ABCT3747 IntroChemBioProcTech

Lecture 3 Separation Processes (Unit operations)

A brief introduction
1. Separation processes in chemical and bioprocess technology (their
i
important
t t role
l andd functions).
f ti )
2. General concepts and characteristics of separation processes.
3 Some
3.
S
common separation/downstream
i /d
processes.

Refs: Geankoplis: Chapter 1 for an overview and other chapters for

various separation processes/unit operations.
More ref: R. Paul Singh UC Davis Resources in food eng
rpaulsingh.com/teachingfirstpage.htm Animations on separation processes
Evaporators;
p
; Membrane Systems;
y
; Driers
2015/9/14

Part I General concepts

1. Separation processes in CBPT
Why separation is needed in chemical and bioprocesses ?
In most cases, the desired product(s) from chemical and bioreactors is (are)
in a mixture with other components, such as un-converted reactants, byproducts and others required for the reaction such as catalysts, and the
components of solvent or reaction medium. Therefore, separation is needed
to recover the products in desired purity and forms.
C
A D C
D BAB
C A C
A+B C+D

A D AD
B
B A

Separation processes in process technology

Separation
p
is a major
j part
p of most chemical and bioprocess
p
plants,
p
havingg
significant influence on productivity, process economy and product quality.
The separation
p
of a product
p
often needs a series of separation
p
processes
p
with
different methods.
Most separation
p
pprocesses are common for chemical and biological
g
pproducts
(but different in the operating conditions).
High-value and low-concentration products usually are more tedious and
costly to separate.
Separation
p
of bioproducts
p
((from bioreactors)) is often more complicated
p
than chemical products (from chemical reactors). Separation of bioproducts
usually accounts for more than 50% of the overall manufacturing cost.
3

Qs: (1) Reactor output (a) probably contains what compounds?

Separation processes in chemical production

(Toluene, Benzene, CH4 and H2); (b) the state of the mixture is

(gas-liquid mixture).
(2) The separation process in the Still is distillation
?

Separation processes
Separation processes

CH2=CH2 + H2O

CH2CH2OH

Ethanol
production
direct hydration
of ethylene
Block
flow diagram
for thebyproduction
of benzene
(unknown author on www)
4

Separation in bioprocess
technology

Process stages

Operations

RAW MATERIALS

Bioprocess plant generally divided into

two processing parts:
1. Upstream processing: for
biochemical conversions in the
fermentors or bioreactors.
2 Downstream processing:
2.
i
f
for
recovery, purification and formulation
of products, which are mostly physical
separation processes.
Most of these are unit
operations or separation
processes in chemical
engineering
5

Unit operations or Separation processes

Unit operationis a conventional term used in chemical industry and
chemical engineering for various separation processes.
processes
Each unit operation is regarded as a separate and distinct step or unit in the
whole process. A given unit operation has the same principles and basic
operations in different production processes.
Unit operations is still widely used but gradually replaced by separation
processes .
processes

2. General process strategies and characteristics

Separation is always based on the difference in a physical property among the
How to achieve
mixture components,
p
such as size, density,
y color, solubility,
y boilingg
separation?
point/volatility, polarity, electrical charge, affinity.

Classification
Cl
ifi ti off separation
ti processes (physical
( h i l mechanisms
h i
off
separation)
1 M
1.
Mechanical
h i l separations:
i
separations
ti
based
b d on size
i and/or
d/ density
d it differences
diff
of the mixture components, mainly for separation of solid from liquid (e.g.
filtration and centrifugation).
g
)
2. Diffusional separations (mass transfer operations): separations based on
molecular movement toward a favourable phase, for separation of dissolved
components (e.g. distillation, adsorption, extraction).
3. Membrane separations: use of a semipermeable membrane to separate
molecules of different sizes or different other properties.
properties
7

Part II Common separation processes

A. Mechanical separation of solid from liquid
1. Filtration
i
i is the mechanical separation of solid particles from a fluid by
passing the fluid through a filtering medium, or septum, on which the solids
are deposited.
p1

Filtration separation is driven by the

pressure
difference (p) between
?
two sides of the filtration medium,
created either by

Slurry
Filter cake
Filter cloth
Support for
filter cloth

1) a higher pressure on upstream side;

2) a vacuum at downstream side; or
Filtration
3) a centrifugal
force.

p = p1-p2

p2

Note: Rate of filtration depends strongly on properties of the slurry,

slurry
compressibility of solid cake and viscosity of liquid.

