FACULTY OF ENGINEERING AND THE BUILT ENVIRONMENT (FEBE)

DEPARTMENT OF CHEMICAL ENGINEERING

MSOCHA3: Multistage Operations 3A

Instructor: Prof. C. Narasigadu

TUTORIAL 4

LU 3 – Liquid-Liquid Extraction

QUESTION 1
Consider the extraction of acetic acid from a dilute water solution into ethyl acetate at 25 oC. Estimate or obtain
the distribution coefficients for each species and the selectivity of the solute to the carrier.

Determine whether the system exhibits:

a) high selectivity
b) high solvent capacity
c) easy solvent recovery

Consider an alternate solvent from the data provided below.

Table 1. LLE data (mass fractions) for the system at 25 oC and 1 atm.
Component Feed Extract Raffinate
Acetic Acid 0.0588 0.0595 0.0564
Water 0.2353 0.0332 0.9242
Ethyl Acetate 0.7059 0.9073 0.0194

Table 2. Selectivity and distribution coefficients for the above feed components with selected solvent.
Component βAC (KA)D (KS)D (KC)D
Ethyl Acetate 29.3 1.055 46.8 0.036
1-Butanol 4.43 1.187 8.76 0.268
Di-isobutyl Ketone 94.8 0.365 1710 0.00385
Methyl Acetate 12.8 1.470 6.50 0.115
Di-isopropyl Ether 102.7 0.453 516 0.00441
QUESTION 2
In a batch solvent extraction experiment, an aqueous solution containing dissolved compounds is contacted with
an equal amount of pure amine solvent. The feed stream has a concentration of 120 g of dissolved ions per kg of
solution (water and dissolved compounds). The equilibrium concentration of the aqueous solution is 15 per kg of
solution. The equilibrium constant is 7 on a mass ratio basis.

a) Consider two successive batch operations, determine the final extraction if 100 g of the aqueous solution
is contacted with 50 g of fresh solvent in each of the two batch operations.
b) Determine the extraction if the fresh aqueous solution is contacted with 100 g of the fresh solvent in two
counter current stages (assuming equilibrium is reached in each).
c) Determine the solvent feed flow in to a 4-stage cross current cascade with an overall recovery of 99% of
the solute. The amount of the fresh aqueous feed fed in is 100 g.

QUESTION 3
A process stream consisting of components A and B is sent to an extraction unit where it is contacted with a
solvent S to extract the solute (B). The following data is available:
• stream flow rate 1000 kg/hr
• concentration of (B) in the stream is 5 wt %
• flow rate of solvent (C) is 500 kg/hr

From a literature source, the distribution coefficient at the process stream conditions is given as
K DB = YB
XB
where KDB is 4.0; YB solute in the solvent; XB solute in the carrier

Calculate the % extracted (i.e. the fraction of benzoic acid removed) for the following cases:
a) a single equilibrium stage
b) three cross current stages with equal portions of solvent
c) three counter current stages
d) an infinite number of cross current stages
e) an infinite number of counter current stages

QUESTION 4
An inlet water solution of 100 kg/hr containing 0.010 wt. fraction acid (A) in water is stripped with a solvent
stream of 200 kg/hr containing 0.0005 wt. fraction acid in a counter-current stage tower. The water and solvent
are essentially immiscible in each other. It is desired to reduce the concentration of the exit water to 0.0010 wt.
fraction A. Determine (analytically) the number of theoretical stages required. Equilibrium data is given in Table
3 below with x as the weight fraction of A in the water solution and y in the solvent.
Table 3. Equilibrium data for Question 4.
x y
0.0010 0.00073
0.0025 0.00212
0.0045 0.00397
0.0080 0.00721
0.0095 0.00860
0.0150 0.01369

QUESTION 5
An aqueous feed solution of 1000 kg/hr of acetic acid-water solution contains 30.0 wt. % acetic acid and is to be
extracted in a counter-current multi-stage process with pure isopropyl ether to reduce the acid concentration to
2.0 wt. % acid in the final raffinate. Use the equilibrium data in Table 4.

a) Calculate the minimum solvent ratio that can be used.

b) If the S/F ratio is equal to 3.15 × S/Fmin, determine the composition and amount of the streams leaving
the cascade as well as the number of theoretical stages required.
c) What is the composite of the solute (solvent-free basis) in the exiting extract stream?

