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Tarapur N-46
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Tarapur N-46
What is an azeotrope?
An azeotrope is a mixture of two or more liquids in such a ratio that its composition cannot be changed by simple distillation. This occurs because, when an azeotrope is boiled, the resulting vapor has the same ratio of constituents as the original mixture. These mixture are also called constant boiling mixture.
What is Pervaporation?
Pervaporation is the selective evaporation of one of the components of a liquid mixture using a membrane. The word pervaporation itself is a combination of the words permeation, the transport through a membrane, and evaporation, the phase transition from the liquid to the vapor phase. It is not a pressure driven process such as several filtration processes and reverse osmosis. Instead, the driving force is due to the fact that on the feed side the chemical potential is higher than on the permeate side, similar to what is found in gas separation membranes. The gradient in chemical potential is maximized by using high feed temperatures and low pressures on the permeate side. Alternatively to pervaporation, membranes can often be used in vapor permeation mode as well. In this case the feed is fully vaporized. These kinds of membrane processes are beneficial for the separation of e.g. azeotropes. In distillation the complete liquid feed is evaporated leading to high energy demands. By replacing distillation by the pervaporation membranes or combining the two processes large energy savings are possible. -It is the only membrane process where phase transition occurs -The heat of vaporization has to be provided. -Mass transport is achieved by lowering the activity of the permeating component on permeate side.
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Mechanism of Pervaporation:
-Sorption of selective component. -Diffusion through the membrane. -Desorption into permeate side in vapor phase.
Pervaporation Membranes: The membranes used in pervaporation processes are classified according to the nature of the separation being performed. Hydrophilic membranes are used to remove water from organic solutions. These types of membranes are typical made of polymers with glass transition temperatures above room temperatures. Polyvinyl alcohol is an example of a hydrophilic membrane material. Organophilic membranes are used to recover organics from solutions. These membranes are typically made up of elastomeric materials (polymers with glass transition temperatures below room temperature). The flexible nature of these polymers makes them ideal for allowing organic to pass through. The selectivity of pervaporation membranes can vary substantially and has a critical effect on the overall separation obtained. The figure belows shows the concentration of acetone in the permeate as a function of the concentration in the feed. The two membranes shown have dramatically different properties. The pervaporation selectivity varies with concentration. At 20 wt% acetone in the feed, silicone rubber has a pervaporation selectivity of approximately 16 favouring acetone; the cross linked polyvinyl alcohol (PVA) membrane has a pervaporation selectivity of only 0.3 and selectively removes water. The acetone-selective, silicone rubber membrane is best used to treat dilute acetone feed streams, concentrating most of the acetone in a small volume of permeate. The water-selective, polyvinyl alcohol membrane is best used to treat concentrated acetone feed streams containing only a few percent water. Most of the water is then removed and concentrated in the permeate. Both membranes are more selective than distillation, which relies on the vapour-liquid equilibrium to achieve a separation.
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Examples of membranes available: 1. NaY zeolite membrane for the pervaporation separation of methanolmethyl tert-butyl ether mixtures. 2. PVA (poly vinyl alcohol) pervaporation membranes. 3. Polymer membranes. 4. Silica Membranes Factors Affecting Membrane Performance According to the solution-diffusion model, higher fluxes can be obtained with an increased thermal motion of the polymer chains and the diffusing species. Properties of the polymers that affect diffusion include the "backbone" material, degree of cross linking, and porosity. Molecular-level interactions between membranes and diffusing species are expressed via a permeability constant used in the Arrhenius relationship:
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Pervaporation Characteristics 1. Molecular Flux Molecular flux is the amount of a component permeated per unit area per unit time for a given membrane.
Where, Ji = Flux of component "i" (moles/h cm2) Qi = Moles of component "i" permeated in time "t" A = Effective membrane surface area (cm2) 2. Permselectivity The performance of a given membrane can be expressed in terms of a parameter called permselectivity:
Assuming the density of the components in the feed is the same, then: Where, X = Weight fraction V = Volume fraction p = Density Superscripts "p" and "f" denote "permeate" and "feed" respectively while "i" and "j" represent individual components.
