Multi-component Gas-Liquid System

Separation processes involves multi-phase system.

For example: (1) Xylene isomers are separated by crystallization process. A xylene melt (liquid) is cooled down and p-xylene crystallizes first (solid) at 13.3C, separating p-xylene from o- and m-xylenes (2) Nitrogen is produced by distillation process. Air (gas) is cooled down to -182C condensing oxygen (liquid) from the air mixture. Air (gas) can also separated by adsorption process where nitrogen is trapped in zeolite (solid: nitrogen-zeolite). Air (gas) can be passed through a membrane (solid: added 1-phase) that allow oxygen to permeate through the membrane.
Read 237-238 for more examples. 1) Please find from web what are leaching, supercritical fluid extraction and stripping processes. 2) Please find out where did I find the boiling point data for p-xylene and oxygen (Hint: they are in your book)

Vapor-liquid Equilibrium (VLE)

Single component representation of VLE
(1) Clapeyron Equation (Chpt 6.1b) (2) Antoine Equation (review previous handouts) (3) Cox Chart (see Fig. 6.1-4) (4) Tabulated data (5) DePriestler Chart plots the K-value = Y/X or y/x Note y is the mass or (Y) mole fraction in gas phase x is the mass or (X) mole fraction in liquid phase

But the most common separation process chemical engineer work with is distillation involving gas-liquid separation.
3) Give three other examples of gas-liquid separation processes besides distillation.

Note: (4) Why is K-value the same for both mass and mole fraction units?

DePriestler Chart
How to use the DePriestler Chart
For Example: You are given T = 150 C and P = 400 kPa, you wanted to know the K-value of n-octane. (1) mark 150 C on the temperature scale, (2) mark 400 kPa on the pressure scale, (3) draw a line between 150 C and 400 kPa then read the K-value from the scale of n-octane. K is 0.5 this means that at this condition there would be twice as much octane in liquid than in vapor. Kvalue 150 C

DePriestler Chart
Example: A pure compound has a K-value of 0.25 at 30 C and atmospheric pressure. Based on the given, determine what is the unknown compound. What would be the K-value of this compound if the temperature was increased to 100 C.
(5) Please outline the procedure for solving this example. Also, what is the significance of K-value larger than 1?

101.3 kPa

400 kPa

30 C

DePriestler Chart
What is the relationship of K-value to vapor-liquid equilibrium? Homework (due 18-April 2003). Please plot the T-x-y diagram by excel for a mixture containing n-butane and n-pentane at 200 kPa pressure.

KA = YA/XA YA = KA XA = A(PA*/PT ) XA K(T,P)

Activity coefficient accounting for nonideal solution Note A = 1 for ideal system following Raoults Law therefore K-value is corrected vapor pressure!

How do we use K-value for representing equilibrium? For Example: Binary mixture of A and B will have KA(T,P) and KB(T,P). Please write a procedure for constructing a Tdew-y and Tbubble-x diagram given that the pressure is fixed at 1 bar.
(1) Create a Table with columns for temperature (T), KA, KB, XA, YA (2) Mark P on the DePriestler Chart. (3) Find the boiling point temperature of pure A and pure B (1) point 1: P point 2: KA = 1=Y/X from axis of A compount Note for pure compound Y = X = 1 at boiling point temperature (2) draw a line from point 1 to point 2 extending to T-axis (3) read TA (4) repeat for B (4) Input 10 temperature points in T-column between T1=TA and T10=TB, using Ti+1 = Ti + (TA-TB)/10. (5) Find KA(Ti) and KB(Ti) using the method shown before. (6) Calculate XA from: KAXA + KBXB = YA + YB = 1 XA = 1-KB/KA-KB (7) Calculate YA from: KAXA

Bubble and Dew point Temperatures

The bubble point temperature is the temperature at which a bubble of vapor is formed in a liquid solution:

Bubble and Dew point Temperatures

Example: A solution containing 0.3 mol fraction of methanol and 0.7 mole fraction of water is to be separated by distillation. At what temperature will the solution starts to boil (i.e., bubble point temperature) and at what temperature will all the feed solution be vaporized (i.e., dew point temperature). Please note the pressure was kept at 1 atm. Given: Feed is 0.3 mol frac. methanol P = 1 atm (1) Find PVT data of methanol-ethanol. The most convenient is T-xy diagram. If this is not available use Antoine equation making an assumption that methanol-ethanol is an ideal solution (i.e., Raoults Law is applicable) For this example, we will use the T-xy diagram from
http://www.svce.ac.in/~msubbu/SolvedProblems/MT/VaporLiquidEquil.htm.

Note: The composition of the bubble is different from the liquid and is richer in the more volatile component.

The dew point temperature is the temperature at which a drop of liquid is formed in vapor mixture: Note: The composition of the dew is different from the vapor and is richer in the less volatile component. (2)

In order to find the bubble point temperature, you have to refer to the definition of a bubble point. You have to make an assumption that the feed (0.3 mol frac. methanol) is liquid and you need to find the temperature at which a bubble will form. X = 0.3 mol frac. methanol This point (3) will be on the bubble temperature line below the dew point line. (Please note: dew point is higher than bubble point)

The bubble and dew point temperatures are important for it tells you what is the range of operating temperature during separation of a mixture by distillation.

Bubble and Dew point Temperatures

(4) To find the dew point, we need to assume that all feed are vapor since the definition of dew point is that all are vapor with one drop of liquid. The answer can be found on the dew temperature line (4).

Bubble and Dew point Temperatures

Please visit the website:

http://www.chem.mtu.edu/~tbco/cm205/cm205_txy_tutorial.html

The site teaches how to set-up an excel file for the calculation of bubble and dew point temperatures given the Antoine equations of the components in the mixture. ** (2) Please write a similar excel program following the method illustrated in the site. Please explains what are the assumptions made at each stages of the calculation.

Please read section 6.4b-6.4d. ** (3) What is difference between Raoults and Henrys Law and under what condition can they be used?

(5)

As an exercise can you tell me what are points 1 and 2? Also, what are the composition of the vapor bubble in the liquid at the bubble temperature and the dew at equilibrium with the vapor at dew point temperature?

** (1) What is the significance of bubble and dew point temperature for distillation? Please explain in detail.

Other Types Equilibria

Please read section 6.5-6.7 Solid in Liquid A solid solute can dissolve in a liquid solvent to form a solution: Examples: (1) salt in water (2) benzoic acid in toluene (3) sugar in coffee

Solid in Liquid
Crystallization and filtration are two methods of separating solid from a solution. Crystallization process involves precipitation of the dissolved solid by changing the temperature or addition of crystallization or precipitation agents. Crystallization is an integral part of chemical separation and purification process. Most pharmaceuticals as well as proteins are separated and purified by crystallization. Filtration is a physical method of separating suspended solids from liquid. It involves a fiber or mesh to retain the solids. Can you describe in you own word what is the difference between (1)solution, (2) colloid and (3) suspension of solids in liquid? **(5) Problem 6.80

The maximum amount of solute that can be dissolve in a given amount of solvent is known as Solubility. Once the maximum is reached the solution is said to be saturated and additional amount of solute added will precipitate as crystals. These crystals are at equilibrium with the dissolved solid. However, under certain condition a solution can dissolve more solute and reach supersaturation, There are many factors that affect solubility. Visit the website shown below for more information about solubility.
http://www.chem.lsu.edu/lucid/tutorials/solubility/Solubility.html

** (4) What are the factors that affect solubility? Also answer the sample problems in the website.

Liquid Solution
The presence of a solute in a liquid can have a different physical properties compared to the pure liquid. Colligative solution properties refer to the change in vapor pressure, boiling point, freezing point and osmotic pressure of the solution with increasing amount of solute. The colligative properties depends only on the concentration of the dissolved solutes and not on the chemical nature of the solute material. Please read this website for more information on the colligative properties: http://www.chem.uidaho.edu/~honors/collig.html