Table 4. Equilibrium data for acetic acid-water-isopropyl ether system at 293 K.

Water Layer (wt. %) Isopropyl Ether Layer (wt. %)
Acetic Isopropyl Acetic Isopropyl
Acid Water Ether Acid Water Ether
0 98.8 1.2 0 0.6 99.4
1.41 97.1 1.5 0.37 0.7 98.9
2.89 95.5 1.6 0.79 0.8 98.4
6.42 91.7 1.9 1.93 1.0 97.1
13.30 84.4 2.3 4.82 1.9 93.3
25.50 71.1 3.4 11.40 3.9 84.7
36.70 58.9 4.4 21.60 6.9 71.5
44.30 45.1 10.6 31.10 10.8 58.1
46.40 37.1 16.5 36.20 15.1 48.7

Construct a right angled triangle diagram using the graph paper provided.
QUESTION 6
The tie-lines given in Table 5 are available for a partially miscible system consisting of solvents B and C, and a
solute A. Now 2.0 kg/s of a feed containing 60 % A and 40 % B is to be extracted by solvent C in cross current
extractor equivalent to three theoretical stages: the flow of solvent C being 0.91 kg/s to each stage.

What are the compositions of the raffinate and extract leaving the third stage and what is the flow rate of each
stream? What is the maximum possible concentration of A in the feed which could be handled?

Use the equilateral triangle diagram.

Table 5. Equilibrium data for Question 6.

Raffinate Phase (% by mass) Extract Phase (% by mass)
A B C A B C
70 25 5.0 71.6 4.8 23.6
60 37 3.0 62.5 2.5 34.0
50 48 2.0 52.0 3.1 44.9
40 58.5 1.5 41.9 3.1 55
30 68.5 1.5 31.9 3.0 65.1
20 79 1.0 22.0 2.9 75.1
10 89 1.0 11.1 2.1 86.8

QUESTION 7
Repeat the problem in Question 6 assuming counter-current operation. The feed is 2.0 kg/s with composition of
60 % A and 40 % B and solvent flow rate is 3 × 0.91 kg/s.

If the maximum concentration of A leaving the plant is as for the co-current extractor, how many theoretical
stages are required?

Use the equilateral triangle diagram.

 Useful Formula Sheet

𝑞 𝐹 𝑧 𝛼𝑥
𝑦=( ) 𝑥 − (𝑞−1) 𝑦=
𝑞−1 1+𝑥(𝛼−1)

𝑅 1 𝑉𝐵 +1 1
𝑦=( ) 𝑥 + (𝑅+1) 𝑥𝐷 𝑦=( ) 𝑥 − (𝑉 ) 𝑥𝐵
𝑅+1 𝑉𝐵 𝐵

𝐿 𝐷 𝐿′ 𝐵
𝑦 = 𝑥 + 𝑥𝐷 𝑦= 𝑥− 𝑥𝐵
𝑉 𝑉 𝑉′ 𝑉′

𝐿 𝐵 1
𝑅= =
𝐷 𝑉′ 𝑉𝐵

𝑙𝑜𝑔{[(𝑥𝑖,𝑁+1 )⁄𝑥𝑖,1 ][𝑥𝑗,1 ⁄(𝑥𝑗,𝑁+1)]} 𝑙𝑜𝑔[(𝑑𝑖 ⁄𝑑𝑗 )(𝑏𝑗 ⁄𝑏𝑖 )]

