Chapter 8

8.1 Liquid liquid Extraction Column

Liquid liquid extraction is one of the common method used in industries. Basically, liquid liquid
extraction is the separation of the components of a liquid mixture by treatment which one or more of
the desired components is preferentially soluble. In this process, it is essential that the liquid-mixture
feed and solvent are at least partially if not completely immiscible. Fundamentally, three stages are
involved. First is to bring the feed mixture and the solvent into intimate contact resulting the separation
of the two phases. Then the solvent from each phase will be removed and recovered (R.K Sinnot).

Liquid-liquid extraction is an important unit operation and finds applications in industries such as
refinery, pharmaceutical industries, metallurgical industries and other industries. In biofuel industry, the
purity level of biodiesel has strong effect on fuel properties, engine performance and engine life.
Therefore, a purification step is necessary. In biodiesel production plant, water washing method is used
in order to purify biodiesel. The main purpose of water washing is to separate FAME from the glycerol,
methanol and catalyst. This process also can remove other contaminant in the system that might
interfere with the next step of producing high purity level of biodiesel (shuchen: intro to process
engineering design).

8.2 Extractor Unit Selection

The selection of extractor type depends upon many factors including the required number of theoretical
stages or transfer units, required production rate, tolerance to fouling, ease of cleaning, availability of
the required materials of construction, as well as the ability to handle high or low interfacial tension,
high or low density difference, and high or low viscosities. Figure## below shows simplified guidance
flowchart for selection of extractor.
 Hence, from the guidance flowchart above, reciprocating plate column type of extractor has
been chosen for the water washing process. Since the water washing in biodiesel production is a process
that will cause the formation of emulsion, Karr Reciprocating Plate Extractor which is a descendent of
reciprocating plate column will be used. This is because Karr Reciprocating Plate Extractor is an extractor
that is well suited with mixtures with emulsifying tendency (PERRY 15-59). Emulsion formation is caused
by the reaction of unreacted waste cooking oil and soap with water. Figure## below shows the Karr
Reciprocating Plate Column with its main components.
 Figure##

Chemical Design of Karr Reciprocating Plate Extractor

Selection of Solvent

-Method on Designing the Karr Reciprocating Plate Column

1) Determination of mass fraction of key component

2) Calculate the maximum slope of operating line of the system.

3) Determination of the feed mass flow rate to the solvent mass flow rate, m f m s , and the operating
solvent flow rate, ms .
4) Calculate the mass fraction of key component in the entering light phase, y1k , in the light
phase.

5) Determine the extraction factor, AE .

6) Calculate the number of equilibrium stages, N e by using the Kremser-Souders-Brown

theoretical stage equation.

7) Calculate the cross sectional area, A , by dividing by the total volumetric flow rate (the sum of
the volumetric flow rates for both phases) by the total volumetric flow rate per unit of extractor
cross-sectional area, obtained from the Minimum NETS and Volumetric Efficiency for the Karr,
Reciprocating-Plate Extractor table.

8) Hence, the diameter, D , can be calculated.

9) Find height equivalent tower stages (HETS), at D1 by obtaining required data from the Effect
of Interfacial Tension on HETS for RDC and RPC Extractors table.
10) Calculate the extractor height, Z .

Summary of Flow Rate and Composition each Stream

The data of mass flow rate is obtained from Aspen simulation, hence the molar flow rate, mole fraction
and mass fraction of each stream is calculated and tabulated in tables below.

Feed stream

Component Flow rate Molar flow rate Mole fraction Mass Fraction
( kg / h ) ( kmol / h )
Methanol 529.968 16.54081 0.60 0.15
FAME 2292.05 7.730494 0.28 0.66
Glycerol 237.31 2.576831 0.09 0.069
Sulphuric Acid 29.006 0.295746 0.01 0.008
Triacylglycerol 374.69 0.423169 0.015 0.11

Extract stream

Component Flow rate Molar flow rate Mole fraction Mass Fraction
( kg / h ) ( kmol / h )
Methanol 529.968 16.54081 0.16 0.56
FAME - - - -
Glycerol 237.31 2.576831 0.01 0.25
Sulphuric Acid 29.006 0.295746 0.002 0.03
Water 153.3645 153.3645 0.89 0.16

Raffinate stream
 Component Flow rate Molar flow rate Mole fraction Mass Fraction
( kg / h ) ( kmol / h )
Methanol
FAME 2292.05 7.730493 0.88 0.856
Glycerol
Triacylglycerol 374.687 0.42317 0.05 0.14
Water 12.178 0.675997 0.07 0.004

Solvent Stream

Component Flow rate Molar flow rate Mole fraction Mass Fraction
( kg / h ) ( kmol / h )
Water 2775.08 154.0404 1 1

Selection of Key Component

In biodiesel water washing liquid liquid extraction system, to design the Karr Reciprocating Plate
Extractor, methanol will be selected as the key component. This is due to its solubility of methanol in
both feed and solvent stream. Methanol (solute) also has higher affinity towards the solvent which is
water. Hence, making it easier to separate methanol from FAME. Even though, glycerol is also soluble
and miscible with both water and FAME, glycerol is not selected as the key component as the amount is
too small compared to methanol.

