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Subject: 1304 332 Unit Operation in Heat transfer Instructor: Chakkrit Umpuch Department of Chemical Engineering Faculty of Engineering Ubon Ratchathani University

**Here is what you will learn in this chapter.
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5.1 Introduction to Extraction Processes 5.2 Equilibrium Relations in Extraction 5.3 Single- Stage Equilibrium Extraction 5.4 Equipment for Liquid-Liquid Extraction 5.5 Continuous Multistage Countercurrent Extraction

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**5.1 Introduction to Extraction Processes
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³When separation by distillation is ineffective or very difficult e.g. closeboiling mixture, liquid extraction is one of the main alternative to consider.´

**What is Liquid-liquid extraction (or solvent extraction)?
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Liquid-Liquid extraction is a mass transfer operation in which a liquid solution (feed) is contacted with an immiscible or nearly immiscible liquid (solvent) that exhibits preferential affinity or selectivity towards one or more of the components in the feed. Two streams result from this contact:

**a) Extract is the solvent rich solution containing the
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desired extracted solute.

b) Raffinate is the residual feed solution containing little solute.

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**5.1 Introduction to Extraction Processes
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Liquid-liquid extraction principle

When Liquid-liquid extraction is carried out in a test tube or flask the two immiscible phases are shaken together to allow molecules to partition (dissolve) into the preferred solvent phase.

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5 . Aqueous layer contains a weak acetic acid solution with a small amount of ethyl acetate.5. The amount of water in the extract and ethyl acetate in the raffinate depends upon their solubilites in one another.1 Introduction to Extraction processes An example of extraction: Extract Acetic acid in H2O + Raffinate Ethyl acetate Organic layer contains most of acetic acid in ethyl acetate with a small amount of water.

4 = 1 Equilateral triangular diagram (A and B are partially miscible.2 Single-stage liquid-liquid extraction processes Triangular coordinates and equilibrium data Each of the three corners represents a pure component A.xC yB = 1.0 .yC 6 .2 + 0. and the distance to base AC represents xB. B.) xB = 1. xA + xB + xC = 0.4 + 0. B.yA . or C. Point M represents a mixture of A.xA . The perpendicular distance from the point M to the base AB represents the mass fraction xC.0 . The distance to the base CB represents xA.5. and C.

Liquid C dissolves completely in A or in B. Liquid A is only slightly soluble in B and B slightly soluble in A. An original mixture of composition M will separate into two phases a and b which are on the equilibrium tie line through point M. The two-phase region is included inside below the curved envelope. The two phases are identical at point P.Liquid-Liquid phase diagram where components A and B are partially miscible. 7 . the Plait point.

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Point A = 100% Water Point B = 100% Ethylene Glycol Point C = 100% Furfural Point M = 30% glycol. C.5% water. 7% furfural The miscibility limits for the furfural-water binary system are at point D and G. 81. P and DEPRG in the ternary-mixture. 40% water. 45% glycol or on the saturation curve.Ex 5. 25ºC.2% furfural Point R = 11. the second phase occurs when mixture composition is 10% water. 9 . 45% furfural. ethylene glycol-furfural-water.5% glycol. Point P (Plait point). E. 30% furfural Point E = 41. the two liquid phases have identical compositions. Liquid-Liquid equilibrium. M.1 Define the composition of point A. DEPRG is saturation curve. 48. R. 10% water. if feed 50% solution of furfural and glycol. B. for example.8% glycol.101 kPa.

Equilibrium data on rectangular coordinates The system acetic acid (A) ± water (B) ± isopropyl ether solvent (C). The solvent pair B and C are partially miscible.xA . xB = 1.0 .0 .xC yB = 1.yA .yC Liquid-liquid phase diagram 10 .

60. and xB = 0.10.3. 10 kg of acetic acid (A). What are the compositions of the two equilibrium phases? Solution: Composition of original mixture is xc= 0.EX 5.2 An original mixture weighing 100 kg and containing 30 kg of isopropyl ether (C). and 60 kg water (B) is equilibrated and the equilibrium phases separated. 11 . xA = 0.