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The feed is allowed to flow along one side of the membrane and a fraction of the feed (permeate) passes through the membrane and leaves in the vapour phase on the opposite side of the membrane. The "vapour phase" side of the membrane is either kept under a vacuum or it is purged with a stream of inert carrier gas. The permeate is finally collected in the liquid state after condensation. The liquid product is rich in the more rapidly permeating component of feed mixture. The retentate is made up of the feed materials that cannot pass through the membrane. The activity a component in a mixture is proportional to the composition of that particular component in the mixture. The composition is dependent on the partial pressure and the saturation vapour pressure. In general, by decreasing the pressure on the permeate side a very low concentration feed solution can be concentrated up to 90%.
Existing Process for Separation of Solvent Mixture. Mayur Malpani / IIT Roorkee / Summer Training 2010
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Problems faced: 1. Glycerin step used to separate out moisture which involves loss of EA. 2. Additional step used to retain this EA. 3. EA (b.p 77 C) forms azeotrope with ethanol (78.3 C) which is difficult to separate. 4. More time required for the process which decreases production.
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Base 500 target production: 3000MT per year (approximately 350 kg/hr) Solvent Mixture Produced (Approximately in ratio 1:1 with Base 500) = 350 kg/hr Composition of Solvent Mixture S.No Component 1 Ethanol 2 Methanol 3 Toluene 4 Ethyl Acetate 5 Moisture
Percentage(%) 10 31 31 26 2
Physical Properties of the Components Component Ethanol Methanol Toluene Ethyl Acetate Moisture Boiling Point(C) 78.3 65 110 77 100 Antoines Coefficient(A,B,C) 8.04494,1554.3,222.65 7.87863,1473.113,230 6.95464,1344.8,219.482 7.09808,1238.71,217 8.07131,1730.63,233.426 Density (kg/m3) 789 791 867 894 1000 Molecular Mass (grams/mol) 46 32 92 88 18
[Antoines Equation (
), P is pressure in mm Hg , T is temperature in C]
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Design of Pervaporation Unit: Components to be separated as (Toluene + EA) and (Ethanol+Methanol+Moisture) The most important part of a pervaporation unit is the selection of a suitable membrane for a particular permeate component. Pervaporation unit can be designed in two ways:1) Selecting a component to permeate and then selecting the membrane 2) Selecting the membranes from the available and then determining the suitable one. Since the membranes available are mostly hydrophilic in nature I decided to go by the first option. Atomic size of Methanol is closer to water, hence I selected Methanol to proceed further in designing. Two options available for the methanol were 1. Polymer blend membranes of Poly Acrylic Acid (PAA) and Poly Vinyl Alcohol (PVA) 2. Micro porous methylated silica membranes Polymer blend membranes are restricted in working by their stability at high temperatures. Hence this option was not considered further although the methanol flux obtained from these membranes is nearly same as from the silica membranes. MODIFIED METHYLATED SILICA MEMBRANES These membranes are known for separation of organics by pervaporation. In the paper Methanol Separation from organics by pervaporation with modified silica membranes by members of Energy Research Centre of the Netherlands details about how nearly pure methanol can be obtained from even a low concentration mixture of 5% methanol. Graph for methanol-toluene mixture from the paper:
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The flux obtained from this membrane for a 35wt % Methanol Toluene mixture is about 3.7kg/m2hr with the permeate almost being the methanol(about 99.9%). Assumptions: 1. Since Ethanol has very low flux rate (.05-.1 kg/m2hr) through silica membrane, it is neglected in final permeate. 2. Since Water is more permeable than methanol, all water permeates along with the methanol. 3. No toluene and ethyl acetate in the final permeate.
