Ekstraksi Cair-cair

Headline

1. Introduction to Extraction Processes

2. Equilibrium Relations in Extraction
3. Equipment for Liquid-Liquid Extraction
4. Single- Stage Equilibrium Extraction
5. Continuous Multistage Countercurrent
Extraction

2
5.1 Introduction to Extraction Processes

“Ketika pemisahan dengan penyulingan tidak efektif atau sangat sulit

contohnya Ketika titik didih campuran berdekatan, ekstraksi cair adalah
salah satu alternatif utama untuk dipertimbangkan"

What is Liquid-liquid extraction (or solvent extraction)?

Ekstraksi Cairan-Cairan adalah operasi perpindahan massa di mana
larutan cair (umpan) dikontak dengan cairan (pelarut) yang tidak
bercampur atau hampir tidak bercampur yang menunjukkan afinitas
preferensial atau selektivitas terhadap satu atau lebih komponen dalam
umpan. Dua aliran dihasilkan dari kontak ini:
a. Ekstrak adalah larutan kaya pelarut yang mengandung zat terlarut
yang diinginkan.
b. Raffinate adalah larutan sisa umpan yang mengandung sedikit zat
terlarut

3
5.1 Introduction to Extraction Processes

Liquid-liquid extraction principle

Ketika ekstraksi cair-cair dilakukan dalam tabung reaksi atau labu, dua
fase yang tidak bercampur dikocok bersama untuk memungkinkan
molekul untuk partisi (larut) ke dalam fase pelarut yang disukai.

4
5.1 Introduction to Extraction processes

An example of extraction:

Extract
Acetic acid in H2O Lapisan organik mengandung sebagian
besar asam asetat dalam etil asetat dengan
sedikit air.
+
Raffinate
Lapisan berair mengandung larutan asam
Ethyl acetate
asetat lemah dengan sejumlah kecil etil
asetat.

Jumlah air dalam ekstrak dan etil asetat dalam rafinasi tergantung pada
kelarutannya satu sama lain.

5
5.3 Equipment for Liquid-Liquid Extraction

Introduction and Equipment Types

Seperti dalam proses pemisahan distilasi, dua fase dalam ekstraksi cair-
cair harus bersentuhan dengan tingkat turbulensi yang tinggi untuk
mendapatkan laju perpindahan massa yang tinggi.

Distillation: Cepat dan mudah karena perbedaan densitas

yang besar (Vapor-Liquid).
Liquid extraction: Perbedaan densitas antara dua fase tidak besar
dan pemisahan lebih sulit.

Mixing by mechanical
Liquid extraction equipment agitation

Mixing by fluid flow

themselves
22
Mixer-Settles for Extraction

Separate mixer-settler Combined mixer-settler

7
Plate and Agitated Tower Contactors for Extraction

Perforated plate tower Agitated extraction tower

8
Packed and Spray Extraction Towers

Spray-type extraction tower Packed extraction tower

9
5.2 Single-stage liquid-liquid extraction processes
Koordinat segitiga dan data kesetimbangan

Masing-masing dari tiga sudut

mewakili komponen murni A, B,
atau C.
Titik M mewakili campuran A, B,
dan C.
Jarak tegak lurus dari titik M ke
dasar AB mewakili fraksi massa
xC. Jarak ke pangkalan CB
mewakili xA, dan jarak ke
pangkalan AC mewakili xB.

xA + xB + xC = 0.4 + 0.2 + 0.4 = 1

Equilateral triangular diagram xB = 1.0 - xA - xC

(A dan B Sebagian larut.)
yB = 1.0 - yA - yC
1
0
Liquid-Liquid phase diagram where components A and B are partially
miscible.

C cair larut sepenuhnya dalam A atau dalam B.

Cairan A hanya sedikit larut dalam B dan B sedikit larut dalam A.
Wilayah dua fase termasuk di dalam di bawah amplop melengkung.
Campuran asli komposisi M akan terpisah menjadi dua fase a dan b yang berada pada
garis ikatan kesetimbangan melalui titik M.
Dua fase identik pada titik P, titik Anyaman. 1
1
1
2
Ex 5.1 Define the composition of point A, B, C, M, E, R, P and DEPRG in
the ternary-mixture.

Titik A = 100% Air

Titik B = 100% Etilena Glikol Titik C = 100%
Furfural
Titik M = 30% glikol, 40% air, 30% furfural
Titik E = 41,8% glikol, 10% air, 48,2% furfural
Titik R = 11,5% glikol, 81,5% air, 7% furfural
Batas ketidaksesuaian untuk sistem biner air-
furfural berada pada titik D dan G.
Titik P (Titik anyaman), memiliki dua fase cair
komposisi yang identik.
DEPRG adalah kurva saturasi; misalnya, jika
umpan 50% larutan furfural dan glikol, fase kedua
terjadi ketika komposisi campuran adalah 10%
air, 45% furfural, 45% glikol atau pada kurva
saturasi.

