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**Note: Practice Problems are marked either R: Recommended or FE: Further Enrichment
**

1. (R) Consider a process for converting lignocellulosic materials into ethanol. The ethanol

made via fermentation is separated from the solid residue to produce a process

stream that we will assume to be ca. 20% (w/w) ethanol, the rest being water. A

multi-stage distillation operation is used to produce 95.6% (w/w) ethanol fuel. If

the product stream has 20% of the mass flow rate of the feed stream, calculate the

composition of the waste stream and the fractional mass of the ethanol lost to waste.

Answer:

First, draw PFD:

2

F = 1000 kg/h

x1E=0.2

1

x1W =0.8

feed

Distillation

tower

Heat exchanger

5

6

reflux

product

3

waste

Assumptions:

-Steady-state

-Basis:

Given:

-x1E = 0.20 kgE/kg1

-x6E = 0.956 kgE/kg6

-E: ethanol; W: water

-No generation

-No consumption

-Streams 1, 3, and 6 containethanol and water

-Control volume defined overentire process, as shown

Goal: Find x3E, x3W,

Mass Balance:

**ACCN = IN – OUT + CONS – GEN
**

ACCN, GEN, CONS = 0

IN = OUT

IN = ; OUT =

x6E=0.956

x6W =0.044

Mass Balance for Ethanol:

**ACCN = IN – OUT + GEN – CONS
**

IN = OUT

IN =

; OUT =

In general:

m3E

m3E

kg

kg1

hr

kg

8.8 E

0.011 E

m3 0.80m1

hr 0.80kg3 1000kg1

kg3

kg

x 3E 0.011 E

kg1

x 3E

Now,(xij) = 1

x 3E x 3W 1

x 3W 1 x 3E (1 0.011)

x 3W 0.989

kgW

kg

0.989 W

kg1

kg1

kgW

kg1

**2. (R) Like distillation, which relies on establishing equilibrium between a vapor and a
**

liquid phase,

liquid-liquid extraction is another equilibrium separation process.

Here, a solute of interest is preferentially extracted from a complex solution by an

immiscible solvent. (Think back to your separatory funnel experiment in Intro Chem

lab.) The key challenge is to find an appropriate immiscible solvent that has a high

affinity for the solute of interest, but is also non-toxic and environmentally safe.

Supercritical CO2 is one such solvent. At high pressure and ambient temperature, it

behaves as an interesting “hybrid” between a liquid and a gas. On one hand, it can fill

a container like a gas; on the other, its density is comparable to that of a liquid. It

therefore has solvent-like extraction properties. After equilibrium has been

the mass flow rates of the beer streams in and out of the process are the same. steady state unit operation. the marketed product must have less than 0. Your fermentation-derived beer contains 10% w/w ethanol. (ii) In part b. Answer: a) First.achieved between the feed stream and the inlet supercritical fluid.25. x0 B. leaving the solute of interest behind. You wish to use supercritical CO2 to make a new brand of non-alcoholic beer. assume that the equilibrium constant K is the same for both stages of the process. how much does this process add to the cost of a liter of non-alcoholic beer? b) Your marketing consultant has advised you to keep the incremental of making the beer non-alcoholic to less than $1/pint. continuous. draw PFD: Beer CO2 B. Design a continuous process that achieves this target with no more than two stages. also at high pressure. a) First evaluate a single-stage. y1 Assumptions: -Steady-state Beer CO2 . That is. Under typical operating conditions. the two (immiscible) fluids are separated and CO2 is depressurized. If supercritical CO2 costs 10 cents per kilogram. and the CO2 and beer are drained into separate tanks. At equilibrium. To obtain a non-alcoholic label. the mass fraction of ethanol in beer (x) and supercritical CO2 (y) are related by the relationship y = K(T. K=1. y0 S.1% w/w ethanol. The effluent is allowed to separate into two phases. Decaffeination of coffee beans and dry cleaning of clothes are two examples of large-scale industrial processes that use supercritical CO2 as an extraction solvent. x1 S. and the mass flow rates of the CO2 streams in and out of the process are also the same. Hints: (i) Assume that the mass of ethanol exchanged between the beer and the supercritical CO2 phases is negligible relative to the beer stream and the CO2 stream.P)x. Both the beer and supercritical CO2 are pumped into a stirred tank at high pressure. At that point CO2 gas is purged.