Mass of methanol to permeate per hour = 108.5 kg Flux considered for the calculation taking the account of the composition of the mixture =3.5kg/m2hr. Membrane area required =
2
Now the modules are available in tubular form with membrane outer diameter 14mm and one module may contain up to 25 tubes. So considering the above available parameters, One module with 24 tubes and 2m2 area gives the length 2m. Result Mayur Malpani / IIT Roorkee / Summer Training 2010
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Module: Tubular No. of tubes = 24 Outer Diameter of tube = 14 mm Membrane Support: Ceramic Module Length: 2m No. of modules required
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M1
M2
FIG. PERVAPORATION PROCESS OUTLINE Mayur Malpani / IIT Roorkee / Summer Training 2010
M4
M3
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The heat required for the vaporaisation of the methanol is obtained from the sensible heat of the mixture, so the unit has to be divided in different section so as to heat the material to the feed temperature 60C, to obtain the optimum flux. The retentate temperatures after passing through the modules will be
*Heat Capacity of the mixture is based on the composition wt% average as shown below.
The heat exchangers that are employed for achieving the required feed temperatures are described below:
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*HE 5 is employed to heat the feed material of Distillation Column 1 to their boiling point. Heat Load is same for
HE 2, 3 & 4.
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Pressure swing distillation is based on the fact that the azeotropes are pressure dependent i.e. the composition of azeotropes varies with pressure. Hence this fact is utilized in the separation of azeotropic mixture, where two different columns are used operating under different pressure. In other words, it is a method for separating a pressure-sensitive azeotrope that utilizes 2 columns operated in sequence at 2 different pressures For example, consider the case of a minimum-boiling azeotrope with T-x-y curves at P2 as shown in the Figure below. As the pressure is reduced to P1, the azeotropic concentration moves toward a smaller percentage of A (xP2 to xP1).
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2 columns operating at different pressures can thus help us to separate the azeotropic mixture, thereby giving the pure components as final products. The total feed F1 to Column T-1 operating at the lower pressure P 1 is the sum of the fresh feed F at mole fraction xF, and the recycled distillate D2 at mole fraction xD2 (close to azeotropic mole fraction xP2). The mole fraction of the total feed F1 is xF1 , and it is richer in A than the azeotropic mole fraction of xP1 at pressure P1. The bottoms leaving column T-1 is almost pure A. The distillate leaving T-1 is D1 , having the mole fraction xD1 . This mole fraction is richer in A than the azeotropic mole fraction of xP1, but less rich in A than the azeotrope mole fraction of xP2 . Distillate D1 is sent to Column T-2 as feed F2 . Nearly pure B is obtained from bottom of T-2, and the distillate D2 is recycled to Column T-1.
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The changes on the phase diagram are shown the Figure below.
Design of the process. Our aim is to separate out Ethanol and Ethyl Acetate , so as to recover nearly all of the ethyl acetate. But, since toluene is also present in the initial mixture we will have to consider such a design so that we have ethyl acetate with toluene as bottoms from first column and ethanol from the second. From the table given below, it is clear that Ethanol-EA azeotrope is pressure dependent and percentage of ethanol increases with increase in pressure. Taking data from the "Enhanced Design Report on Rich Traceability" by University of Newcastle Upon Tyne, at P=10 bar , the composition (mol%) of the mixture becomes 70 EtOH 30 EA i.e. wt % 55 EtOH - 45 EA. The two distillation columns will be operated under 10 bars and 1 bar. The composition at 1bar is given in the table below and reference of 10 bars is stated above.
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Stream 1
L2
Stream 4
Stream 5
R C
Reboiler Condenser
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Consideration in the distillation columns: -Since at P=10 bars the boiling point of toluene will be very high compared to ethanol and ethyl acetate , almost all the toluene will remain in the liquid state and will not disturb the ethanolethyl acetate system. Details of different streams (only taking ethanol and ethyl acetate as the participating constituents in the distillation process). STREAM 1 2 (1+2) 3 4 5 COMPONENT(EtOH-EA) BOTH BOTH BOTH BOTH EA(also toluene is present) EtOH Wt%(EtOH-EA) 27.77-72.23 31-69 28.88-71.12 55-45 99 99 Mol%(EtOHEA) 51.4-48.6 45-55 43.7-56.3 70-30 99 99 MASS(kg/hr) 126+(108.5) 65.625 191.625+(108.5) 100.625 91+(108.5) 35
The above data is prepared by doing mass balance on distillation column 1 and the known inputs were: 1. Composition of stream 2 (azeotrope at P= 1bar) 2. Distillate composition at P=10 bars (azeotrope) 3. Mass of bottoms drawn. Below are the tables which gives the details of the distillation columns 1 & 2 operating at 10 bars and 1 bar respectively.