04.02 = 0.12.30.02 mass fraction.10 is plotted as point h.94.0.00 ± 0. 3.94 = 0. The composition of the extract (ether) layer at g is yA = 0. 2.12 ± 0.04 . Composition of xC = 0. and xB = 1. The tie line gi is drawn through point h by trial and error. 12 .86. The raffinate (water) layer composition at i is xA = 0. and yB = 1.Liquid-liquid phase diagram 1.02.0. yC = 0. xC = 0.00 . 4. xA = 0.

Phase diagram where the solvent pairs B-C and A-C are partially miscible.´ 13 . ³The solvent pairs B and C and also A and C are partially miscible.

3 Single-Stage Equilibrium Extraction Derivation of lever-arm rule for graphical addition Extract layer =V Raffinate Layer= L An overall mass balance: A balance on A: V L!M Vy A Lx A ! Mx AM 5.2 Where xAM is the mass fraction of A in the M stream.3 14 .5.1 5. A balance on C: VyC LxC ! MxC M 5.

7) L (kg ) V M ! M (kg ) L V (5.6 shows that points L.4) Sub 5.1 into 5. 5. Lever arm¶s rule L(kg ) V M ! V (kg ) L M (5. M.5) Sub 5.2 L y A x AM ! V x AM x A (5.1 into 5.1 into 5.8) 15 .3 x A x AM (5.Derivation of lever-arm rule for graphical addition Sub 5.6) Eqn. and V must lie on a straight line.3 L y C xC M ! V xC M x A xC xC M ! xC M y C x AM y A (5.

0.94. which is a reasonably close check on the material-balance method. 5.5 kg.04) L(0.8 units.2 ! ! ! M 100 gi 5.8 Solving. Solution: Substituting into eq. 16 .02.04.2. Determine the amounts of V and L.Ex 5. The original mixture contained 100 kg and xAM = 0.1 are for the extract layer (V) yA = 0.10. and xC = 0.10.10) Solving the two equations simultaneously.0 and V = 25.5 kg and V = 27. and for the raffinate layer (L) xA = 0. using the lever-arm rule.8. L L h g 4. the distance hg in Figure below is measured as 4. 5. yB = 0. and yC = 0.2 units and gi as 5. xB = 0. where M = 100 kg and xAM = 0. Then by eq.12. V (0.12) ! 100(0.1 V L ! M ! 100 Substituting into eq. Alternatively. L = 72.3 The compositions of the two equilibrium layers in Example 5.86. 5. L = 75.02.

0 5.11 17 .10 5.5. An overall mass balance: A balance on A: A balance on C: L0 V2 ! L1 V1 ! M 5.2 Single-stage liquid-liquid extraction processes Single-state equilibrium extraction We now study the separation of A from a mixture of A and B by a solvent C in a single equilibrium stage.9 L0 x A0 V2 y A 2 ! L1 x A1 V1 y A1 ! Mx AM L0 xC 0 V2 y C 2 ! L1 xC1 V1 y C1 ! MxC M x A x B xC ! 1.

xAM. 4. M in the Figure. We calculate M. and xCM by using equation 5. The amounts of L1 and V1 can be determined by substitution in Equation 5. 18 . 1. 5. Plot L0.9-5. L0 and V2 are known. V2.11.To solve the three equations. the equilibrium-phase-diagram is used. which locates the compositions of L1 and V1.9-5.11 or by using leverarm rule. 3. Using trial and error a tie line is drawn through the point M. 2.

xB 0 ! 0.Ex 5.157 Given: xc 0 ! 1 x A0 xB 0 ! 1.33 19 .4 A mixture weighing 1000 kg contains 23.235 0.5 wt% acetic acid (A) and 76.765 and y A 2 ! 1.0 0. Solution Given: L0 ! 1000kg and V2 ! 500kg Given: L0 V2 ! 1000 500 ! M ! 1500kg x A0 ! 0.235) (500)(0) ! (1500) x AM x AM ! 0.5 wt% water (B) and is to be extracted by 500 kg isopropyl ether (C) in a single-stage extraction.235.0 L0 x A0 V2 y A 2 ! Mx AM (1000)(0. Determine the amounts and compositions of the extract and raffinate phases.765 ! 0 L0 xC 0 V2 yC 2 ! MxC M (1000)(0) (500)(1) ! (1500) xC M xCM ! 0.