Keseimbangan cair-cair, etilen glikol-furfural-air, 25ºC, 101 kPa.

Equilibrium data on rectangular coordinates

Sistem asam asetat (A) - air (B) -

pelarut isopropil eter (C).
Pasangan pelarut B dan C
sebagian larut..

xB = 1.0 - xA - xC

yB = 1.0 - yA - yC

Liquid-liquid phase diagram

14
EX 5.2 Campuran asli yang beratnya 100 kg dan mengandung 30 kg
isopropil eter (C), 10 kg asam asetat (A), dan 60 kg air (B) disetimbangkan
dan fase kesetimbangan dipisahkan. Berapa komposisi dari dua fase
keseimbangan?

Larutan:
Komposisi campuran asli adalah xc = 0,3, xA = 0,10, dan xB = 0,60.

15
Liquid-liquid phase diagram

1. Plot titik h pada komposisi xC =

0.30, xA = 0.10.
2. Garis tie line gi ditarik melalui
titik h melalui coba-coba.
3. Komposisi ekstrak (ether)
layer at g is yA = 0.04, yC =
0.94, and yB =
1.00 - 0.04 - 0.94 =
0.02
mass fraction.
4. The raffinate (water) layer
composition at i is xA = 0.12,
xC = 0.02, and xB = 1.00 –
0.12 – 0.02 = 0.86.

16
Diagram fase di mana pasangan pelarut B-C dan A-C sebagian larut.

"Pasangan pelarut B dan C dan juga A dan C sebagian larut."

17
5.3 Single-Stage Equilibrium Extraction

Derivation of lever-arm rule for graphical

addition

An overall mass balance: VLM 5.1

A balance on A: Vy A  Lx A  MxAM 5.2

Where xAM is the mass fraction of A in the M stream.

A balance on C: VyC  LxC  MxC M 5.3

18
Derivation of lever-arm rule for graphical
addition
Sub 5.1 into 5.2 L y A  x AM (5.4)
V  xA
x AM

Sub 5.1 into 5.3 L yC  xC M (5.5)


V x
 xC
CM

Equating 5.4 and xC  x C M  yC

x CM (5.6)
5.5 and rearranging
xA  xA M 
x AM
 yA

Eqn. 5.6 shows that points L, M, and V must lie on a straight line. By
using the properties of similar right triangles,

Lever arm’s rule L(kg) VM (5.7)

V (kg)  LM

L(kg) VM (5.8)
M (kg)  L V
19
Ex 5.3 The compositions of the two equilibrium layers in Example 5.1 are for
the extract layer (V) yA = 0.04, yB = 0.02, and yC = 0.94, and for the raffinate
layer (L) xA = 0.12, xB = 0.86, and xC = 0.02. The original mixture contained
100 kg and xAM = 0.10. Determine the amounts of V and L.

Solution: Substituting into eq. 5.1

VLM
Substituting into eq. 5.2, where 100
M = 100 kg and xAM = 0.10,

V (0.04)  L(0.12)  100(0.10)

Solving the two equations simultaneously, L = 75.0 and V = 25.0. Alternatively, using
the lever-arm rule, the distance hg in Figure below is measured as 4.2 units and gi
as 5.8 units. Then by eq. 5.8,
L L hg 4.2
  
M 100 gi 5.8
Solving, L = 72.5 kg and V = 27.5 kg, which is a reasonably close check on the
material-balance method.

20
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.

5.9
An overall mass balance: L0 V 2  L1 V 1  M

A balance on A:
L0 x A0
V 2 y A 2  L1 xA1 V 1 yA1  MxAM 5.10

A balance on C: V 2 y C 2  L1 xC1 V 1 yC1  MxC M 5.1

L0 x C0
1
x A  x B  xC  1.0
21
To solve the three equations, the equilibrium-phase-diagram is used.

1. L0 and V2 are known.

2.We calculate M, xAM, and xCM by
using equation 5.9-5.11.
3. Plot L0, V2, M in the Figure.
4.Using trial and error a tie line is
drawn through the point M, which
locates the compositions of L1 and V1.
5.The amounts of L1 and V1 can be
determined by substitution in
Equation 5.9-5.11 or by using lever-
arm rule.

