Lecture 13

Distillation Applications:
Low-Temperature Separations

L13–1 Distillation System Design 2015

 Case studies

1. Ethylene production
2. Liquefied natural gas (LNG)

L13–2 Distillation System Design 2015

 Intended learning outcomes
Intended learning outcomes: Students will…

• develop an appreciation of the application of low-

temperature separations and associated refrigeration
systems in practice
• understand the principles and role of mixed refrigerants
and expanders in industrial refrigeration cycles
• explore the challenges associated with design of low-
temperature separations

L13–3 Distillation System Design 2015

 1 Ethylene production

• Olefins are produced by steam cracking of light hydrocarbons

• Light hydrocarbon feed can come from a petroleum refinery:

Ethane Ethylene
or valuable
Propylene
LPG Steam chemical
or Cracking Butadiene products
Light Process Aromatics
naphtha
or Butylenes
Gas oil useful
Pyrolysis gasoline refinery
streams
Hydrogen

• Some of the steam cracker products are of use to refineries

• Some are sold for their chemical feedstock value
L13–4 Distillation System Design 2015
 Ethylene production – overview
Simplified process flow diagram:
Ethylene cracking (front-end demethaniser)
Feedstock Pyrolysis
liquid Cracking Primary Acid gas fuel oil
fractionation removal

Hydrogen
Methane
Drying and Demethaniser De-ethaniser Ethylene
chilling fractionation Ethylene

Propane + Ethane recycle

Propene Propene
Debutaniser Depropaniser
fractionation
C4 material

Pyrolysis gasoline

• Light hydrocarbons separated using sequence of distillation columns

• Refrigerated condensation required – extremely energy-intensive
Ullmann's Encyclopedia of Industrial Chemistry, Wiley-VCH Verlag GmbH, 2005, knovel.com
L13–5 Distillation System Design 2015
 Ethylene production – cracking
• Hydrocarbon feed is preheated and mixed with steam
o Steam-to-feed weight ratio 0.2 to 1.0
• Mixture is heated in radiant section of a furnace
o Temperature 800 to 900°C
o Residence time less than 1 second
o Pressure 2 to 6 bar
Steam

Furnace
L13–6 Distillation System Design 2015
 Ethylene production – product cooling
• The mixture is cooled rapidly (to 300 to 400°C) to quench
the reactions by high pressure steam generation
• In the primary fractionator, further cooling takes place
o Heavier components are removed as pyrolysis fuel oil
• In the quench tower, circulating water cools the gas to 70°C
Pyrolysis Gas
Quench tower
Primary
Steam Fractionator
Feed

HP Steam
Generation Circulating
quench
water
Quench
oil
Pyrolysis
Fuel Oil
L13–7 Distillation System Design 2015
 Ethylene production – separation
• Pyrolysis gas is compressed to 35 bar
• It is purified to remove H2S and CO2 and dehydrated
• It is cooled to around –100°C and separated by cryogenic distillation
H2, CH4 H2 Ethylene

Pyrolysis H2S, CO2

& H2O Cold Ethylene
Gas Box Acetylene
Column
Removal
Conversion

Demethanizer

Deethanizer Ethane
Propylene

Propylene
Column

Propane

Butanes and Heavier

L13–8 Distillation System Design 2015
 GCC of ethylene cold-end process+

Demethaniser
reboiler
C2 splitter reboiler

Deethaniser C2 splitter condenser

condenser

Demethaniser
condenser

[ MW ]
+Wu, Guodong, PhD Thesis, UMIST, 2000
L13–9 Distillation System Design 2015
 Ethylene production –
refrigeration system
• Ethylene/propylene cascade
o typically 6 refrigeration levels
o typical cooling process to –140°C to –160°C
o open and closed loop arrangements used
• High levels of heat integration between refrigeration
system and the process
o designs depend on downstream fractionation process
• Design of the refrigeration system must consider
o collection of the condensate and vapour from each stage of each
refrigeration loop (2–6 stages)
o energy requirements
o avoiding freezing of components (e.g. acetylene, butadiene,
benzene)
o choice of construction materials for cryogenic conditions
Wiley Critical Content – Petroleum Technology, 2007, Vol. 2, Ch. 5, p. 779, John Wiley & Sons www.knovel.com
L13–10 Distillation System Design 2015
 Ethylene production – refrigeration

Relative costs of refrigeration system for ethylene plant

Ullmann's Encyclopedia of Industrial Chemistry, Wiley-VCH Verlag GmbH, 2012

(citing R. Orriss, MW Kellogg Co., Houston, Texas, June 1985)
L13–11 Distillation System Design 2015
 Mixed refrigerants – Introduction
Pure refrigerant Mixed refrigerant
• Pure refrigerants evaporate and • Mixture evaporates and
condense at constant temperature condenses over temperature
• Large power demand if range
evaporation temperature is low • Reduced temperature difference
relative to process temperature reduces power demand