235.0) = (xA0. yC1) M(0.1.33) = (xAM.03) = (xA1.0.89) = (yA1.0.0.157. yC2) V1 (0. xC0) 20 .V2 (0. xCM) L1(0.2. xC1) M L0(0.1) = (yA2.

03) V1 (0.177.03 and yC1 = 0.5 From the graph: xC1 = 0.500 Solving eq(2) and eq(3) to get L1 and V1.1.86kg and V1 ! 525.2.33) L1 29. (1) L1 xC1 V1 yC1 ! MxC M L1 (0.89.5V1 ! 1.2 and yA1 = 0.03 and yC1 ! 0. y A1 ! 0.2) V1 (0. L1 x A1 V1 y A1 ! Mx AM L1 (0. (2) L1 ! 914.1) ! (1500)(0.67V1 ! 16. xC1 ! 0.89) ! (1500)(0.1.28kg Answer 21 x A1 ! 0.157) L1 0.From the graph: xA1 = 0.89 .

Distillation: Rapid and easy because of the large difference in density (Vapor-Liquid). the two phases in liquidliquid extraction must be brought into intimate contact with a high degree of turbulence in order to obtain high mass-transfer rates. Liquid extraction: Density difference between the two phases is not large and separation is more difficult.3 Equipment for Liquid-Liquid Extraction Introduction and Equipment Types As in the separation processes of distillation.5. Mixing by mechanical agitation Mixing by fluid flow themselves Liquid extraction equipment 22 .

Mixer-Settles for Extraction Separate mixer-settler Combined mixer-settler 23 .

Plate and Agitated Tower Contactors for Extraction Perforated plate tower Agitated extraction tower 24 .

Packed and Spray Extraction Towers Spray-type extraction tower Packed extraction tower 25 .

14 Balance on component A gives L0 x A0 V N 1 y AN 1 LN x AN V1 y A1 ! L0 V N 1 LN V1 5.12 5.13 5.12 and 5.13 L0 xC 0 V N 1 yC N 1 ! L N xC N V1 yC1 ! MxC M x CM ! x AM ! L0 xC 0 V N 1 y CN 1 L0 V N 1 ! LN xCN V1 y C1 LN V1 Combining 5.5.4 Continuous multistage countercurrent extraction Countercurrent process and overall balance An overall mass balance: A balance on C: L0 V N 1 ! L N V1 ! M 5.15 26 .

2. Also. Usually. and M as in the figure. a straight line must connect these three points.4 Continuous multistage countercurrent extraction Countercurrent process and overall balance 1. Plot points L0. L0 and VN+1 are known and the desired exit composition xAN is set. M. 3.5. VN+1. LN. and V1 must lie on one line. LN and V1 must also lie on the phase envelope. 27 .

yAN+1 = 0. The desired exit acetic acid concentration in the aqueous phase is 4%. below. yCN+1 = 1. Calculate the compositions and amounts of the ether extract V1 and the aqueous raffinate LN.0) ! 0.0.70. L0 = 200kg/h.5 Pure solvent isopropyl ether at the rate of VN+1 = 600 kg/h is being used to extract an aqueous solution of L0=200 kg/h containing 30 wt% acetic acid (A) by countercurrent multistage extraction. xC0 = 0. VN+1 and L0 are plotted.Ex 5.75 200 600 x AM ! L0 x A0 VN 1 y AN 1 200(0. xCM ! L0 xC 0 VN 1 yCN 1 L0 VN 1 ! 200(0) 600(1. In figure below. xA0 = 0.04. Also. Solution: The given values are VN+1 = 600kg/h. and xAN = 0. since LN is on the phase boundary. Use equilibrium data from the table. substituting into eqs. For the mixture point M.30.075 ! 200 600 L0 VN 1 28 .04.30) 600(0) ! 0. xB0 = 0. it can be plotted at xAN = 0.