22
Ex 5.4 A mixture weighing 1000 kg contains 23.5 wt% acetic acid (A) and
76.5 wt% water (B) and is to be extracted by 500 kg isopropyl ether (C) in a
single-stage extraction. Determine the amounts and compositions of the
extract and raffinate phases.

Solution Given: L0 1000kg andV 2  500kg

Given: L0 V 2 1000 500 M 1500kg

xA0  0.235, xB0  0.765and y c 2 1.0

L0 xA0 V 2 y A2  MxAM
(1000)(0.235)  (500)(0)  (1500)xAM
 0.157
x AM

Given: x c0  1  x A0  x B0 1.0  0.235 0.765 0

L0 xC0 V 2 y C2  MxC M

(1000)(0) (500)(1)  (1500)xC M

 0.33 19
xCM
V2 (0,1) = (yA2, yC2)
V1 (0.1,0.89) = (yA1, yC1)

M(0.157,0.33) = (xAM, xCM)

L1(0.2,0.03) = (xA1, xC1)

M
L0(0.235,0) = (xA0, xC0)

24
From the graph: xA1 = 0.2 and yA1 = 0.1;

L1xA1 V1 yA1  MxAM

L1(0.2) V1(0.1)  (1500)(0.157)

L1  0.5V1 1,177.5 (1)

From the graph: xC1 = 0.03 and yC1 = 0.89;

L1xC1 V1 yC1  MxC M

L1(0.03) V1(0.89)  (1500)(0.33)

L1  29.67V1  16,500 (2)

Solving eq(2) and eq(3) to get L1 and V1;

L1  914.86kg and V1 
525.28kg Answer
25
xA1  0.2, yA1  0.1, xC1  0.03and yC1  0.89
5.4 Continuous multistage countercurrent extraction

Countercurrent process and overall balance

An overall mass balance: L0 V N 1  L N V 1  M 5.12

A balance on C: V 1 yC1  MxC M 5.13

L0 x C0  V N 1 y CN 1  L N x CN

 V1 yC1 5.14
Combining 5.12 and 5.13  L0 xC 0  V N 1 y CN 1  L N xCN
xCM LN  V1
L0  V N 1
 V1 yA1
Balance on component A gives x AM L x V y L x
 0 A0L N 1 AN 1  N ANL 
5.15
0 N N 1
V1 V
26
Stage-to-stage calculations for countercurrent extraction.

Total mass balance on stage 1 L0 V 2  L1 V 1 5.16

Total mass balance on stage n V n 5.17

Ln1 V n1  Ln

From 5.16 obtain difference Δ in L0 V1  L1 V 2   5.18

flows

Δ is constant and for all   L0 V1  Ln Vn1  LN V N 1  .... 5.19

stages

x  L0 x0 V 1 y1  Ln x n V N 1 y N 1  ... 5.20

V n1 y n1  L N x N

27
Stage-to-stage calculations for countercurrent extraction.

Δx is the x coordinate of point

Δ

x   L0 x0 V1 y1  Ln xn V n1 yn1  LN x N V N 1 y N 1 5.21

L0 V1 Ln  Vn1 L N  VN
1

5.18 and 5.19 can be written

as
L0   V1 Ln   V n 1 L N    V N 1 5.22

28
Stage-to-stage calculations for countercurrent
extraction.
1.Δ is a point common to all streams passing each
other, such as L0 and V1, Ln and Vn+1, Ln and Vn+1,
LN and VN+1, and so on.
2.This coordinates to locate this Δ operating point
are given for x cΔ and x AΔ in eqn. 5.21. Since the
end points VN+1, LN or V1, and L0 are known, xΔ can
be calculated and point Δ located.
3. Alternatively, the Δ point is located graphically in
the figure as the intersection of lines L0 V1 and LN
VN+1.

4.In order to step off the number of stages using

eqn. 5.22 we start at L0 and draw the line L0Δ,
which locates V1 on the phase boundary.
5.Next a tie line through V1 locates L1, which is in
equilibrium with V1.
6.Then line L1Δ is drawn giving V2. The tie line
V2L2 is drawn. This stepwise procedure is
repeated until the desired raffinate composition LN
is reached. The number of stages N is obtained to
perform the extraction. 29
 Ex 5.6 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. The exit acid concentration in the aqueous phase is 10 wt%.
Calculate the number of stages required.

Solution: The known values are VN+1 = 450, yAN+1 = 0, yCN+1 = 1.0, L0 = 150, xA0
= 0.30, xB0 = 0.70, xC0 = 0, and xAN = 0.10.

1. The points VN+1, L0, and LN are plotted in Fig. below. For the mixture point M,
substituting into eqs. 5.12 and 5.13, xCM = 0.75 and xAM = 0.075.

