liquid equilibrium data is by measurement.
It is not possible to completely purify a mixture of components by distillation, as this would require each component in the mixture to have a zero partial pressure. If ultra-pure products are the goal, then further chemical separation must be applied. When a binary mixture is evaporated and the other component, e.g. a salt, has zero partial pressure for practical purposes, the process is simpler and is called evaporation in engineering.
Batch distillation:
Heating an ideal mixture of two volatile substances A and B (with A having the higher volatility, or lower boiling point) in a batch distillation setup (such as in an apparatus depicted in the opening figure) until the mixture is boiling results in a vapor above the liquid which contains a mixture of A and B. The ratio between A and B in the vapor will be different from the ratio in the liquid: the ratio in the liquid will be determined by how the original mixture was prepared, while the ratio in the vapor will be enriched in the more volatile compound, A (due to Raoult's Law, see above). The vapor goes through the condenser and is removed from the system. This in turn means that the ratio of compounds in the remaining liquid is now different from the initial ratio (i.e. more enriched in B than the starting liquid).
The result is that the ratio in the liquid mixture is changing, becoming richer in component B. This causes the boiling point of the mixture to rise, which in turn results in a rise in the temperature in the vapor, which results in a changing ratio of A : B in the gas phase (as distillation continues, there is an increasing proportion of B in the gas phase). This results in a slowly changing ratio A : B in the distillate.
If the difference in vapor pressure between the two components A and B is large (generally expressed as the difference in boiling points), the mixture in the beginning of the distillation is highly enriched in component A, and when component A has distilled off, the boiling liquid is enriched in component B.
Continuous distillation:
Continuous distillation is an ongoing distillation in which a liquid mixture is continuously (without interruption) fed into the process and separated fractions are removed continuously as output streams as time passes during the operation. Continuous distillation produces at least two output fractions, including at least one volatile distillate fraction, which has boiled and been separately captured as a vapor condensed to a liquid. There is always a bottoms (or residue) fraction, which is the least volatile residue that has not been separately captured as a condensed vapor.
Continuous distillation differs from batch distillation in the respect that concentrations should not change over time. Continuous distillation can be run at a steady state for an arbitrary amount of time. Given a feed of in a specified composition, the main variables that affect the purity of products in continuous distillation are the reflux ratio and the number of theoretical equilibrium stages (practically, the number of trays or the height of packing). Reflux is a flow from the condenser back to the column, which generates a recycle that allows a better separation with a given number of trays. Equilibrium stages are ideal steps where compositions achieve vapor-liquid equilibrium, repeating the separation process and allowing better separation given a reflux ratio. A column with a high reflux ratio may have fewer stages, but it refluxes a large amount of liquid, giving a wide column with a large holdup. Conversely, a column with a low reflux ratio must have a large number of stages, thus requiring a taller column.
Continuous distillation requires building and configuring dedicated equipment. The resulting high investment cost restricts its use to the large scale
General improvements:
Both batch and continuous distillations can be improved by making use of a fractionating column on top of the distillation flask. The column improves separation by providing a larger surface area for the vapor and condensate to come into contact. This helps it remain at equilibrium for as long as possible. The column can even consist of small subsystems ('trays' or 'dishes') which all contain an enriched, boiling liquid mixture, all with their own vapor-liquid equilibrium.
There are differences between laboratory-scale and industrial-scale fractionating columns, but the principles are the same. Examples of laboratory-scale fractionating columns (in increasing efficiency) include:
Air condenser
Vigreux column (usually laboratory scale only)
Packed column (packed with glass beads, metal pieces, or other chemically inert material)
Spinning band distillation system.
The application of distillation can roughly be divided in four groups: laboratory scale, industrial distillation, distillation of herbs for perfumery and medicinals (herbal distillate), and food processing. The latter two are distinctively different from the former two in that in the processing of beverages, the distillation is not used as a true purification method but more to transfer all volatiles from the source materials to the distillate.
The main difference between laboratory scale distillation and industrial distillation is that laboratory scale distillation is often performed batch-wise, whereas industrial distillation often occurs continuously. In batch distillation, the composition of the source material, the vapors of the distilling compounds and the distillate change during the distillation. In batch distillation, a still is charged (supplied) with a batch of feed mixture, which is then separated into its component fractions which are collected sequentially from most volatile to less volatile, with the bottoms (remaining least or non-volatile fraction) removed at the end. The still can then be recharged and the process repeated.
In continuous distillation, the source materials, vapors, and distillate are kept at a constant composition by carefully replenishing the source material and removing fractions from both vapor and liquid in the system. This results in a better control of the separation process.
Idealized distillation model:
The boiling point of a liquid is the temperature at which the vapor pressure of the liquid equals the pressure in the liquid, enabling bubbles to form without being crushed. A special case is the normal boiling point, where the vapor pressure of the liquid equals the ambient atmospheric pressure.
It is a common misconception that in a liquid mixture at a given pressure, each component boils at the boiling point corresponding to the given pressure and the vapors of each component will collect separately and purely. This, however, does not occur even in an idealized system. Idealized models of distillation are essentially governed by Raoult's law and Dalton's law, and assume that vapor-liquid equilibria are attained.