90.Using these coordinates.017 is obtained. 5. LN = 136 kg/h and V1 = 664 kg/h. By substituting into Eqs.12 and 5. 29 .13 and solving. This gives yA1 = 0. 1) Point M is plotted in Figure below.08 and yC1 = 0. 2) We locate V1 by drawing a line from LN through M and extending it until it intersects the phase boundary. 3) For LN a value of xCN = 0.

5.Stage-to-stage calculations for countercurrent extraction.20 30 ..16 obtain difference in flows L0 V2 ! L1 V1 Ln 1 Vn 1 ! Ln Vn L0 V1 ! L1 V2 ! ( 5. Total mass balance on stage 1 Total mass balance on stage n From 5...17 5.16 5. 5.19 (x ( ! L0 x0 V1 y1 ! Ln x n Vn 1 y n 1 ! LN x N V N 1 y N 1 ! .18 is constant and for all stages ( ! L0 V1 ! Ln Vn 1 ! L N V N 1 ! ...

18 and 5. x is the x coordinate of point x( ! L0 x0 V1 y1 Ln x n Vn 1 y n1 LN x N V N 1 y N 1 ! ! L0 V1 Ln Vn 1 L N V N 1 5.Stage-to-stage calculations for countercurrent extraction.22 31 .21 5.19 can be written as L0 ! ( V1 Ln ! ( Vn 1 LN ! ( V N 1 5.

Then line L1 is drawn giving V2.21. Alternatively. which locates V1 on the phase boundary. is a point common to all streams passing each other. and so on. x can be calculated and point located. and L0 are known. such as L0 and V1. 1. 32 . Ln and Vn+1. Ln and Vn+1. 2. which is in equilibrium with V1. 6. This stepwise procedure is repeated until the desired raffinate composition LN is reached.Stage-to-stage calculations for countercurrent extraction. Next a tie line through V1 locates L1. the point is located graphically in the figure as the intersection of lines L0 V1 and LN VN+1.22 we start at L0 and draw the line L0 . The tie line V2L2 is drawn. 5. This coordinates to locate this operating point are given for x c and x A in eqn. Since the end points VN+1. LN or V1. 3. LN and VN+1. 5. In order to step off the number of stages using eqn. 5. The number of stages N is obtained to perform the extraction. 4.

70. Solution: The known values are VN+1 = 450.30. below. 3.10. xB0 = 0. L0. For the mixture point M. This construction is not shown.Ex 5.895. substituting into eqs. The exit acid concentration in the aqueous phase is 10 wt%. yCN+1 = 1.0.6 Pure isopropyl ether of 450 kg/h is being used to extract an aqueous solution of 150 kg/h with 30 wt% acetic acid (A) by countercurrent multistage extraction. and xAN = 0. The lines L0V1 and LNVN+1 are drawn and the intersection is the operating point as shown.075. 33 .75 and xAM = 0.072 and yC1 = 0. xCM = 0. L0 = 150. Calculate the number of stages required. xA0 = 0. The points VN+1. xC0 = 0. 1. The point M is plotted and V1 is located at the intersection of line LNM with the phase boundary to give yA1 = 0.12 and 5. 2. and LN are plotted in Fig. yAN+1 = 0. 5.13.

which has gone beyond the desired LN. 34 . A line L2 gives V3.21 to locate point . Starting at L0 we draw line L0 . A tie line through V2 gives L2. A final tie line gives L3. Line L1 is next drawn locating V2. 4. 5.1. A tie line through V2 gives L2.5 theoretical stages are needed.) 3. Then a tie line through V1 locates L1 in equilibrium with V1. the coordinates of can be calculated from eq. about 2. A line L2 is next drawn locating V2. Hence. Alternatively. which locates V1. 5. 2. 6. (The tie-line data are obtained from an enlarged plot.

