Using Separations in Chemical

Processing

reactor

separato
r

raw
materials

products
recycle stream

Where are separations

needed?
Purification of reactor feeds
Purification of products for sale
Purification of waste for safe disposal

Separations as Unit
Operations
The specific design of the separator
depends on the chemical
composition of the feed, and the
desired purity of the product
However, the general design
principals are independent of the
chemistry

Column distillation

At an oil refinery, fractional distillation columns

separate hydrocarbons into separate streams,
cuts or fractions
A multi-purpose distillation column for mineral oils and
chemicals
40 trayswith multiple feed entry options, capacity: up to 45 mt/h
mode: vacuum, atmospheric or pressure up to 3 bar
temperature: up to 320C

Flash vaporization

ash drum for hydrocarbon vapor recovery

Water desalination plant in Cyprus

Multistage flash distillation

Absorption and stripping

A column filled with an amine

solution is used to absorb H 2S and
CO2 from sour natural gas

A steam stripping column

removes H2S and CO2 to
regenerate the amine

Liquid-liquid extraction
Mixer-settlers used for continuous,
counter-current liquid-liquid extraction of
rare-earth ions

Leaching

Cyanide leaching of gold ore, Nevada

Sublimation

Sublimation of HgI2 for use in semiconductor

manufacturing, as well as in detectors for X-ray
and -ray imaging

Crystallization

Multiple-Effect Crystallizer for Sodium

Sulfate (Na2SO4) Refining

Crystallizer for Salt (NaCl)

Chromatography

Chromatography columns

Membrane filtration

Water Treatment Plant. Each white vessel

contains seven spiral-wound membrane units.

Why is good design important for

separations?
Separations equipment can be 50-90 % of
the capital investment in a chemical plant
Separations can also represent 40-70 % of
operating costs
Purity requirements depend on market
tolerance
High separations costs tolerated for high
value-added products

Examples
1. Petroleum refining
crude oil gasoline, diesel, jet fuel, fuel oil, waxes, coke, asphalt

2. Pharmaceuticals

sub-ppm level of metal catalyst required for human consumption

3. Semiconductors
SiO2 SiCl4 Si
Metallurgical grade (97%) for alloying with steel and Al: $1/kg
Solar grade for photovoltaics (99.99 %): $80/kg

4. Water treatment
Industrial wastewater vs. potable water
Some impurities ok (Ca2+); others not (Hg2+)

Process Diagram for Ethylene hydration:

C2H4 + H2O C2H5OH

Why do separations cost a

lot?
unmixing causes reduction in entropy
this is not spontaneous
achieve by adding an external separating
agent
Energy (distillation)
Material (e.g. extraction)
Barrier (e.g. membrane)
Gradient (e.g. electrophoresis)

Table 1. Separation Unit Operations based on Phase Creation or

Addition

vertical drum

horizontal drum

valve
column with trays (stages)

heat exchangers

condensor
reboilers

Table 1, cont. Separation Unit Operations Based on Phase Creation or

Addition

heater

Table 1, cont. Separation Unit Operations Based on Phase Creation or

Addition

Table 2. Separation Unit Operations based on a Solid Separating

Agent

Table 3. Separation Unit Operations Based on the Presence of a

Barrier

Table 4. Separation Unit Operations Based on an Applied Field or

Gradient

Equilibrium-staged
separations
Make use of thermodynamics to
achieve spontaneous separation
But thermodynamics also dictates
the limits of the separation

Definitions of equilibrium
vapor

thermal equilibrium: Tliq = Tvap

mechanical equilibrium: Pliq = Pvap

liquid

chemical equilibrium: liq = vap

(chemical potential)

Equilibrium is dynamic: molecules continue to vaporize and

condense, but at equal rates, so there is no net change in either
phase.
Rate of approach to equilibrium depends on:
(1) rate of mass transfer
proportional to (a) mass transfer coefficients K i = f(T), and (b)
interfacial area
(2) concentration gradient
becomes very small as equilibrium is approached, time

Consider a single
equilibrium stage
V and L are in equilibrium with each
other; they are streams leaving the
same equilibrium stage.
V and L are not in equilibrium with
F,
i.e., iL = iV iF

vapor product

T, P

feed

vapor

flow rate F
TF, PF
composition zi

liquid

flow rate V
T, P
composition yi

liquid product

if > 1 chemical species present,

then xi yi
therefore separation has occurred
vapor-liquid equilibrium (VLE) limits

flow rate L
T, P
composition xi

25

Cascade of equilibrium
stages
What if we need more separation than one equilibrium stage can provide?
Feed one of the two product streams (e.g., L) to another equilibrium stage

stage
1

V2

stage
2

V3

L2

stage
2
L3

Creates many vapor streams with different compositions

If we combine (mix) them, we destroy some of the separation
we created

Better Alternative:
Counter-current cascade
F

Variable pressure cascade

P1 > P2 > P3

1
L1

V2

2
L2

compressor
replace
replace

V1

1
L1

V2

by
2

by
L2

V3

3
L3

V1

Variable temperature cascade

T1 > T 2 > T 3

V3

3
L3

An even better alternative

F

V1

Integrate the heat exchangers:

allow contact between condensing
vapor and vaporizing liquid streams

L1

liquid
downcomer

1
V2

2
L2

weir
V3

perforated tray

V1
1

V2

L1

V3

L2

vapor
3
L3

L3

integrated column is isobaric and nonisothermal

Thermodynamic
considerations
Perfect separation requires an infinite number of
equilibrium stages
The engineer specifies the number of stages
required for an acceptable degree of separation
Equilibrium is not achieved on each stage in a finite
time
theoretical stage: assume equilibrium is
achieved
actual stage: equilibrium is not achieved (< 100
% efficiency)
We always need more than the theoretical number of
stages to achieve the desired separation

General design procedure for

equilibrium-staged separations
1. Obtain relevant equilibrium data
*

(where?)
2. Determine no. of theoretical stages
required
3. Determine no. of actual stages
required (requires knowledge of
stage efficiency)

* Focus of this course.