Raoult's law assumes that a component contributes to the total vapor pressure of the mixture in proportion to its percentage of the mixture and its vapor pressure when pure, or succinctly: partial pressure equals mole fraction multiplied by vapor pressure when pure. If one component changes another component's vapor pressure, or if the volatility of a component is dependent on its percentage in the mixture, the law will fail.
Dalton's law states that the total vapor pressure is the sum of the vapor pressures of each individual component in the mixture. When a multi-component liquid is heated, the vapor pressure of each component will rise, thus causing the total vapor pressure to rise. When the total vapor pressure reaches the pressure surrounding the liquid, boiling occurs and liquid turns to gas throughout the bulk of the liquid. Note that a mixture with a given composition has one boiling point at a given pressure, when the components are mutually soluble.
An implication of one boiling point is that lighter components never cleanly "boil first". At boiling point, all volatile components boil, but for a component, its percentage in the vapor is the same as its percentage of the total vapor pressure. Lighter components have a higher partial pressure and thus are concentrated in the vapor, but heavier volatile components also have a (smaller) partial pressure and necessarily evaporate also, albeit being less concentrated in the vapor. Indeed, batch distillation and fractionation succeed by varying the composition of the mixture. In batch distillation, the batch evaporates, which changes its composition; in fractionation, liquid higher in the fractionation column contains more lights and boils at lower temperatures.
The idealized model is accurate in the case of chemically similar liquids, such as benzene and toluene. In other cases, severe deviations from Raoult's law and Dalton's law are observed, most famously in the mixture of ethanol and water. These compounds, when heated together, form an azeotrope, which is a composition with a boiling point higher or lower than the boiling point of each separate liquid. Virtually all liquids, when mixed and heated, will display azeotropic behaviour. Although there are computational methods that can be used to estimate the behavior of a mixture of arbitrary components, the only way to obtain accurate vapor-liquid equilibrium data is by measurement.
It is not possible to completely purify a mixture of components by distillation, as this would require each component in the mixture to have a zero partial pressure. If ultra-pure products are the goal, then further chemical separation must be applied. When a binary mixture is evaporated and the other component, e.g. a salt, has zero partial pressure for practical purposes, the process is simpler and is called evaporation in engineering.
Batch distillation:
Heating an ideal mixture of two volatile substances A and B (with A having the higher volatility, or lower boiling point) in a batch distillation setup (such as in an apparatus depicted in the opening figure) until the mixture is boiling results in a vapor above the liquid which contains a mixture of A and B. The ratio between A and B in the vapor will be different from the ratio in the liquid: the ratio in the liquid will be determined by how the original mixture was prepared, while the ratio in the vapor will be enriched in the more volatile compound, A (due to Raoult's Law, see above). The vapor goes through the condenser and is removed from the system. This in turn means that the ratio of compounds in the remaining liquid is now different from the initial ratio (i.e. more enriched in B than the starting liquid).
The result is that the ratio in the liquid mixture is changing, becoming richer in component B. This causes the boiling point of the mixture to rise, which in turn results in a rise in the temperature in the vapor, which results in a changing ratio of A : B in the gas phase (as distillation continues, there is an increasing proportion of B in the gas phase). This results in a slowly changing ratio A : B in the distillate.
If the difference in vapor pressure between the two components A and B is large (generally expressed as the difference in boiling points), the mixture in the beginning of the distillation is highly enriched in component A, and when component A has distilled off, the boiling liquid is enriched in component B.
Continuous distillation:
Continuous distillation is an ongoing distillation in which a liquid mixture is continuously (without interruption) fed into the process and separated fractions are removed continuously as output streams as time passes during the operation. Continuous distillation produces at least two output fractions, including at least one volatile distillate fraction, which has boiled and been separately captured as a vapor condensed to a liquid. There is always a bottoms (or residue) fraction, which is the least volatile residue that has not been separately captured as a condensed vapor.
Continuous distillation differs from batch distillation in the respect that concentrations should not change over time. Continuous distillation can be run at a steady state for an arbitrary amount of time. Given a feed of in a specified composition, the main variables that affect the purity of products in continuous distillation are the reflux ratio and the number of theoretical equilibrium stages (practically, the number of trays or the height of packing). Reflux is a flow from the condenser back to the column, which generates a recycle that allows a better separation with a given number of trays. Equilibrium stages are ideal steps where compositions achieve vapor-liquid equilibrium, repeating the separation process and allowing better separation given a reflux ratio. A column with a high reflux ratio may have fewer stages, but it refluxes a large amount of liquid, giving a wide column with a large holdup. Conversely, a column with a low reflux ratio must have a large number of stages, thus requiring a taller column.
Continuous distillation requires building and configuring dedicated equipment. The resulting high investment cost restricts its use to the large scale
General improvements:
Both batch and continuous distillations can be improved by making use of a fractionating column on top of the distillation flask. The column improves separation by providing a larger surface area for the vapor and condensate to come into contact. This helps it remain at equilibrium for as long as possible. The column can even consist of small subsystems ('trays' or 'dishes') which all contain an enriched, boiling liquid mixture, all with their own vapor-liquid equilibrium.
There are differences between laboratory-scale and industrial-scale fractionating columns, but the principles are the same. Examples of laboratory-scale fractionating columns (in increasing efficiency) include:
Air condenser
Vigreux column (usually laboratory scale only)
Packed column (packed with glass beads, metal pieces, or other chemically inert material)
Spinning band distillation system.
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