the line will be straight when plotted on an xy diagram. y = mass fraction A in V stream. The solute A is relatively dilute and is being transferred from L0 to VN+1. ¨ x © Ld 0 ©1 x 0 ª ¨ x ¸ ¨ y ¸ © © ¹ V d N 1 ¹ ! L d N ©1 x ©1 y ¹ ¹ N 1 º N ª ª º ¨ x ¸ ¨ y ¸ © © ¹ V d n 1 ¹ ! L d n ©1 x ©1 y ¹ ¹ n 1 º n ª ª º ¸ ¨ y ¸ ¹ V d 1 ¹ © ¹ ©1 y ¹ 1 º ª º ¨ y ¸ ¸ © ¹ V d 1 ¹ ©1 y ¹ ¹ 1 º ª º 5.5. and x = mass fraction A in L stream. the stage calculations are made more easily. If y and x are quite dilute.4 Continuous multistage countercurrent extraction Countercurrent-Stage Extraction with Immiscible Liquids If the solvent stream VN+1 contains components A and C and the feed stream L0 contains A and B and components B and C are relatively immiscible in each other.24 Where L/ = kg inert B/h. V/ = kg inert C/h. 35 .23 ¨ x © Ld 0 ©1 x 0 ª 5.24) is an operating-line equation whose slope § L//V/. (5.

The equilibrium data are as follows (C5).7 An inlet water solution of 100 kg/h containing 0.0185 36 .00746 0. X 0.001959 0.00988 0.00682 0.010 wt fraction nicotine (A) in water is stripped with a kerosene stream of 200 kg/h containing 0.0202 y 0.00454 x 0.001010 0.00246 0. with x the weight fraction of nicotine in the water solution and y in the kerosene. Determine the theoretical number of stages needed. The water and kerosene are essentially immiscible in each other.0010 wt fraction nicotine. It is desired to reduce the concentration of the exit water to 0.0005 wt fraction nicotine in a countercurrent stage tower.00904 0.Ex 5.00500 y 0.000806 0.

yN+1 = 0.0kg water / hr ! V / ! V (1 y) ! VN 1 (1 y N 1 ) ! 200(1 0. 5.0005) ! 199. the line is straight.010. VN+1 = 200 kg/h. giving N = 3.23 and solving. The equilibrium line is also shown. These end points on the operating line are plotted in Fig.010) ! 99. The inert streams are Ld L(1 x) ! L0 (1 x0 ) ! 100(1 0. y1 = 0. below. Since the solutions are quite dilute.Solution: The given values are L0 = 100 kg/h.9kg ker osene / hr Making an overall balance on A using eq. 37 .00497. x0 = 0.8 theoretical stages.0010.0005. xN = 0. The number of stages are stepped off.

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9 1. Solve for the amounts both algebraically and by the lever-arm rule. A single-stage extraction is performed in which 400 kg of a solution containing 35 wt% acetic acid in water is contacted with 400 kg of pure isopropyl ether. What percent of the acetic acid is removed? 39 .Homework No. Calculate the amounts and compositions of the extract and raffinate layers.

) 40 .Homework No. 100 kg of water contacts the outlet organic phase from the first stage. 100 kg of water contacts the outlet organic phase from the first stage. (b) If a multiple four-stage system is used and 100 kg fresh water is used in each stage. 100 kg of water contacts the outlet organic phase from the second stage. For the third stage. calculate the overall percent recovery of the acid in the total outlet water. and so on. For the third stage. For the second stage. Pure water is to be used to extract acetic acid from 400 kg of a feed solution containing 25 wt% acetic acid in isopropyl ether. calculate the outlet extract and raffinate streams for the first stage using 400 kg of feed solution and 100 kg of water.10 1. (a) If 400 kg of water is used. calculate the percent recovery in the water solution in a one-stage process. (Hint: First.

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