001)) S = 79..92/ L Beer b) There are two ways to configure such a multi-stage unit operation.-Equilibrium -Beer = 1 g/cm3 1 kg/hr 1 L/hr -B = Beer. we find the incremental cost per L kg hr kg $ 79. First. y1 = Kx1 Goal: Calculate S/B Mass Balance for Ethanol:ACCN = IN – OUT + GEN – CONS ACCN. CONS = 0 0 = IN – OUT 0 = (Bx0 + Sy0) – (Bx1+ Sy1) Sy0 = 0 Sy1 = B(x0 – x1) From equilibrium y1 =Kx1 S = B(x0 – x1)/Kx1 S = (1 kg/h) (. x1 = .25 -At equilibrium.001)/((1. Let’s look at both. no consumption Basis: 1 kg Beer/hr Control volume as shown Given: -x0 = 0. S = Supercritical CO2 . the beer is sequentially passed through both stages.1 .2 kg CO2/h Now.10 hr kgBeer LBeer kgCO2 Incremental cost = $7.2 CO2 1 1 Beer . draw a PFD: . Cross-Current configuration: Here.1 (kg EtOH/kg Beer). y = mole fraction of ethanol in CO2 -Bin = Bout = B. Sin = Sout = S -No generation. and one-half of the supercritical CO2 is used in each stage.001 -y0 = 0 -K = 1.x = mole fraction of ethanol in beer.25)(. GEN.

x0 S. y0 Beer B. y2= Kx2 -Note: we will have 4 equations and 4 unknowns! Goal: Calculate S/B Mass Balance for Ethanol on Control Volume #1: Steady-state separation ACCN = IN – OUT + GEN – CONS ACCN. y = mole fraction of ethanol in CO2 -B0 = B1 = B2 = B. CONS = 0 0 = IN – OUT 0 = (Bx0 + Sy0) – (Bx1+ Sy1) Sy0 = 0 Bx0 = Bx1 + Sy1 Beer .x = mole fraction of ethanol in beer. y1 = Kx1. y2 CO2 Assumptions: -Steady-state -Equilibrium -Beer = 1 g/cm3 1 kg/hr 1 L/hr -B = Beer.x2 2 S. S = Supercritical CO2 . y1 CO2 B. no consumption -Basis: 1 kg Beer/hr Given: -x0 = .CO2 CO2 S. y0 B.001 -y0 = 0 -K = 1. x2 = . Sin = Sout = S (for both streams) -No generation. GEN. x1 1 S.25 -At equilibrium.1 (kg EtOH/kg Beer).

which is less than the goal of $1/pint Beer Counter-Current Method: Here.4 kg CO2/hr used by both streams together) Now. the beer and CO2 are introduced into different stages. and their direction of flow is “cross-current”.Mass Balance for Ethanol on Control Volume #2: Steady-state separation ACCN = IN – OUT + GEN – CONS ACCN. .2 kg CO2/hr (or 2S = 14.001)S 2 2((1)(1. GEN.4 kgCO2 /hr kgBeer 1 LBeer $ . solving for the new cost per pint of Beer 14. CONS = 0 0 = IN – OUT 0 = (Bx1 + Sy0) – (Bx2 + Sy2) Sy0 = 0 Bx1 = Sy2 + Bx2 Now.25)(.10 kgBeer /hr LBeer 2 pint Beer kgCO2 New cost = $0.1) 0 S = 7.001)S (1)2 (.72/pint Beer. remember that because we are at equilibrium y1 = Kx1 and y2 = Kx2 From the mass balance on #2: Bx1 = Sy2 + Bx2 and y2 = Kx2 x1 = x2(SK + B)/B From the mass balance on #1: Bx 0 Bx1 Sy1 y1 Kx1 (SK B) B SK(SK B) Bx 0 (SK B)x 2 x 2 B 2 2 B x 0 (BSK B )x 2 (SK) 2 x 2 (BSK )x 2 Bx 0 Bx1 SKx1 x1 x 2 (K 2 x 2 )S 2 2(BKx 2 )S B 2 (x 2 x 0 ) 0 Now.252 .001 . we plug in our given numerical values (1.

