Advanced chemical separation technology

Assoc Prof. Dr. Yin Li （李音）

School of Biological and Chemical Engineering
Cherryli1986@126.com
Office: Key lab building room 224
 Introduction of myself
My research area: Production of novel adsorbents, adsorptive separation

Some of my publications:
1 Li Y, Meas A, Shan S D, Yang R Q, Gai X K. Production and optimization of bamboo hydrochars for
adsorption of Congo red and 2-naphthol, Bioresource Technology, 207, 2016, 379-386.
2 Li Y, Lu X Y, Yang R Q, Tong W J, Xu L J, de Bondelon L, Wang H P, Zhu J, Ge Q. Adsorption of berberine
hydrochloride onto mesoporous carbons with tunable pore size, RSC Advances, 2016, 6: 28219-28228.
3 Li, Y, Fu J, Deng S G, Lu X Y. Optimization of Mesoporous Carbons for Efficient Adsorption of Berberine
Hydrochloride from Aqueous Solutions, Journal of Colloid and Interface Science, 424,2014, 104-112
4 Li, Y, Yuan B, Fu J, Deng S G, Lu X Y. Adsorption of Alkaloids on Ordered Mesoporous Carbon, Journal of
Colloid and Interface Science, 408, 181-190, 2013.
5 Li, Y, Liu J B, Cao R F, Deng S G, Lu X Y. Adsorption of myricetrin, puerarin, naringin, rutin, neohesperidin
dihydrochalcone flavonoids on macroporous resins. Journal of Chemical & Engineering Data, 58 (9), 2527–
2537, 2013.
6 Li, Y, Huang J H, Liu J B, Deng S G, Lu X Y. Adsorption of berberine hydrochloride, ligustrazine
hydrochloride, colchicine and matrine alkaloids on macroporous resins. Journal of Chemical & Engineering
Data, 58(5), 1271-1279, 2013.
7 Li, Y, Cao R F, Wu X F, Huang J H, Deng S G., Lu X Y. Hypercrosslinked poly(styrene-co-divinylbenzene)
resin as a specific polymeric adsorbent for purification of berberine hydrochloride from aqueous solutions.
Journal of Colloid and Interface Science, 400, 78-87, 2013.
8 Li, Y, Lu, X. Y. Solubilities of nizatidine in water, methanol, ethanol, acetone and ethyl acetate from (273.15 to
343.15) K. Journal of Chemical & Engineering Data, 55, 2010, 4019-4020.
9 Li, Y, Lu, X. Y. Measurement and correlation of solubilities of nizatidine in methanol +water, ethanol + water
and i-propanol +water mixtures from (273.15 to 303.15) K. Chinese Journal of Chemical Engineering, 20(5),
2012, 937-941.
Assessment methods

Final examination: 60 %

Average Grade & Attendance: 40 %

Attendance
Homework
Class presentation
Today’s topics

Classical separation technologies and the main content

of this course

Liquid-liquid extraction
Separation

All chemistry related industries need separation

processes.

The investment for separation processes could be up

to 50-80% of total investment in chemical industry.

In chemistry and chemical engineering, a separation

process is used to transform a mixture of substances
into two or more distinct products.
Separation

E.g. Crude oil is a mixture of various hydrocarbons

and is valuable in this natural form.

Natural gases
Gasoline
Diesel
Crude oil
Jet fuel
Lubricating oil
asphalt

Boiling point difference Distillation

 mAU

0
20
40
60
80
100
120
140
160

0
2.812
2.530 3.374
3.526
4.480
4.677
5.041
5.356
5.652
5.843
6.115
6.384
6.6337.034
7.867
8.332
8.833
9.248
9.852
10.282
10.742
10.909
12.689
13.417
14.066
14.927
16.822
Separation

17.647
18.175

20
20.822

31.459
34.005

40
VWD1 A, Wavelength=210 nm (20100416\002-0201.D)

48.916

52.668

60
60.722
63.943
80

88.232
91.258
A HPLC profile of the extracts from a herbal plant
100
Another example, extracts from natural resources

min
 Separation

(1) Low concentration, structural diversity of natural

products and coexisting impurities in extracts make
the separation and purification of natural products a
very challenging task.
(2) Most of the natural products are temperature or
light sensitive, some of them can decompose or
their molecular structures could be changed easily
at high temperatures.