Filtrate

Filtration
o sep
separation
o process
p ocess
The most common filtering medium is fabric cloth
with
ith strong
t
mechanical
h i l properties.
ti The
Th fabric
f b i causes
the solid particles to become entangled on the surface
of the cloth, resulting in the formation of a solid layer,
and the build up of the solids on the layer (into a filter
cake).

Filter cloth

As the solid layer increases its thickness, the resistance to the fluid flowing
through the filter increases, so that the rate of filtration will decrease if a
constant pressure (or other driving forces) is applied to the fluid.
Usually the solid (filter cake) is removed periodically from the filter before
the resistance becomes extremely
y high.
g
Note: Filtration process is mainly controlled by the
? solid layer rather than the
filtering medium.
9

2. Centrifugal separation
Centrifugation is to separate materials of different densities
with a force
?
greater than gravity.
Stokess law (background knowledge): the maximum settling
velocity of a rigid particle in a fluid under gravity,
gD p ( p )
2

vt

18

g = gravitational constant (9.81 m/s2),

Dp= particle diameter; p = density of particle,
=density
density of fluid; = viscosity of fluid
fluid.

Centrifugation intensity is given by the ratio of centrifugal

force to g
gravity,
y, called g
g-force
f
with the unit g,
g ,
Fc / Fg =

2r
g

= 2N, the angular velocity of centrifuge; N = rotation

speed common expressed as rpm or rps; r = radial
distance of particle from the centre of centrifuge bowl

Sedimentation velocity of particle under

centrifugal force:

? 2rDp 2 ( p )
vc
18

Q: discuss major factors affecting rate of centrifugation

10

Laboratory centrifuges
Regular operations: solid-liquid separation such as cells, wide ranges: from <
1.0 mL to few hundred ml.
Ultracentrifuges: very high speeds for separation of macromolecules (proteins,
DNA and polymers) in biochemistry. Two classes: preparative and analytical.

Centrifugation
wordpress.com
11

An industrial centrifuge
Tubular bowl centrifuge: simple configuration;
bowl is tall with a small diameter (100-150
(100 150 mm);
can develop about 13,000 g force; widely used in
food and pharmaceutical industries.
Used for longer than most other centrifuges; With a
tube rotating between bearings at each end.
end The
process stream enters at the bottom of the centrifuge
and high centrifugal forces act to separate out the
solids. The bulk of the solids will adhere on the walls
of the bowl, while the liquid phase exits at the top of
the centrifuge. As this type of system lacks a provision
of solids rejection, the solids can only be removed by
stopping the machine
www.lenntech.com/library/clarification/
l t h
/lib
/ l ifi ti /
clarification/centrifugation.htm 12

Filtration versus centrifugation

1. Both belong
g to mechanical separation
p
of solid from liquid.
q
2. Filtration, based on particle size.
3 Centrifuging,
3.
C t if i
b d on density
based
d i difference
diff
(
(can
b used
be
d for
f liquid-liquid
li id li id
separation).
4. Filters are usually simpler and cheaper than centrifuges.
5. Centrifuges can be used for particles which are difficult to filter, e.g., very
small and compressible ones.
Centrifugation applied to filtration: centrifugal filters.
Further reading on filtration and related mechanical separations: Geankoplis Sect
14.1-14.2; 14.4

13

B. Two
Two--phase contact processes
for separation of homogeneous mixtures
To separate or remove one or more components from a homogenous mixture
in gas, liquid or solid phase, the mixture is usually brought into contact with
aanother
?nother phase (creating the separation driving force and environment). During
the contact between the two phases, the components can diffuse from the
original mixture into another phase.
Various 2-phase contact processes
Process

Phases and mass transfer

direction

Distillation (fractional)
Absorption/Scrubbing
Stripping/Desorption
Adsorption
Leaching (Solid-liquid extraction)
Solvent extraction

Liquid Gas (Vapor)

Gas Liquid
Liquid Gas
Gas or Liquid Solid
Solid Liquid
Liquid Liquid

14

3. Distillation
s
o or
o fractional
c o
distillation
ds
o
Distillation is the separation of components in a liquid
mixture or solution
?
by a process involving partial vaporization.
Separation of constituents is based on
?
differences in volatility
(or vapor
pressure, boiling point).

Apparatus for
distillation lab

Q: Describe the apparatus (parts

and functions), experimental
materials, conditions and
procedure.