T T
Process stream Process stream

Large T
Smaller T

Evaporator
Evaporator
(Mixed refrigerant)

H H
Smith, 2005, Chemical Process Design and Integration, Wiley, Ch. 24.11
L13–12 Distillation System Design 2015
 Simple cycles –
Pure and mixed refrigerants
Pure refrigerant Mixed refrigerant
• Complex cycles (multiple levels) • Simpler cycle may suffice
can reduce power demand

T T

H H

L13–13 Distillation System Design 2015

 Mixed refrigerants – Advantages and
disadvantages compared to pure refrigerants

Advantages Disadvantages
 Suitable for non-isothermal cooling  Less useful for isothermal cooling
 Lower T reduces power  Lower T increases heat transfer
requirement area
 Improved thermodynamic efficiency  Design more challenging
 Simpler machinery configuration – o Fluid properties harder to model
improved reliability o Need to be sure T > 0 throughout
 Refrigerant composition – important evaporator
degree of freedom for design and o Selecting refrigerant composition
operation is a challenge

L13–14 Distillation System Design 2015

 Complex cycles using mixed
refrigerants
• Multiple compression stages (with intercooling)
• Multiple evaporation stages (at different pressures)
• Phase separators (economisers)
• Multistream exchangers common
Example: Liquefied natural gas

L13–15 Distillation System Design 2015

 Ethylene production –
Complex mixed refrigeration cycle

ABB Lumus patent, 2003 www.freepatentsonline.com/6637237.html

L13–16 Distillation System Design 2015
 Ethylene production –
Complex mixed refrigeration cycle

• Closed loop mixed refrigerant system

o Mixed refrigerant: methane, ethylene, propylene
o Mixed refrigerant withdrawn from compressor – separated and
part returned to compressor
o Methane-rich vapour fraction produced and two levels of
propylene-rich liquids (light, medium and heavy mixtures)
o Different streams provide various temperatures and levels of
refrigeration in various heat exchange stages .
• Patent claims: versatile (flexible) arrangement,
competitive power consumption, lower overall plant cost

ABB Lumus patent, 2003 www.freepatentsonline.com/6637237.html

L13–17 Distillation System Design 2015
 Summary – Ethylene production
• The cracker gas contains many components that need
separation
o Ethylene is desired product
o Ethane and propane can be recycled
o Other valuable byproducts
• The separation design (distillation sequence) depends on
the cracker gas composition
• The light hydrocarbon products require refrigeration at
temperatures of –100C or lower
o Several duties are nearly isothermal – suitable for pure refrigerants
o Cascaded refrigeration cycles are needed (with complex features)
o Mixed refrigerants are increasingly of interest and can increase
process flexibility and decrease compression costs (operating and/or
capital costs)

L13–18 Distillation System Design 2015

 2 Liquefied natural gas (LNG)

Why liquefy natural gas?

• Gas reservoirs often in remote locations

• Piping gas through long distances is very expensive
• Liquid trading is also more flexible
• For cryogenic liquefaction, the energy requirements are
equivalent to around 10% of the feed.
o Has advantages over chemical conversion to liquids, which
consumes ~35% of the feed’s heating value.

L13–19 Distillation System Design 2015

 Features of LNG Processes

• Product is mainly liquid Energy intensive

methane (–161C)

• Large refrigeration system Capital intensive

• Large power demands Relatively small

heating demands

L13–20 Distillation System Design 2015

 LNG – Process scheme

Linde LNG Technology www.linde-engineering.com/en/images/LNG_1_1_e_10_150dpi19-4577.pdf

L13–21 Distillation System Design 2015
 LNG – Typical plant

• Feed gas compression

• Purification – CO2 and H2O can freeze
o CO2 removal – wash process
o Drying (H2O removal) by adsorber
• Natural gas liquefaction
• LNG storage, loading, metering
• Refrigeration system – multistage compressors,
cryogenic heat exchangers, mixed refrigerant
o Mixed refrigerant cycle make-up and boil-off gas handling system
• Gas turbine with waste heat recovery for hot oil heating
• Other utilities

L13–22 Distillation System Design 2015

 LNG production
Typical capital cost breakdown
Utilities 16%

Product Storage 18%

Gas Liquefaction 50% Other 16%

L13–23 Distillation System Design 2015

 LNG
Refrigeration over a wide temperature range
T*
T*

? ?