Separation methods?
Separation

Here are some classical separation technologies:

Absorption
Adsorption Why these methods?
Centrifugation They based on?
Chromatography
Crystallization
Distillation All separations work by exploiting
Drying differences between the matter to be
Evaporation separated : size, shape, vapor pressure,
Extraction solubility, distribution ratios,
Filtration adsorption/absorption properties, etc.
And so on. And chromatography.
 Separation

 The mixture at hand could exist as a combination of any

two or more states: solid-solid, solid-liquid, solid-gas,
liquid-liquid, liquid-gas, gas-gas, solid-liquid-gas mixture,
etc
 The separated products could differ in chemical properties
or some physical property, such as size, or crystal
modification or other separation into different components.
 Separation processes - general

• Mechanical separations e.g. filtration of a solid

from a suspension in a liquid, centrifugation,
screening etc
• Mass transfer operations e.g. distillation,
extraction etc
Mass transfer operations – nature of
interface between phases

• Gas-liquid contact e.g. absorption,

evaporation, distillation etc
• Liquid-liquid contact e.g. extraction
• Liquid-solid contact e.g. crystallisation,
adsorption
• Gas-solid contact e.g. adsorption, drying etc
Mass transfer operations – controlling
transport phenomenon

• Mass transfer controlling e.g.distillation,

absorption, extraction, adsorption etc
• Mass transfer and heat transfer controlling
e.g. drying, crystallisation
• Heat transfer controlling e.g. evaporation
According to the solubilities of different compounds

• Crystallization 、recrystallization

• Solvating out、salting out

• Adjust the pH value of the solution (e.g.

alkaloids、proteins)
• Precipitation reaction

How about liquid-liquid extraction?

Liquid-Liquid extraction

Liquid-liquid extraction is a useful method to separate

components (compounds) of a mixture
Liquid-Liquid extraction
Let's see an example.
Suppose that you have a mixture of sugar in vegetable oil (it tastes sweet!)
and you want to separate the sugar from the oil. You observe that the sugar
particles are too tiny to filter and you suspect that the sugar is partially
dissolved in the vegetable oil.

What will you do?

Liquid-Liquid extraction

How about shaking the mixture with water

Will it separate the sugar from the oil? Sugar is
much more soluble in water than in vegetable
oil, and, as you know, water is immiscible (=not
soluble) with oil.

Did you see the result? The water phase is the

bottom layer and the oil phase is the top layer,
because water is denser than oil.

*You have not shaken the mixture yet, so sugar is

still in the oil phase.
Liquid-Liquid extraction
By shaking the layers (phases) well, you
increase the contact area between the two
phases. The sugar will move to the phase in
which it is most soluble: the water layer
"like dissolves like"

Now the water phase tastes sweet, because the

sugar is moved to the water phase upon
shaking.
You extracted sugar from the oil with water.
In this example, water was the extraction
solvent; the original oil-sugar mixture was the
solution to be extracted; and sugar was the
compound extracted from one phase to another.
Separating the two layers accomplishes the
separation of the sugar from the vegetable oil
Liquid-Liquid extraction

Did you get it? .....the concept of liquid-liquid extraction?

Liquid-liquid extraction is based on the transfer of a solute

substance from one liquid phase into another liquid phase
according to the solubility difference.

Extraction becomes a very useful tool if you choose a suitable

extraction solvent.

You can use extraction to separate a substance selectively from a

mixture, or to remove unwanted impurities from a solution.
 Liquid-Liquid extraction

In the practical use, usually one phase is a water or

water-based (aqueous) solution and the other an organic
solvent which is immiscible with water.

The success of this method depends upon the difference

in solubility of a compound in various solvents.

For a given compound, solubility differences between

solvents is quantified as the "distribution coefficient"
Liquid-Liquid extraction
Partition Coefficient Kp (Distribution Coefficient
Kd)
When a compound is shaken in a separatory funnel
（separation funnel, separating funnel) with two
immiscible solvents, the compound will distribute
itself between the two solvents.
Normally one solvent is
water and the other solvent is
a water-immiscible organic
solvent.
Most organic compounds are
more soluble in organic
solvents, while some organic
compounds are more soluble
in water.
According to the distribution ratios of different
compounds

Liquid-liquid extraction:
Distribution coefficient (or partition coefficient)K (Kp,
Kd)：
The K of a compound in a certain solvent system with
two phases at a certain temperature and pressure is a
constant.