Sizing of a Karr Reciprocating-Plate Extractor

To size the reactor, method or procedure above will be followed. Because FAME is lighter than the
solvent, water, it is introduced at the bottom and water at the top of the extractor. Data such as flow
rate and mass fraction of each stream are obtained from the mass fraction and mole fraction.

Feed Composition:

Methanol : 529.968 kg/h (0.15 mass fraction)

FAME : 2292.05 kg/h (0.66 mass fraction)

Glycerol : 237.31 kg/h (0.069 mass fraction)

Sulphuric Acid : 20.006 kg/h (0.008 mass fraction)

Triacylglycerol : 374.69 kg/h (0.11mass fraction)

Total flow rate : 3454.024 kg/h

Methanol Recovery:

= 99%
Based on the data obtained by Aspen simulation, the methanol recovery, , should be 100%, but it is
impossible to have 100% of methanol recovery, hence, 99% of methanol recovery value will be used in
the calculation.

Methanol Distribution Coefficient:

K = 2.0

Distribution coefficient is the ratio of concentrations of a compound in a mixture of two immiscible

phases at equilibrium. The value of methanol distribution is estimated by Drew et. Al [].

Continuous Phase Flux:

C = 0.5 gal/min-ft2

Karr Reciprocating Plate Extractor is one type of pulsed-column extractor, where for pulsed-column
extractor, a continuous-phase flux coefficient value of 0.5 is used. [Valle Riesta]

Mass Fraction of Key Component (Methanol) in the Raffinate

x2 k (1 ) x1k

Where

x2 k = Mass fraction of methanol in raffinate

= Methanol recovery

x1k = Mass fraction of methanol in feed

x2 k (1 0.99)0.15

x 2 k 0.0015

Operating Feed to Minimum Solvent Flow Rate Ratio

mf K k x1k y 2 k

mSM x1k x2 k

Where

mf = Operating feed flow rate, kg / h

mSM = Minimum solvent flow rate, kg / h

K = Methanol distribution coefficient

y2k = Mass fraction of methanol at solvent stream

mf 2.0(0.15) 0

mSM 0.15 0.0015

mf
2.02
mSM

Minimum Solvent Flow Rate, kg/h

The minimum solvent flow rate can be calculated by using the operating feed flow rate to minimum
solvent flow rate ratio.

mf
2.02
mSM

m f = total operating feed flow rate = 3454.024 kg/h

Hence,

mf
mSM
2.02
3454.024kg / h
mSM
2.02

mSM 1709.913kg / h

The minimum amount of water flow rate at the solvent stream is 1709.913 kg/h

Operating Solvent Flow Rate, kg/h

mf mf
C
mS mSM

3454.024kg / h
0.5(2.02)
mS

mS 3419.826kg / h
Calculated Value of Mass Fraction of Methanol at the extract stream, y1k

To obtain the mass fraction of methanol at extract, substitute x 2 k 0.0015 , which is the mass fraction
of methanol in the raffinate stream, and m f / mS 1.01 into the equation below:

mf
y1k y 2 k ( x1k x2 k )
ms

y1k 0 1.01(0.15 0.0015)

y1k 0.15

Extraction Factor, AE

Extraction factor is a measure of the ability of the system to separate between two or more components
in a liquid mixture. Extraction factor can be calculated by using the equation below:

mf
( )
mS
AE
Kk

Where

AE = Extraction factor

mf = Operating feed flow rate, kg / h

ms = Operating solvent flow rate, kg / h

K = Methanol distribution coefficient

1.01
AE
2

AE 0.505

Number of Equilibrium Stages, Ne

It is assumed that, in the system, the solutions are dilute so that the operating and equilibrium curves
are linear. Thus, the Kremser-Souders-Brown Equilibrium Stage Equation, can be used to calculate the
number of equilibrium stages [Perry page 15-46].
 x ( y2k / K )
log 1k (1 AE ) AE
NE x2k ( y 2k / K )
1
log
AE
Where,

NE = Number of equilibrium stages

x2 k = Mass fraction of methanol in raffinate

x1k = Mass fraction of methanol in feed

K = Methanol distribution coefficient

AE = Extraction factor

0.15 0
log (1 0.505) 0.505
NE 0.0015 0
1
log
0.505

N E 5.73 equilibrium stages 6 equilibrium stages

Determination of Height Equivalent Tower Stage, HETS

HETS is co-related with the interfacial tension of components in a mixture. The common method to
determine HETS is by using the Effect of Interfacial Tension on HETS for the RDC and RPC Extractors
table. However, the interfacial tension data of the components in this process does not appear to be
available.