15

Continuous Distillation
General flow diagram of continuous distillation
Top or overhead
h d
product (high A;
low B)
Vapor

Feed
A+B

Liquid

Distillation
column
L

C d
Condenser

Reboiler
Bottom product
(low A; high B)

Applications of distillation One of the most important separation processes

in chemical process industries.
Oil refining:
fi i
petroleum
l
iinto severall ffractions
i
suchh as li
light
h gases, naphtham,
hh
gasoline, kerosene, fuel oils, lubricating oils and asphalt).
Distillation of liquid air to produce pure oxygen for use in steel-making, in rockets,
and medical applications.
Ethanol (alcohol)-water separation.

16

Oil refining
fi i process (simplified)
( i lifi d)

17

4.. Absorption
bso p o (gas
g s absorption)
bso p o )
Removal of a solute component from
its gaseous mixture by means of a
liquid which dissolves the solute gas.
Common equipment: Packed tower
(column), filled with packings to
pro ide the gas-liquid
provide
gas liq id contact area.
area
Gas enters at the bottom and liquid at
the top.
top Counter-current
Counter current flow of gas
and liquid thru the towers for
maximum driving force.
Figure130.mht

www.separationprocesses.com/Absorption/GA_Chp04.htm

(Driving force = difference between actual

and equilibrium concentrations)

Absorption
p
in a p
packed tower
18

Gas absorption
Applications:
IIn coke
k plants,
l
to absorb
b b by-product
b
d gases, suchh as ammonia
i with
i h water,
and benzene and toluene with oil.
R
Remove CO2 and
d H2S ffrom natural
t l or synthetic
th ti gas by
b solution
l ti off
amines and alkaline salts.
Air pollution control: pollutants in gaseous effluents.
effluents
Note: find more details of these applications.
Synonyms of gas absorption: scrubbing so the equipment called absorber
or scrubber.
The reverse process of absorption is stripping (in strippers), the removal of
a solute from liquid solution by a gas.
Further reading on absorption: Geankoplis 10.2; 10.4A, 10.6A,B.

19

5. Extraction
Extraction ( , ): the use of a liquid solvent to dissolve and remove
the target components from a solid material (solid-liquid extraction) or from a
liquid solution (liquid-liquid extraction ).

5.1. SolidSolid-Liquid Extraction

Solid-liquid extraction (leaching): use of a liquid solvent to extract the
constit ents from a solid matter.
constituents
matter
Daily life examples: making tea; cooking soup; herbal medicine decoction.
Industrial
d i l processes: metals
l (e.g.
(
C Co,
Cu,
C Ni,
i Au)
A ) ffrom ores with
i h aqueous
acids; intracellular products from biomass; sugar from sugar cane; active
ingredients of herbs.
Major process factors: Properties of solvent, solid properties and particle
size, solid-liquid
q
ratio, temperature,
p
ppressure, mixingg conditions
20

Soxhlet extraction: a common lab practice

wikipedia

http://en.wikipedia.org
http://webpages.marshall.edu/ vanhoose3/soxhletex
http://webpages.marshall.edu/~vanhoose3/soxhletex
tractionapparatus.html
21

5.2 LiquidLiquid-liquid Extraction

Liquid-liquid or solvent extraction: selected extraction of a solute from a
y of the solute in two solvents.
solution based on the difference in the solubility
Applications: plant/vegetable oils (e.g. soybean, peanut, olive and corn) with
nn-hexane;
hexane; penicillin from water with amyl acetate; benzene from crude oil and
coal.

Theory:
K=Y/X, partition or distribution
coefficient, an equilibrium constant
at given temp and pH.
Y, X= solute concentrations in the
Y
light (L) and heavy (H) phase,
respectively.

Extracting
solvent

L, Y

Solution

H, X
Before mixing

Mixing

Phase separation

Liquid-liquid extraction

22

Extraction process units

Further reading on L-L extraction: Geankoplis Sect 12.5A; 12.6.

23

Solvent polarity and dielectric constant

The most common strategy for selecting extracting solvents is based on polarity
b
because
lik
like dissolves
di l
like.
lik
Polarity is closely correlated with the dielectric constant D, a measure of the
degree of molecular polarization of a compound.
compound
Dielectric constants of solvents at 25 oC in order of polarity (Stanbury
Table 10.1 )
Solvent

Solvent

Hexane (least polar)

1.90

Acetone

20.7

Benzene

2.28

Ethanol

24.3

Chloroform

4.87

Methanol

32.6

Ethyl acetate

6.02

Water (most polar)

78.5
24

Extraction of a medicinal fungus with solvents of

different polarities

PE
PE extract

Solid
EtOAc

Solid
lid
EtOAc extract S
EtOH
EtOH extract

Solid
Water

Water extract

120
Growth (%
% of controll)

Fungal mycelium dry

powder

100

F1 mycelium
Natural Cs

80
60
40
20
0
PE
extract

EtOAc
extract

EtOH
extract

Water
extract

P.S.