𝑁𝑚𝑖𝑛 = 𝑁𝑚𝑖𝑛 =
𝑙𝑜𝑔𝛼𝑖,𝑗 𝑙𝑜𝑔𝛼𝑚

1⁄2 𝑑 𝑑 𝑁min
𝛼𝑚 = [(𝛼𝑖,𝑗 )𝑁 (𝛼𝑖,𝑗 )1 ] (𝑏𝑖 ) = ( 𝑏𝑟 ) (𝛼𝑖,𝑟 )𝑚
𝑖 𝑟

𝑁
𝑓𝑖 𝑓𝑖 (𝑑𝑟 ⁄𝑏𝑟 )(𝛼𝑖,𝑟 )𝑚min
𝑏𝑖 = 𝑁 𝑑𝑖 = 𝑁
1+(𝑑𝑟 ⁄𝑏𝑟 )(𝛼𝑖,𝑟 )𝑚min 1+(𝑑𝑟 ⁄𝑏𝑟 )(𝛼𝑖,𝑟 )𝑚min

𝑧𝑖
∑𝑖 𝑧𝑖 𝐾𝑖 = 1 ∑𝑖 =1
𝐾𝑖

𝑧𝑖 (1−𝐾𝑖 ) 𝑧𝑖
𝑓{𝑇} = ∑𝐶𝑖 =0 𝑥𝑖 =
1+Ψ(𝐾𝑖 −1) 1+Ψ(𝐾𝑖 −1)

𝑧𝑖 𝐾 𝑖 𝐿∞ [(𝑥𝑖,𝐷 ⁄𝑥𝑖,∞ )−(𝛼𝑖,𝑗 ) (𝑥𝑗,𝐷 ⁄𝑥𝑗,∞ )]

∞
𝑦𝑖 = = 𝑥𝑖 𝐾𝑖 =
1+Ψ(𝐾𝑖 −1) 𝐷 (𝛼𝑖,𝑗 ) −1
∞

(𝛼𝑖,𝑟 )∞ 𝑧𝑖,𝐹 (𝛼𝑖,𝑟 )∞ 𝑥𝑖,𝐷

∑ =1−𝑞 ∑ = 1 + (𝑅∞ )min
(𝛼𝑖,𝑟 )∞ −θ (𝛼𝑖,𝑟 )∞ −θ

𝑁−𝑁min 1+54.4𝑋 𝑋−1 𝑅−𝑅min

𝑌= = 1 − exp [( ) ( 𝑋 0.5 )] 𝑋=
𝑁+1 11+117.2𝑋 𝑅+1

2 0.206
𝑁𝑅 𝑧HK,𝐹 𝑥LK,𝐵 𝐵
= [( )( ) ( )]
𝑁𝑆 𝑧LK,𝐹 𝑥HK,𝐷 𝐷

𝑦𝑛 𝑌𝑛 ⁄(1 + 𝑌𝑛 )
𝐾𝑛 = =
𝑥𝑛 𝑋𝑛 ⁄(1 + 𝑋𝑛 )
 𝑌𝑛+1 = 𝑋𝑛 (𝐿′ ⁄𝐺 ′ ) + 𝑌1 − 𝑋0 (𝐿′ ⁄𝐺 ′ )

𝑌𝑛 = 𝑋𝑛+1 (𝐿′ ⁄𝐺 ′ ) + 𝑌0 − 𝑋1 (𝐿′ ⁄𝐺 ′ )

𝐿′
𝐿′𝑚𝑖𝑛 = 𝐺 ′ 𝐾𝑁 (fraction of solute absorbed) ′
𝐺𝑚𝑖𝑛 = (fraction of solute stripped)
𝐾𝑁

𝐴𝑒 −1 𝑆𝑒 −1
𝜙𝐴 = = fraction not absorbed 𝜙𝑆 = = fraction not stripped
𝐴𝑁+1
𝑒 −1 𝑆𝑒𝑁+1 −1

𝐿 𝐾𝑉 1
𝐴= 𝑆= =
𝐾𝑉 𝐿 𝐴

𝜐1 = 𝜐𝑁+1 𝜙𝐴 𝜐1 = 𝑙0 (1 − 𝜙𝑆 )

𝑙𝑁 = 𝜐𝑁+1 − 𝜐1 𝑙𝑁 = 𝑙0 𝜙𝑆

𝐴𝑁+1
𝑖 −𝐴𝑖 𝑆𝑖𝑁+1 −𝑆𝑖
fraction of solute, i, absorbed = fraction of solute, i, stripped =
𝐴𝑁+1
𝑖 −1 𝑆𝑖𝑁+1 −1