2.The point M is plotted and V1 is located at the intersection of line LNM with the
phase boundary to give yA1 = 0.072 and yC1 = 0.895. This construction is not shown.

3. The lines L0V1 and LNVN+1 are drawn and the intersection is the operating point Δ
as shown.

30
1. Alternatively, the coordinates of Δ can
be calculated from eq. 5.21 to locate
point Δ.
2. Starting at L0 we draw line L0 Δ, which
locates V1. Then a tie line through V1
locates L1 in equilibrium with V1. (The
tie-line data are obtained from an
enlarged plot.)
3. Line L1 Δ is next drawn locating V2. A tie
line through V2 gives L2.
4. A line L2 Δ is next drawn locating V2. A
tie line through V2 gives L2.
5. A line L2 Δ gives V3.
6. A final tie line gives L3, which has gone
beyond the desired LN. Hence, about
2.5 theoretical stages are needed.

31
 V3 1
V2 0.95
V1 0.9
0.85
0.8
0.75
0.7
0.65
0.6
0.55
0.5
0.45
0.4
0.35
0.3
0.25
0.2
0.15
0.0999999999999998
0.0499999999999998
-2.22044604925031E-16
3 6 8 8 5 .2 5 .3 5 .4 5 . 5 5 . 6 5 . 7 5 .8 5 .9 5 1
000 E-1 999 999 0.1 0 0.2 0 0.3 0 0.4 0 0.5 0 0.6 0 0.7 0 0.8 0 0.9
0 7 9 9
000 456 999 999
00 44 99 99
000 074 999 999
50 39 49 99 L0
.0 67 L.0 .0
-0 2.5 N0 0
-
Chart Title
0.4

0.35

0.3

0.25

0.2

0.15

0.1

0.05

0
0 0.1 0.2 0.3 0.4 0.5 0.6 0.7 0.8 0.9 1
Homework No.9

1. 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. Calculate the amounts and compositions of the extract
and raffinate layers. Solve for the amounts both algebraically and by
the lever-arm rule. What percent of the acetic acid is removed?

33
Homework No.10

1. Pure isopropyl ether is to be used to extract acetic acid from 400 kg of

a feed solution containing 25 wt% acetic acid in water.
(a) If 400 kg of isopropyl is used, calculate the percent recovery in the
isopropyl solution in a one-stage process.
(b) If a multiple four-stage system is used and 100 kg fresh isopropyl is
used in each stage, calculate the overall percent recovery of the acid in
the total outlet isopropyl ether. (Hint: First, calculate the outlet extract
and raffinate streams for the first stage using 400 kg of feed solution
and 100 kg of isopropyl ether. For the second stage, 100 kg of
isopropyl ether contacts the outlet aqueous phase from the first stage.
For the third stage, 100 kg of isopropyl ether contacts the outlet
aqueous phase from the first stage. For the third stage, 100 kg of
isopropyl ether contacts the outlet aqueous phase from the second
stage, and so on.)

34
Homework No.9 (Solution)

1. 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. Calculate the amounts and compositions of the extract
and raffinate layers. Solve for the amounts both algebraically and by
the lever-arm rule. What percent of the acetic acid is removed?

Solution Given: L0 V 2  400 400 M  800kg

xA0  0.35, xB0  0.65 and y A 2 1.0

L0 xA0 V2 y A 2  MxAM
(400)(0.35)  (400)(0)  (800)xAM
 0.175
x AM

Given: xc0 1 xA0  xB0 1.0  0.35 0.65

0
L0 xC0 V 2 y C2  MxC M

(400)(0) x(400)(1)  (800)xC M 41

CM 
V2 (0,1) = (yA2, yC2)
V1 (0.12,0.87) = (yA1, yC1)

M(0.175,0.5) = (xAM, xCM)

L1(0.22,0.03) = (xA1, xC1)

M

L0(0.35,0) = (xA0, xC0)

36
From the graph: xA1 = 0.22 and yA1 = 0.12;

L1xA1 V1 yA1  MxAM

L1(0.22) V1(0.12)  (800)(0.175)

L1  0.54V1  636.36 (1)

From the graph: xC1 = 0.03 and yC1 = 0.87;

L1xC1 V1 yC1  MxC M

L1(0.03) V1(0.87)  (800)(0.5)

L1  29V1 1,333.33 (2)

Solving eq(1) and eq(2) to get L1 and V1;

L1  623.12kg and V1 
24.49kg Answer
37
xA1  0.23, yA1  0.12, xC1  0.03and yC1  0.88
 V1 (0.12,0.88) = (yA1, yC1)