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The method used for calculating the no. of trays required for Distillation Columns is McCabeThiele Method. Taking the help of the calculator for the McCabe-Thiele method provided by the Prof. Shuzo Ohe on www.s-ohe.com, we find out the no. of trays required and minimum reflux ratio.
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Distillation Column 2 Area calculation of Condensers: Mayur Malpani / IIT Roorkee / Summer Training 2010
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Column 1 7600
Column 2 760
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No. of Trays(eff.= 0.7) Column Diameter Plate Type Bottoms Temperature Condensate Temperature
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20 Sieve 167 149 16 Sieve 77 73
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Pump Specification:
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Introduction:
A pump is a device used to move fluids, such as liquids or slurries, or gases. A pump displaces a volume by physical or mechanical action. Types of pump: Positive Displacement Pumps Buoyancy Pumps Impulse Pumps Velocity Pumps Gravity Pumps Centrifugal Pumps: A centrifugal pump is one of the simplest pieces of equipment in any process plant. Its purpose is to convert energy of a prime mover (a electric motor or turbine) first into velocity or kinetic energy and then into pressure energy of a fluid that is being pumped. The energy changes occur by virtue of two main parts of the pump, the impeller and the volute or diffuser. The impeller is the rotating part that converts driver energy into the kinetic energy. The volute or diffuser is the stationary part that converts the kinetic energy into pressure energy. .
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The amount of energy required to overcome the total friction loss within the system has to be supplied by the pump for a required flow rate.
Pressure is produced at the bottom of the reservoir because the liquid fills up the container completely and its weight produces a force that is distributed over a surface which is pressure.
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This type of pressure is called static pressure. It is independent of the shape of the vessel, what matters is the height.
Where, f = Friction Factor Hf = Frictional Head Loss L = pipe length D = pipe internal diameter v = velocity of fluid Re = Reynolds No.
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The typical values of Leq / D for common piping system components are listed below.
Equivalent length (Leq) of pipe bends Bends 180o (return) bend, R = 5D 90o bend, R=5D 90o bend, R=1,5D 90o square bend 45o bend, R = 1,5 D Tee, flow straight through Tee, flow through side outlet
D = internal pipe diameter
Leq/D 28 16 20 57 16 20 65
Gate valve, open Gate valve 1/4 closed Gate valve 1/2 closed Gate valve 3/4 closed Ball valve Globe valve Needle valve Check valve Check valve, swing type Filter, y-type and bucket
D = internal pipe diameter
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In this process the 2 pumps used are: 1. For supplying the stored material to the pervaporation unit at 2 bars. 2. For supplying the retentate of pervaporation unit to Distillation Column 1 at 10 bars. Pump 1
Pipe Size (m) Flow Rate(kg/hr) System Component Eqvlt. Length of Component(m) No. of Comp. Eqvlt. Length(m)
0.0254
350
5 2 1 2 2
Velocity(m/s) 0.6
Re 33040.977
Pump 2
Pipe Size (m) Flow Rate(kg/hr) System Component Eqvlt. Length of Component(m) No. of Comp. Eqvlt. Length(m)
0.0254
350
3 1 2 1
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0.865836 0.6 0.0254 0.402239
Friction Head(m) Velocity(m/s) 0.6 Re 32804.73 Friction factor 0.00587 Static Head Pressure Head Required Total 0.0615 5 100 105.0615