𝐴𝑖 = 𝐿⁄(𝐾𝑖 𝑉) 𝑆𝑖 = 𝐾𝑖 𝑉⁄𝐿

𝜐1 = 𝜐𝑁+1 𝜙𝐴 + 𝑙0 (1 − 𝜙𝑆 ) 𝑙1 = 𝑙𝑁+1 𝜙𝑆 + 𝜐0 (1 − 𝜙𝐴 )

𝑙𝑁 = 𝑣𝑁+1 + 𝑙0 − 𝑣1 𝑣𝑁 = 𝑣0 + 𝑙𝑁+1 − 𝑙1

𝑙𝑇
𝐻𝐸𝑇𝑃 = 𝑙 𝑇 = 𝐻𝑂𝐺 𝑁𝑂𝐺
𝑁𝑡

1 1 𝐾 1 1 1
= + = +
𝐾𝑦 𝑎 𝑘𝑦 𝑎 𝑘𝑥 𝑎 𝐾𝑥 𝑎 𝑘𝑥 𝑎 𝐾𝑘𝑦 𝑎

𝑙𝑛{[(𝐴 − 1)⁄𝐴][(𝑦𝑖𝑛 − 𝐾𝑥𝑖𝑛 )⁄(𝑦𝑜𝑢𝑡 − 𝐾𝑥𝑖𝑛 )] + (1⁄𝐴)}

𝑁𝑂𝐺 =
(𝐴 − 1)⁄𝐴

𝑙𝑛(1⁄𝐴) 𝑙𝑛(1⁄𝐴)
HETP = 𝐻𝑂𝐺 (1−𝐴)⁄ 𝑁𝑂𝐺 = 𝑁𝑡 (1−𝐴)⁄
𝐴 𝐴

(𝐸) (𝑅)
𝑋𝐵 = 𝐾𝐷′ 𝐵 𝑋𝐵 𝐸𝐵 = 𝐾𝐷′ 𝐵 𝑆⁄𝐹𝐴

(1) (1) (2)

(𝑅) (𝐹) 1 𝑥𝑖 ⁄(1−𝑥𝑖 ) 1−𝑥𝑖
𝑋𝐵 ⁄𝑋𝐵 = = fraction not extracted 𝐾𝐷′ 𝑖 = (2) (2) = 𝐾𝐷𝑖 ( (1) )
1+𝐸𝐵 𝑥𝑖 ⁄(1−𝑥𝑖 ) 1−𝑥𝑖
 (𝑁)
1 𝑋𝐵 (𝑁) (𝐹) (𝑅) (𝐹) 1
Cocurrent cascade: = (𝐹) cross-current:𝑋𝐵 ⁄𝑋𝐵 = 𝑋𝐵 ⁄𝑋𝐵 = (1+𝐸 ⁄
1+𝐸 𝑋𝐵 𝑁)𝑁

= 𝑋𝐵 ⁄𝑋𝐵 = 1⁄ 𝑁
(𝑁) (𝐹) (𝑅) (𝐹)
Counter-current: 𝑋𝐵 ⁄𝑋𝐵
∑𝑛=0 𝐸 𝑛

(𝐾𝐴 )𝐷 = (𝑥𝐴 )II ⁄(𝑥𝐴 )I = (𝛾𝐴 )I ⁄(𝛾𝐴 )II (𝐾𝐶 )𝐷 = (𝑥𝐶 )II ⁄(𝑥𝐶 )I = (𝛾𝐶 )I⁄(𝛾𝐶 )II

(𝑥𝐴 )II ⁄(𝑥𝐴 )I (𝛾 )I⁄(𝛾 )II

(𝐾𝑠 )𝐷 = (𝑥𝑆 )II ⁄(𝑥𝑆 )I = (𝛾𝑆 )I ⁄(𝛾𝑆 )II 𝛽𝐴𝐶 = (𝐾𝐴 )𝐷 ⁄(𝐾𝐶 )𝐷 = = (𝛾𝐴)I⁄(𝛾𝐴)II
(𝑥𝐶 )II ⁄(𝑥𝐶 )I 𝐶 𝐶