K=Cu/CL
Cu：concentration of the component in the top phase；
CL： concentration of the component in the bottom
phase of the solvent system
According to the distribution ratios of different
compounds

Question:
Now we want to separate a mixture with two components of A
and B in a solvent system with chloroform and water, there is 1
g of A and 1 g of B in the mixture, KA =10, KB=0.1, and the
volume ratio of the two solvents is Vchloroform/Vwater=1, the
question is how many distributions should be taken to achieve a
90 % (mass fraction of one component in a certain phase if
higher than 90 %) separation for the two components?
According to the distribution ratios of different
compounds

Solution:
After one time of shaking and settling,
KA ＝ Cwater/ Cchloroform＝10,
and Vchloroform＝ Vwater , C·V=m
so mAwater/ mAchloroform＝ (Cwater ·Vwater )/(Cchloroform·Vchloroform)=10,
which means mAwater＝10 mAchloroform,
And mAwater＝10/11 g
So, after one time of shaking and settling, more than 90 % mass
fraction of A is in the top phase (water), and less than 10 %
mass fraction of A is in the under phase (chloroform).
According to the distribution ratios of different
compounds

In a similar way, we can know that at the same time,

more than 90 % mass fraction of B is in the bottom
phase (chloroform), and less than 10 % mass fraction
of B is in the top phase (water).

So, at these conditions, only one time distribution is

needed to achieve 90 % separation for A and B.
According to the distribution ratios of different
compounds
In this example, KA is much bigger than KB (KA =10,
KB=0.1), and A and B could be separated easily.
What if KA = KB ?
We can also use separation factor β to present whether the
separation is easy to achive.
Separation factor β:
β=KA/KB (notice: KA>KB)
β≥100, one simple liquid liquid extraction can achieve basic
separation (90 %);
100＞β≥10, 10-12 times of liquid liquid extraction;
β≤2, more than 100 times of liquid liquid extraction;
β≈1, KA≈KB?
Previously on Advanced chemical separation
technology

1 Partition Coefficient Kp (Distribution Coefficient Kd)？

K=Cu/CL

2 What if KA = KB ?
Separation can not be realized (in this system).
According to the distribution ratios of different
compounds

Question:
If an aqueous extract from a herbal material contains compound
A which can be extracted by ethyl acetate, and KA =10, and for
each time of liquid-liquid extraction operation, the volume ratio
of the two solvents is 1, after how many times of liquid-liquid
extraction operation with pure ethyl acetate, the concentration
of A in the aqueous solution would be lower than 1 % of the
initial concentration?
According to the distribution ratios of different
compounds
Solution:
The volume of the aqueous phase is presented as V, and the
initial concentration of A is set as 1, after one time of
distribution, the concentration of A in the aqueous phase is
set as x.
Because KA =10, So xV+10xV=V
x=1/11
After two times of contributions, the concentration of A in
the aqueous phase is set as y.
So yV+10yV=（1/11）V
y=1/121=0.83 %
So, after two times of liquid-liquid extraction operation with
ethyl acetate, the concentration of A in the aqueous solution
would be lower than 1 % of the initial concentration.
According to the distribution ratios of different
compounds

For acids, bases or amphoteric compound, the change

of pH value could change the states of these
compounds, and further change their distribution
ratios in a certain solvent system.

For example:
Dissociation of acid in water: HA + H2O≒A- + H3O+
Acids:
pH＜3, exist as HA;
pH＞12, exist as A-
About liquid-liquid extraction

• Commonly used organic solvents：

– cyclohexane, petroleum ether, benzene, chloroform,
ether, ethyl acetate, N-butanol, acetone, ethanol,
methanol
– Polarity: small to big
– Heavier than water: chloroform
– Water-immiscible (part immiscible) organic solvent:
from cyclohexane to N-butanol
– Water-soluble (at free percentage) organic solvents :
acetone to methanol
 Separation methods: chromatographic techniques

Classical or older chromatographic techniques include:

1. Thin-layer chromatography (TLC).
2. Preparative thin-layer chromatography (PTLC).
3. Open-column chromatography (CC).
4. Flash chromatography (FC).

Modern chromatographic techniques are:

1. High-performance thin-layer chromatography (HPTLC).
2. Vacuum liquid chromatography (VLC).
3. Countercurrent chromatography (CC).
4. Gas chromatography (GC).
5. High-performance liquid chromatography (HPLC).
6. Hyphenated techniques (e.g., LC-MS, LC-NMR, LC-MS-NMR).
Development of the separation techniques

Membrane separation molecular imprinting

molecular distillation Reversed Micelles Extraction
chromatographic technique
Supercritical fluid extraction
Double aqueous phase extraction

……
Main contents

•Supercritical fluid extraction

•Chromatographic separation
•Adsorptive separation
•Membrane separation
•Distillation separation
•Others ：Solid-liquid separation,
crystallization, molecular distillation，
molecular imprinting