H
Single mixed H
? ? refrigerant
QRef
H T*
T*
?

H H
Cascaded Pure Refrigerants Mixed refrigerant +
H Pre-Cooling
Two mixed refrigerants,
cascaded
L13–24 Distillation System Design 2015
 LNG
Pure Refrigerants: Cascade Process

Ethylene Methane
Propylene Cycle Cycle
Cycle
3/4 levels 3/4 levels 3/4 levels

Pre-treated
Natural Gas
LNG
NGL Storage

• Lower power consumption than single cycle

• Low heat transfer area
• Complex and expensive – large number of equipment items
Lee, Smith and Zhu, 2002, Optimal synthesis of mixed-refrigerant systems
for low-temperature processes, Ind. Eng. Chem. Res., 41 5016-5028
L13–25 Distillation System Design 2015
 LNG – Single Mixed Refrigerant

Pre-treated
Natural Gas

NGL
LNG
Storage
Compared to pure refrigerants...
• Smaller temperature differences
• Less machinery
• Usually higher refrigerant flow rate
• Compositions can be adjusted to operating conditions
L13–26 Distillation System Design 2015
 LNG – Multi-stage mixed refrigerant

Pre-Treated
Natural Gas

LNG
NGL Storage

Del Nogal, Kim, Perry and Smith, 2008, Optimal design of mixed
refrigerant cycles, Ind. Eng. Chem. Res., 47(22) 8724-8740

Number of stages Relative power requirement

1 1
2 0.93
3 0.90
4 0.88
5 0.87
L13–27 Distillation System Design 2015
 Use of expanders in refrigeration
• What is an expander?
o A device in which a fluid is expanded Condenser
to produce work 4 3
o Reciprocating, radial-flow and axial-
flow designs applied Expander Compressor
• After expansion in an expander,
1 2
refrigerant stream… Evaporator
o pressure reduces
P Ideal expander
o temperature reduces
o enthalpy decreases (process is not 4 Condenser 3
adiabatic) Constant s

o entropy is constant (ideal expander) Constant h

o liquid fraction is greater than when 1 Evaporator 2
pressure is let down through
expansion valve H
Smith, 2005, Chemical Process Design and Integration, Wiley, Ch. 24.7
L13–28 Distillation System Design 2015
 Expanders – Advantages and
disadvantages compared to expansion valves

Advantages Disadvantages
 Reduced compression  Equipment cost may be
requirements… very high – large capital
 …power recovered investment*
 …greater liquid fraction  Expansion valve is
entering evaporator simpler, more reliable
and more flexible with
respect to flow rate

* Therefore… expanders are most useful in large-scale

plants (e.g. ethylene plant, LNG)
Smith, 2005, Chemical Process Design and Integration, Wiley, Ch. 24.7
L13–29 Distillation System Design 2015
 LNG – Expander cycle

Pre-Treated
Natural Gas LNG
Storage
NGL

• Pure component gas refrigerant (usually N2 or CH4)

• Turbine expansion allows a wider temperature drop than valves
• Simple, but high capital investment
• Several expanders could be accommodated at different levels

L13–30 Distillation System Design 2015

 LNG – Dual Mixed Refrigerant

NGL

Pre-treated
natural gas

LNG
Compressor Compressor Storage
('warm') ('cold')

Two mixed refrigerant circuits in cascade

L13–31 Distillation System Design 2015

 LNG – Propane pre-cooled
mixed refrigerant
Dominant technology by far
End Flash Fuel

Pre -Treated LNG N2

Natural Gas Rejection
Storage
HP C3 MP C3 LP C3 LLP C 3
Dehydration /
Hg Removal
C3
Compressor NGL

HP C 3 MP C 3 LP C 3 LLP C 3

C3
Network

HP MR LP MR
Compressor Compressor

L13–32 Distillation System Design 2015

 Summary – LNG

• Large-scale operation, relatively simple separation

process
• Very low temperature required to liquefy natural gas
o Cascaded multistage multilevel refrigeration cycles used
o Process expanders help reduce power demand through power
recovery and by increasing liquid fraction in evaporator inlet
• A wide range of refrigeration cycle configurations is
applied
o Scale of process affects process economics significantly

L13–33 Distillation System Design 2015

 Summary

• Ethylene production and natural gas liquefaction are

important applications of low-temperature separations
• Advanced process designs are needed to achieve high
efficiency, low power consumption and high yields.
• Advanced design options commonly implemented
▸ complex and cascaded refrigeration systems
▸ mixed refrigerant cycles
▸ complex distillation arrangements
▸ advanced heat integration options
▸ high-performance heat exchange equipment
▸ expanders for power recovery

L13–34 Distillation System Design 2015