Inhibiting effects on B16 tumor cell growth of different

solvent extracts of F1 (Cs-HK1) fungal mycelium and
natural Cs (dose 100 g/ml, 2-day treatment; P.S.
polysaccharide extract.
extract

Solid

SequentialextractionofCsfungalmyceliumwith
differentsolvents(PE=petroleum,EtOAc =ethyl
acetate,EtOH =ethanol). Zhangetal.2015.

25

C. Concentration and polishing of products

6. Evaporation is to concentrate a solution by vaporizing and removing part of
the solvent ((mostlyy water).
) Applications:
pp
concentration of aqueous
q
solutions of
sodium hydroxide, sodium chloride, sugar.
- In most evaporation processes
processes, the liquid solution is heated to boiling by steam.
steam
In most cases, solution flows through tubes and steam flow outside the tubes.

Cooling,
condensing
d i

lab evaporation
p
apparatus

Heating,
evaporating

A vertical
evaporator
26

7. Crystallization
Crystallization: the formation of solid particles within a homogenous phase,
mostly in a liquid solution
solution. Crystallization usually occurs at late stage of product
processing, after which the crystal product is dried and ready for packaging and
sale.
To crystallize the solute in a liquid solution, the solution is first concentrated to
supersaturation, mostly through either of the following two ways or their
combination in a crystallizer, (1) Cooling, for solutes with a solubility increasing
rapidly with T; (2) Evaporation, for solutes with solubility independent of T.
Water
Feed
solution

Concentration
(e g evaporation)
(e.g.

Conc.
Crystallization
solution

Magma Solid-liquid
separation
ti

Crystal

Mother liquor recycle

A common crystallization process (mother liquor: the remaining solution after removal
27
of crystals; magma: two-phase mixture of crystals and mother liquor)

8 Drying of solid (dehydration)

8.
Drying is to remove the moisture content of a material, usually water
(moisture) from a solid (for dehydration of solid).
Common drying method/process: the solid to be dried is brought into
contact with a stream of hot air (drying air), which vaporizes the water in the
solid and carries away
y the water vapor.
p
Drying air (low
humidity H1)
Wet solid (high
moisture X1)
A solid is dried from 80% to 5% moisture (wt%) in a
dryer. The drying air enters the dryer with a moisture
content of 0.002 kg
g water/kg
g dry
y air and leaves at 0.2
kg water/kg dry air. For 100 kg/h of solid fed to the
dryer, calculate the mass flow rate of drying air fed to
the drier and that of air leaving the dryer. (Ans: 399.5
kg/h; 478.5 kg/h)

Dryer
Dryer

Output air (higher

humidity H2)
Dry solid (low
moisture, X2 )

Material balances: water removed from solid = water gain in air

water free
free-dry
dry solid and dry air in = out.
out
28

D. Membrane Processes
- Membrane separation: use of a semipermeable membrane as a barrier
which only allows certain molecules to pass through.
Q: Compare membrane separation with filtration for the differences and
similarities.
i il iti

9. Dialysis (
())
-

Dialysis is the removal of small solute molecules from a liquid with a

membrane which allows for the small solutes but not large molecules to
diffuse through.

On the other side of the membrane is another liquid,

liquid the dialysing liquid,
liquid
which contains lower concentrations of the small solutes.

29

Separation
p
mechanism and application
pp
of dialysis
y
- Small solute molecules diffuse from the solution to the dialysing liquid
through membrane due to concentration difference.
difference

Large molecule
Small solute molecule

Dialysis membrane

Applications:
- Bioseparation: remove salts from a protein solution (such as after salting
out or precipitation).
precipitation)
- Medical application: Hemodialysis, use of artificial kidneys to remove
small solutes including urea, uric acid, creatinine, phosphates and excess
amounts of chloride from the blood of kidney patients.
30

10 Reverse osmosis (RO

10.
RO))
- Principles: Reverse osmosis (RO) is the use of a high pressure to force
the flow of solvent (e.g., water) molecules in the reverse direction of
osmotic pressure.
Osmosis (spontaneous)

Reverse osmosis (forced)

pressure

Osmotic
pressure

Water

Pure
water

Water
Ethanol
or salt
solution

Semipermeable membrane

Water

Pure
water

Ethanol
or salt
solution

Semipermeable membrane

Q: what is osmotic pressure?