Liquid-Liquid Equilibrium
Solutes have different affinity to different solvents. Ionic salts have greater affinity for water compared to organic solutes. The later will dissolve more in an organic solvent. The difference in the solubility of solute in different solvent is the basis of liquid extraction. Liquid extraction find uses in pharmaceutical, cosmetic and food productions. However, it has limited use in petrochemical due to the cost of solvent. Unlike distillation, mixture is obtain and further separation steps are needed to obtain a pure product and recover the solvent.
Liquid extraction uses solvent that is immiscible or partially immisible with the solution to be extracted. A miscibility chart is available at the website: http://www.chromatography.co.uk/TECHNIQS/Other/Miscibility.htm

Homework #4 due May 9, 2003 (1) 6.52 (2) 6.92 (3) Group: 6.58

Miscibility
Two liquids are said to be miscible if upon mixing, a single phase solution is obtained. (Single phase no separation) Immiscible liquids will separate out into two or more distinct phases after mixing.

Distribution Coefficient
Distribution coefficient or partition ratio measures the amount of solute dissolved in the extraction solvent (S) compared to the original solution (A). Distribution Coefficient for Acetic Acid Solvent Distribution Coefficient @ 20C 1.6 0.9 0.7 0.06 0.01 Miscibility with water (wt.% @ 20C) >10 10 2 0.05 0.015

Some of the liquids will dissolved into each other for a partially immiscible liquids. (Two or more phases one can separate each phases based on the difference in the liquid density) Miscibility can be induced by added foreign material to a miscible phase liquids. Example 1: hexane and ethanol are initially miscible. Addition of a few drops of water causes phase separation.

n-Butanol Ethyl Acetate MIBK Toluene n-Hexane

Visit the website: http://www.cheresources.com/extraction.shtml to know more about solvent selection. ** (1) What should be characteristics of a good extraction solvent? ** (2) If acetic acid is to be removed from water, which of the above solvent will you use and why?

Small amount of water is totally miscible with ethanol, but water is immiscible with hexane. The presence of water causes the separation of ethanol from hexane.

Miscibility
Two liquids are said to be miscible if upon mixing, a single phase solution is obtained. (Single phase no separation) Immiscible liquids will separate out into two or more distinct phases after mixing.

Distribution Coefficient
Distribution coefficient or partition ratio measures the amount of solute dissolved in the extraction solvent (S) compared to the original solution (A). Distribution Coefficient for Acetic Acid Solvent Distribution Coefficient @ 20C 1.6 0.9 0.7 0.06 0.01 Miscibility with water (wt.% @ 20C) >10 10 2 0.05 0.015

Some of the liquids will dissolved into each other for a partially immiscible liquids. (Two or more phases one can separate each phases based on the difference in the liquid density) Miscibility can be induced by added foreign material to a miscible phase liquids. Example 1: hexane and ethanol are initially miscible. Addition of a few drops of water causes phase separation.

n-Butanol Ethyl Acetate MIBK Toluene n-Hexane

Visit the website: http://www.cheresources.com/extraction.shtml to know more about solvent selection. ** (1) What should be characteristics of a good extraction solvent? ** (2) If acetic acid is to be removed from water, which of the above solvent will you use and why?

Small amount of water is totally miscible with ethanol, but water is immiscible with hexane. The presence of water causes the separation of ethanol from hexane.

Example: Problem 6.92 Given: Solute: Penicillin (P) Original solvent: water (W) Extraction solvent: butyl acetate (B) Water-butyl acetate are immiscible K = mass fraction P in B/mass fraction P in W pH K 2.1 25 4.4 1.38 5.8 0.10

Solution: Basis of calculation = 100 Kg acidified broth.