001 -y2 = 0 -K = 1. x2 = . y1 = Kx2.y0 B.x = mole fraction of ethanol in beer. x0 1 S. x2 S.25 -At equilibrium. CONS = 0 0 = IN – OUT 0 = (Bx0 + Sy1) – (Bx1 + Sy0) Mass Balance for Ethanol on Control Volume #2: Steady-state separation ACCN = IN – OUT + GEN – CONS ACCN. GEN. y1 Assumptions: -Steady-state -Equilibrium -Beer = 1 g/cm3 1 kg/hr 1 L/hr -B = Beer. x1 2 S. no consumption -Basis: 1 kg Beer/hr Given: -x0 = . CONS = 0 0 = IN – OUT 0 = (Bx1 + Sy2) – (Bx2 + Sy1) Sy2 = 0 Bx1 = Sy1 + Bx2 B.1 (kg EtOH/kg Beer). y0= Kx1 -Note: we will have 4 equations and 4 unknowns! Goal: Calculate S/B Mass Balance for Ethanol on Control Volume #1: Steady-state separation ACCN = IN – OUT + GEN – CONS ACCN. S = Supercritical CO2 .Beer CO2 B. S0 = S1= S2 = S (for both streams) -No generation. y = mole fraction of ethanol in CO2 -B0 = B1 = B2 = B. y2 Beer CO2 . GEN.

but the counter-current method’s efficiency is nearly twice that of the cross-current. (R) Mixtures of benzene and toluene are commonly produced in the production of gasoline. this value beats our goal of $1/pint of Beer. A 50.252 .001)S 2 (1)(1.10 kgBeer /hr LBeer 2 pint kgCO2 New cost per pint of beer = $0.25)(. solving for the new cost per pint of Beer 7. a.001)S (1)2 (.38/pint of Beer Again.6 kg CO2/hr Now.Now. mol% benzene-toluene mixture is fed to a flash drum at 95°C. remember that because we are at equilibrium y1 = Kx2 and y0 = Kx1 From the mass balance on #2: Bx1 = Bx2 + Sy1 y1 = Kx2 Bx1 = Bx2 + SKx2 x1 = x2(B+SK)/B From the mass balance on #1: B(x0-x1) = S(y0-y1)) remember that y0 = Kx1 and y1 = Kx2 (B SK) B (B SK) Bx 0 (B SK)x 2 SKx 2 ( 1) B B 2 x 0 (B 2 SKB)x 2 (SK) 2 x 2 Bx 0 Bx1 SK(x1 x 2 ) x1 x 2 (K 2 x 2 )S 2 (BKx 2 )S B 2 (x 2 x 0 ) 0 Now we plug in our given numerical values (1.54xB.001 . The equilibrium relationship at this temperature is yB=1. Assuming the .1) 0 S = 7. These chemicals are often separated by distillation for use as solvents and precursors in the production of other chemicals. 3.6 kgCO2 /hr kgBeer 1 L $ .

v. vi. Place 760 (mmHg) in all cells in the system pressure column.96. C=219. For benzene: A=6. For toluene: A=6.89. which is in this case benzene. use Raoult’s law to solve for yB and yT. Fill in the calculated system pressure column by referencing the vapor pressure and liquid mol fraction columns (recall Raoult’s law and Dalton’s law). The system pressure will remain the same for all data points and is a characteristic that must be reported for all Txy diagrams. Use your Txy diagram to plot the feed stream to the flash drum in part a.77. vii. xB (mol fraction benzene in the liquid). You can do this by guess and check or using the solver or goalseek functions in Excel. Reference the adjacent temperature cell but do not fill in a temperature value yet. iii. Create an Excel spreadsheet that contains the following columns: P (system pressure-given). P(sytem pressure-calculated). B. B=1346. You are now going to create your own Txy diagram. Use this equation to fill the cells in your vapor pressure columns. You can solve for the vapor pressures at a specific temperature using the Antoine equation: where A. iv.53.yB (mol fraction benzene in the vapor).89. Plot T vs. pT* (vapor pressure of toluene). xT (mol fraction toluene in the liquid). ii.vapor and liquid products from the flash drum have the same flow rate. You can now solve for T by using the constraint that the given system pressure and the calculated system pressure must be equal. follow the steps below: i.69. Leave the T column blank for now. 0. pB* (vapor pressure of benzene). and yT (mol fraction toluene in the vapor). To do this. Txy diagrams are often constructed for the more volatile component. c. Are these molar compositions consistent with those you calculated in part a? . Also use the Txy diagram to determine the vapor and liquid compositions emerging from this flash drum. 0. T (system temperature).05. 0. and C are constants that depend on the material. Use these numbers to fill in the xT column. B=1203.15…etc. calculate the molar composition of these streams.10. C=219. b. xB and yB on the same plot. Finally. Fill the xB column with 0. which shows the liquidvapor equilibrium of benzene-toluene mixtures as a function of temperature.