M(0.175,0.5) = (xAM, xCM)

L1(0.23,0.03) = (xA1, xC1)

M

Lever arm’s rule

L1(kg) VM L1(kg) 0.38 L1(kg)  0.44x800

M (kg)  L V M (kg)  0.86 0.44 352kg

L(kg) VM L(kg) 0.38 V (kg)  352/ 0.81

V (kg)  LM V (kg)  0.47  0.81 434.57kg
38
The amount and composition of extract are

Answer
L1  325kg * xA1  0.23, xC1  0.03and xB1  0.74

The amount and composition of raffinate are

Answer
V1  434.57kg * yA1  0.12, yC1  0.88 and yB1 
0*The correction of amount of extract and raffinate depends on the
identification of points on the graph. The value obtained from Lever’s arm
rule is more reliable personally.

The percent of acetic acid removed is about

Answer
=(400x0.35-325x0.23)x100% = 46.6%
400x0.35

39
Homework No.10

1. Pure isopropyl ether is to be used to extract acetic acid from 400 kg of

a feed solution containing 25 wt% acetic acid in water.
(a) If 400 kg of isopropyl is used, calculate the percent recovery in the
isopropyl solution in a one-stage process.
(b) If a multiple four-stage system is used and 100 kg fresh isopropyl is
used in each stage, calculate the overall percent recovery of the acid in
the total outlet isopropyl ether. (Hint: First, calculate the outlet extract
and raffinate streams for the first stage using 400 kg of feed solution
and 100 kg of isopropyl ether. For the second stage, 100 kg of
isopropyl ether contacts the outlet aqueous phase from the first stage.
For the third stage, 100 kg of isopropyl ether contacts the outlet
aqueous phase from the first stage. For the third stage, 100 kg of
isopropyl ether contacts the outlet aqueous phase from the second
stage, and so on.)

40
Solution a):
Given: L0 V 2  400 400 M 
800kg
xA0  0.25, xB0  0.75 and y A 2 1.0
L0 xA0 V2 y A2  MxAM
(400)(0.25)  (400)(0)  (800)xAM
 0.125
x AM

Given: xc0 1 xA0  xB0 1.0  0.35 0.75

0
L0 x C 0 V 2 y C 2  MxC M

(400)(0) (400)(1)
  (800)xC M
xCM
0.5

41
V2 (0,1) = (yA2, yC2)
V1 (0.09,0.9) = (yA1, yC1)

M(0.125,0.5) = (xAM, xCM)

L1(0.17,0.03) = (xA1, xC1)

M

L0(0.25,0) = (xA0, xC0)

42
From the graph: xA1 = 0.17 and yA1 = 0.09;

L1xA1 V1 yA1  MxAM

L1(0.17) V1(0.12)  (800)(0.125)

L1  0.71V1  588.24 (1)

From the graph: xC1 = 0.03 and yC1 = 0.9;

L1xC1 V1 yC1  MxC M

L1(0.03) V1(0.9)  (800)(0.5)

L1  30V1 1,333.33 (2)

Solving eq(1) and eq(2) to get L1 and V1;

L1  570.18kg and V1 
25.43kg Answer
43
xA1  0.17, yA1  0.09, xC1  0.03and yC1  0.9
Solution b):
Given: L0 V 2  400100 M 
500kg
First stage xA0  0.25, xB0  0.75 and y A 2 1.0
L0 xA0 V 2 y A2  MxAM
(400)(0.25)  (100)(0)  (500)xAM
 0.2
x AM

Given: xc0 1 xA0  xB0 1.0  0.35 0.75

0
L0 x C 0 V 2 y C 2  MxC M

(400)(0)  (100)(1)
  (500)xC M
xCM
0.2

44
V2 (0,1) = (yA2, yC2)
V1 (0.12,0.86) = (yA1, yC1)

M(0.2,0.2) = (xAM, xCM)

L1(0.17,0.03) = (xA1, xC1)

L0(0.25,0) = (xA0, xC0)

M

45
From the graph: xA1 = 0.17 and yA1 = 0.09;

L1xA1 V1 yA1  MxAM

L1(0.17) V1(0.12)  (800)(0.125)

L1  0.71V1  588.24 (1)

From the graph: xC1 = 0.03 and yC1 = 0.9;

L1xC1 V1 yC1  MxC M

L1(0.03) V1(0.9)  (800)(0.5)

L1  30V1 1,333.33 (2)

Solving eq(1) and eq(2) to get L1 and V1;

L1  570.18kg and V1 
25.43kg
Answer
xA1  0.17, yA1  0.09, xC1  0.03and yC1  0.9 52