Acidified broth
m = 100 Kg 1.5 wt.% pennicilin

Extraction Unit 1

Raffinate 1
pH = 2.1 90% Extraction

Extract 1

Analysis: The penicillin was transferred from the original fermentation broth to butyl acetate solvent (Extract 1) at low pH leaving the impurities in the original solution (Raffinate 1). The bulty acetate solvent was recovered (Raffinate 2) and the pure penicillin dissolve back in water (Extract 2) at high pH. Find: (a) completely label the flowchart. **(3) do a degree of freedom analysis to show that all labeled variables can be determine.

90% of pennicilin was removed and 10% remains in the Raffinate. Water and butyl acetate are immiscible therefore all water will leave with Raffinate 1 and butyl acetate with Extract 1. Material balance water phase: water mwin = m(1-x) = 100 Kg (1-0.015) = 98.5 Kg = mwout penicillin mpin = (mp) Rout + (mp)Eout mpin = 100 Kg(0.015) = 1.5 Kg = (mp)Rout + 0.9 (1.5 Kg) (mp) Rout = 0.15 Kg

Solution: Continue...

Solution: Continue...

mR = 34.65 Kg 0 wt.% penicillin

Acidified broth
m = 100 Kg 1.5 wt.% penicillin

Extraction Unit 1

Raffinate 1
pH = 2.1 90% Extraction mR = 98.65 0.15 wt.% penicillin

Acidified broth
m = 100 Kg 1.5 wt.% penicillin

Extraction Unit 1

Raffinate 1
pH = 2.1 90% Extraction mR = 98.65 0.15 wt.% penicillin

Extract 1

Extract 1
mR = 36 Kg 3.75 wt.% penicillin

mwout = 98.5 Kg (mp) wout = 0.15 Kg Raffinate = 98.65 Kg, Penicillin (xR) = 0.15 wt.% Material balance in organic phase (i.e., butyl acetate) solvent mBin = mBout = [m(1-(xp)]Eout penicillin mpin = (mp)Rout + (mp)Eout Note: (mp)Ein = 0 (mp)Eout = 1.35 Kg = (mxp)Eout Note Raffinate 1 and Extract 1 are at equilibrium at pH 2.1 K = xE/xR = 25 **(4) Please conduct similar analysis of extraction unit no. 2.

K = xE/xR = 25

Note: xR = xR = 0.15 wt.%

xE = 25 (0.15 wt.%) = 3.75 wt.% = (xp)Eout (mxp)Eout = (mE)out(xp)Eout = (mE)out(3.75%) = 1.35 Kg (mE)out = 36 Kg

Distribution Coefficient
Distribution coefficient or partition ratio measures the amount of solute dissolved in the extraction solvent (S) compared to the original solution (A). Distribution Coefficient for Acetic Acid Solvent Distribution Coefficient @ 20C 1.6 0.9 0.7 0.06 0.01 Miscibility with water (wt.% @ 20C) >10 10 2 0.05 0.015

Adsorption on Solid Surfaces

Adsorbent are large surface area solids that can remove adsorbate molecules present in air or liquid. The removal is by attaching the adsorbate onto the surface by either weak physical bonds (physiadsorption) or strong chemical bonds such as chemisorption.

n-Butanol Ethyl Acetate MIBK Toluene n-Hexane

Physical adsorption or physisorption

Bonding between molecules and surface is by weak van der Waals forces.

Chemical bond is formed between molecules and surface.

Visit the website: http://www.cheresources.com/extraction.shtml to know more about solvent selection. ** (1) What should be characteristics of a good extraction solvent? ** (2) If acetic acid is to be removed from water, which of the above solvent will you use and why?

Chemical adsorption or chemisorption

Adsorbent are used to remove odor from air, to remove dyes and heavy metals from wastewater. The pollutants are usually transferred from air or water to solid phase, generating secondary waste in form of solid waste. Most adsorbate adsorb on surface follows the Langmuir adsorption isotherm.
**(5) Please describe in you own word what is a Langmuir isotherm. Please state the main assumption and its meaning. Absorption

Adsorption