39)+50(yB) 50=19. yB Toluene.61 50=50(0.5+50(yB) yB=0.50.50)=50(xB)+50(yB) 50=50(xB)+50(1. zT F (mol/hr) Flash Drum T=95°C 1 Benzene. We were also given that zB=zT=0. so let’s take a basis of F=100 mol/hr. yT 2 V (mol/hr) Benzene. yT=0. We aren’t given a flow rate. Draw a PFD: Benzene. Let’s write our mass balances: Overall: F=L+V Benzene: FzB=LxB+VyB And we have our equilibrium relationship: yB=1.39.39 . xB Toluene.54xB) 50=127xB xB=0. We were told that V=L. so we know that V=L=50 mol/hr.61. zB Toluene.54xB We can solve this system of equations for xB and yB: 100(0.Answer: a. xT 3 L (mol/hr) Our control volume will be around the flash drum. xT=0.

00014 760.9187 85.526 328.7926 0.00005 760.6893 92.97987 1 yT 1 0.08988 0.50839 0.432 401.43355 0.00033 760.305 459.00069 760 760 760 760 760 760.8161 89.85 1287.85 0.754 419.7 0.3573 81.91012 0.49161 0.70508 0.65 0.21133 0.309 630.917 317.b.92 1230 1176.17726 0.61923 0.55 0.56645 0.4 0.24 1419.55564 0.95 0.62648 0.2227 90.09 1081.3131 80.7 0.25 0.95 1 xT 1 0.073 809.55 0.29 1576.75 0.8205 95.3 0.25 0.35 0.29492 0.11678 0.37352 0.75 0.572 The calculated pressure=xBpB*+xTpT* and yB=xBpB/P.895 760 pT* 760 712.14583 0.04172 0.75165 0.978 927.1 0. Pcalculated 760.00001 yB 0 0.00018 760 760.467 108. The excel spreadsheet should look something like this: P (given) 760 760 760 760 760 760 760 760 760 760 760 760 760 760 760 760 760 760 760 760 760 xB 0 0.45 0.15 0.65 0.024 102.099 306.05 0 T 110.53 1666.8 0.02013 -1E-08 .747 506.651 438.09 100.004 295.8 0.78867 0.38077 0.66736 0.059 104.982 961.2203 93.4 0.10962 0.619 836.153 563.7159 84.39 895 864.4949 96.3 0.4656 88.428 595.899 369.2074 0.527 384.33264 0.05 0.211 783.45 0.9 0.2 0.24835 0.05 533.1676 86.2 0.39 1350.5564 83.85 0.1 0.00002 760.44436 0.9 0.301 669.5 0.15 0.4377 82.427 355 341.89038 0.85417 0.06492 0.6 0.28865 0.22 1494.924 482.3031 pB* 1765.93508 0.5 0.54 1127.95828 0.00008 760.65 998.82274 0.71135 0.00002 760.35 0.204 106.00022 760 760 760.88322 0.6 0.25 1038.249 98.00023 760 760 760.

These streams are shown with yellow triangles below. The liquid and vapor streams have compositions on the blue and red curves respectively (blue: bubble point curve.The Txy diagram: c. red: dewpoint curve) at 95°C. We see that the liquid stream is ~40% benzene and the vapor stream is ~61% benzene. The feed is shown as a black triangle at 50% benzene and 95°C. . These numbers are consistent with those calculated in part a.