To solve this problem, [Karr and Lo], comes out with an alternative method to find HETS where the HETS
for an extractor can be estimated by using scaling rule developed by them and the experimental values
of HETS was summarized in the Minimum HETS and Volumetric Efficiency for the Karr Reciprocating-
Plate Extractor table. Before that, we must determine whether the extraction system is low interfacial
tension system (MIBK, acetic acid, water system) or high interfacial tension system (o-xylene, acetic acid,
water system).

According to [dsaczxxv], the extraction system of biodiesel purification (water washing) process is a low
interfacial tension system. This can be proved by the formation of emulsion in the system. Emulsification
is one of the indication that the extraction system is low interfacial tension system.
From the table above, extractor with 12 inches (0.305 m) diameter which is estimated to be close to the
calculated diameter is selected. Then, the solvent or extractant of the extraction system must be
determine in order to choose the right combination of extractant and dispersed phase. In water
washing extraction system, the solvent (water) is dispersed at the top of the extractor, (take note that in
MIBK-Acetic acid-Water system, when water is selected as solvent, water will be dispersed at the top of
the extractor because the density is higher than MIBK). Hence, this will narrow down the choice of
extractor into only 3 which is in the blue box. Then, between these three, choose the extractor that give
the maximum volumetric efficiency (red box).

After deciding the extractor from the table, minimum HETS and the total volumetric throughput can be
determined.

Minimum HETS = 11.05 stages

 Total Volumetric Throughput = 1694 gal/(h)(ft2) or 69.023 m3/(m2)(h)

Cross-sectional Area of Extractors Column

In order to calculate the column cross-sectional area, volumetric flow rate of both inlet streams is
required.

mf
Feed stream volumetric flow rate =
f

mf = Operating feed flow rate, kg / h

f = Density of component at feed stream

mS = Operating feed flow rate, kg / h

S = Density of component at feed stream

Feed stream volumetric flow rate:

529.968kg / h 2292.05kg / h 237.31kg / h 29.006kg / h 374.69kg / h

792kg / m 3 873.9kg / m 3 1260kg / m 3 1840kg / m 3 875kg / m 3

3.92m 3 / kg

Solvent stream volumetric flow rate:

3419.826kg / h

1000kg / m 3

3.42m 3 / h
Then, substitute the value of volumetric flow rate obtained into the equation below to obtain the cross-
sectional area of the extractors column

[( m f / f ) (mS / S )]
A
JT

A = Cross-sectional area of extractors column

JT = Total volumetric flow rate per unit area

[(3.92 3.42)m 3 / h]
A
69.023m 3 / m 2 h

A 0.106m 2
Then, substitute the value of cross-sectional area of the extractors column into the equation below to
obtain the diameter of the column.

D 2
A
4
1/ 2
4(0.106m 2 )
D

D 0.367m or 14.45inches

Karr Reciprocating-Plate Extractor Scale Up

In order to maximize the production of biodiesel and also to increase the level of purity of biodiesel, Karr
Reciprocating-Plate Extractor must be scaled up from pilot to commercial scale. Equation below is used
for this step:
0.38
HETS C DC

HETS D
Where,

HETS C = Height equivalent tower stages at commercial scale

HETS = Height equivalent tower stages at pilot scale

Because D obtained is less than 30 inches or 0.762m, standard pipe size which is the Schedule 10S pipe
will be used. Schedule 10S pipe has an inside diameter of 10.42 inches and the most common used pipe
for extraction unit system. Hence, the scaling up calculation can be proceeded.
0.38
10.42
HETS C 11.05
12

HETS C 10.473inches , 0.266m

20% increment is done to prevent flooding at the extractors column. Therefore, the design of HETSc
after 20% increment is 12.567 inches. Then by using equation below, total height of extraction tower
can be calculated [Karr and Lo].

Extractor Height

After obtaining the HETSC, the height of the extractor can be calculated by using equation below

Z E N E ( HETS C ) D

Z E 6(12.567) 14.45
Z E 89.85inches or 2.28m

Top and Bottom Settler

Finally is to add top and bottom sections which will act as settlers to separate the phases. The diameter
of both settlers is 50% greater than the extractor diameter and the height of each settler is equal to the
settler diameter [buku madam ila xmau, kerekkk].

Therefore, the total height for both settlers is:

Z S 2(1.5)(10.42) 31.26inches or 0.794m

Total Height of Karr Reciprocating-Plate Extractor Tower

Z ZE ZS

Z (89.85 31.26)inches

Z 121.11inches or 3.076m