Further reading on membrane processes: Geankoplis Sect 13.1; 13.9A; 13.11.

31

Reverse
eve se os
osmosis
os s
-

Applications of reverse osmosis: water purification, dewatering and the

separation
ti off components
t in
i a mixture.
i t
P
Process
examples:
l
(1) production of milk-based products

Find more details

of these processes.

(2) dewatering of sugar solution

(3) concentration of antibiotics

(4) desalination (of sea water) and wastewater treatment.

Desalination of sea water by RO
Reverse
osmosis

Seawater pretreatment
processes

RO water
to post-treatment

HPP
(Microorganisms, suspended
solids, organic/inorganic matters)

Brine concentrate

Brine disposal

http://www.lenntech.com/desalination/general/reverse-osmosis-desalination-process.htm

32

11. Ultrafiltration
Ultrafiltration (UF): the separation of macromolecules (polymers) such as
proteins with molecular weights 1000-1,000,000 Da. High-pressure process,
up to 145 psi (10 bar).
Separation mainly based on the size of molecules: membrane acting as a
molecular filter and its pore size controls the molecules to pass through.
The solvent and small solute molecules pass through the membrane, collected
as permeate; larger solute molecules not passing thru membrane are
recovered in a concentrated solution as retentate.

Feed
Retentate (conc.
macromolecues)
M b
Membrane

Filtrate/Permeate
Filt
t /P
t
(small molecules)

33

12 Microfiltration (MF)
12.

MF is a membrane p
process for separating
p
g microorganisms
g
such as
bacteria, yeasts and viruses, and other small particles such as colloidal
dispersions of clays, latex particles (typically 0.02-10 m).

The pressure range for MF is usually lower than UF (though MF is often

covered under UF).

Bioprocess applications: sterilization of liquid and air, fermentation broth

clarification.

Food process: sterilization of fruit juices, as an alternative to

pasteurization which leads to precipitate (calcium citrate) formation, to
produce sparkling clear juices.
YouTube Bioprocessing
p
g Part 2: Separation/Recovery
p
y 11 min;; Part 3 Purification
total 20 min from 8.0 min: Tangential flow filtration (UF)
34

Summary of Lecture 3
1. The importance and concepts of separation processes in chemical and
bioprocesses.
2. Solution p
properties
p
in evaporation
p
and crystallization,
y
, solubility
y and
saturation.
3 Have a general knowledge of various separation processes,
3.
processes e.g.,
eg
classification and characteristics, the separation mechanism/principle,
q p
structure and operation,
p
, major
j factors/conditions,, and major
j
equipment
applications.

Assignment 2: 3 Qs on Separation processes in chem/bio- technology Selflearning exercise, no need to submit

35

Review questions (sample)

1. Describe the processes/operations presented in a given flowchart of a processing plant.
2 Compare the similarities and differences between filtration and UF.
2.
UF *
3. Tell the major differences between dialysis and UF?
4. Retentate and permeate in membrane proc: location (relative to mem), composition.
5. Sketch the concentration change/profile of components being separated, e.g. solute A
in both phases along an absorption tower; A&B along a distillation tower
6 Sketch
6.
Sk t h th
the change
h
of,
f (1) filt
filter cake
k thi
thickness
k
with
ith ti
time in
i a plate-and-frame;
l t
df
(2) rate
t
of filtration (filtrate vol/time) with time in a batch and a continuous filter, respectively.

* Similarities: (1) both having a mechanical barrier; (2) both driven by pressure
difference. Differences: (1) filtration controlled by filter cake but UF by the
membrane;
b
(2) UF membrane
b
iis hi
highly
hl selective
l i but
b filtering
fil i medium
di
is
i not; (3)
filtration for insoluble solids but UF for macromolecules in solution; (4) cake formed
in filtration but not in UF.
36

Review questions (sample)

Specify the most suitable separation process for each of the following tasks
and
d ddraw a simple
i l flow
fl chart
h for
f eachh showing
h i the
h major
j process unit
i andd
input and output materials involved:
1) To
T remove SO2 in
i the
h effluent
ffl
or flue
fl gas from
f
a coal-burning
l b i power plant.
l
2) To separate benzene and toluene liquid solution.
3) To concentration of orange juice.
4) To remove small amount of salts from a protein solution (with a membrane
process).
5) To remove inorganic ions from tap water (to de-ionized water).

37