Answer: a. we will consider the control volume shown below. Calculate the molar compositions of the two product streams obtained from the distillation column if the column has (i) one stage and (ii) three stages with a reflux ratio of 10. Styrene. Why might this process be attractive. notwithstanding the poorer atom economy of this process compared to that in problem 4ab? Give at least two reasons. K2=0. the precursor of polystyrene.25. The styrene-rich liquid outlet stream is removed at a rate of 75mol/h. The feed stream enters at a rate of F=1. Consider only the distillation column. Polystyrene is currently produced at a rate of 1010kg/year. K3=0.35. (i) For a one-stage distillation. What fraction of the styrene in the feed is recovered in the liquid product stream for parts a) (i) and (ii)? c. is produced industrially through the following set of chemical reactions: a. The Raoult’s law constants for styrene for stages 1. with a styrene mole fraction of =0. 2. (R) Recall Practice Problem 11 from Module 5. respectively.0*102mol/h and is composed of styrene and ethyl benzene.4.65.45. b. The following alternative method for producing styrene is being considered: + CH3OH + H2O + H2 This process generally works under excess toluene conditions with a recycle stream of toluene. . and 3 are K1=0.

xs. and y are mole fractions. and L are molar flow rates and z. F. First. (ii) We can visualize three distillation stages as follows: . x. write a mole balance on styrene Finally. we will use in Raoult’s law We are given F. zS. Following the nomenclature in the modules. which leaves us with V. and ys as unknowns. We have three equations. so we can solve for the unknowns. write the overall mole balance: Next.V.Ethyl benzene and styrene are the two species to be separated. and L.

do a mole balance on the entire system: Styrene mole balance on the entire system: Mole balance on just the first stage: Styrene mole balance on just the first stage: Mole balance on the third stage: Styrene mole balance on the third stage: Raoult’s law The reflux ratio R .First.

The solutions (to two sig figs) turn out to be (Additional sig figs were carried through the calculation despite the fact only two are reported here. so we can solve the system.Our unknowns are and we have eleven equations. Answers may vary slightly depending on the point at which sig figs were truncated). You can solve this system with software or by hand using algebra. For part (i) For part (ii) c. 1) Single reactor .So the compositions of the aromatic-rich product streams are b.

3) Toluene is cheaper than benzene. so long as it has a water composition below 10mol%. which will allow for a more effective distillation. Will a single-stage distillation column suffice? If not. (R) Recall Practice Problem 9 from Module 3. The vapor is removed at a rate of 50mol/h. 4-methylthiazole (4-MT) is an important intermediate in the production of pharmaceuticals. Assume that the actual volume of the CSTR is 100L and that the concentration of all components other than acetone. 5. will a 2-stage distillation column with a reflux ratio of 10 suffice? The Raoult’s law constants (yi=Kixi. where xi and yi are the mole fractions of . Two processes for making 4-MT are shown below: (i) (ii) a. The product stream from the CSTR is to be purified using distillation. water. Practice Problem 10 of Module 4 and Practice Problem 5 of Module 9. The acetone-rich stream from the distillation column can be recycled. and 4-MT in the feed stream of the distillation column can be ignored.2) The difference between the boiling points of toluene and styrene is greater than the difference between the boiling point of ethyl benzene and styrene.

10.25. We need more stages. For the second stage.The feed flow rate is The acetone does not react in the second reaction. b. 0. and 4-MT. this mole fraction is too high with one stage. Answer: a.45. No. respectively. 0. The requirement is that .55. Draw an overall PFD for process (ii).15 for acetone. and 0. From Practice Problem 10 of Module 4 and Practice Problem 5 of Module 9 we see that The molar composition of the feed stream is Overall mole balance Water mole balance Raoult’s Solving by substitution. Overall mole balance Overall water mole balance Mole balance on first stage Water mole balance on first stage Raoult’s: Reflux . respectively. water.species i in the liquid and vapor phases. For two stages. respectively) for the first stage are 0. and 0. the constants are 0.30.

Solving by substitution. Overall mole balance Overall water mole balance Mole balance on first stage Water mole balance on first stage Raoult’s: Reflux .

Yes. two stages with R=10 works. .

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