Refrigeration (Kylteknik)

Refrigeration (Kylteknik)
course # 424519.0 v. 2017
5. Low temperatures, liquefied gases,

Stirling engines, LNG, dry ice
Ron Zevenhoven
Åbo Akademi University
Thermal and Flow Engineering Laboratory / Värme- och strömningsteknik
tel. 3223 ; ron.zevenhoven@abo.fi
ÅA 424519 Refrigeration / Kylteknik
5.1 Gas refrigeration and

liquefaction
Åbo Akademi Univ - Thermal and Flow Engineering Piispankatu 8, 20500 Turku 12.2.2017 2/84
Gas liquefaction options
 Liquefied gases can be produced by cooling a gas until
it partially forms a liquid, and removing this liquid
product, by gas-liquid separation.
(Feb. 2017)
 The necessary cooling effect can be achieved by
expansion cooling
Pictures: http://www.linde-gas.com/en/index.html
– Using a turbine or other expansion machine
(allows for very limited liquid formation):
reversed Brayton cycle, reversed Stirling cycle
– Using a throttling device,
making use of the
Joule-Thomson effect
 For pre-cooling, a vapour
- compression process can be
used
5.2 Stirling cycles
See also A11: chapter 13.10

and TV08
Carnot, Stirling, Ericsson cycles
 Carnot cycle: reversible
– Heat addition at constant T
– Adiabatic expansion
– Heat rejection at constant T T,s and p,v
– Adiabatic compression diagrams for
 Stirling cycle: reversible Carnot →
– Heat addition at constant T and
– Heat rejection at constant v Stirling ↓
– Heat rejection at constant T power
– Heat addition at constant v cycles
 Ericsson cycle: reversible
– Heat addition at constant T
– Heat rejection at constant p
– Heat rejection at constant T
– Heat addition at constant p
Stirling cycle, Stirling engine

See for principle also http://www.cs.sbcc.net/~physics/flash/heatengines/stirling.html (Feb. 2017)
 Heat is temporarily stored in the

regenerator, going from
temperature TH to TL during step 2-3
(and vice versa when returning to
state 1) Picture: ÇB98 Picture: T06
12.2.2017 Åbo Akademi Univ - Thermal and Flow Engineering 6/84
Piispankatu 8, 20500 Turku
A Stirling cooler
TL
TH
“The cooler consists essentially of only two moving parts - a piston and a
displacer. The displacer shuttles the working gas (helium) between the
compression and expansion spaces.
The phasing between the piston and displacer is such that when the most
of the gas is in the ambient compression space, the piston compresses
the gas while rejecting heat to the ambient. The displacer then displaces
the gas through the regenerator to the cold expansion space.
After this, both displacer and piston allow the gas to expand in this space
while absorbing heat at a low temperature.”
Picture and source: http://www.ohio.edu/mechanical/thermo/Intro/Chapt.1_6/Chapter3b.html (Feb 2017)

Stirling refrigeration cycles /1

 The working gas in the cycle is
hydrogen or helium (high
thermal conductivity!)
 The Stirling cycle is difficult to
achieve in practice since heat
transfer requires temperature
differences
→ regenerator has efficiency
< 100%, and pressure drop
 Nonetheless of interest due to
efficiency potential and (for
engines) emissions control
(Ford, GM, Philips) Stirling gas refrigerator (Philips)
Picture: S90
Stirling refrigeration cycle /2
 Stirling refigeration devices
(”cryogenerators”) allow for
cooling down to -250°C at up to
several MW cooling power
See also: http://www.stirlingcryogenics.com/ (Feb 2017)

 Efficiency: COP ~ 0.5· COPcarnot
Evaporation
 Compact, simple, low noise Stirling
 Temperature-range flexible Claude
Joule-Thomson
With repeated strokes,

lower and lower
temperatures can be
reached
5.3 Joule-Thomson effect

(see also 3.3)
Gas expansion: Joule-Thomson effect /1
 Throttling (= isenthalpic pressure
 T 
reduction of gases) can have a  T 
   0    0
 p  h  p h
temperature effect as a result of
 T 
deviations from ideal gas    0
 p  h
behaviour:
 h 
h  h(p,T) and     for non  ideal gas Liquid-vapour
 p  T dome
 T   p   h 
using dh   or           
 p h  h  T  T p
 T      h 
   µJT      with Joule  Thomson coefficient µJT
 p h  p   h  c p  p  T
   
 h  T  T p
 For the states (for example in a T,s diagram) where
(∂T/∂p)h > 0, reducing pressure will give a lower
temperature: the Joule-Thomson effect Picture: S90
Gas expansion: Joule-Thomson effect /2

 At the inversion temperature
of a gas, µJT = 0
 Application: cooling and
liquefaction of gases
 Some tabelised data:
Air at 1 atm:
µJT ~ 2K/MPa at ~ 20°C
µJT ~ 4K/MPa at ~ -100°C
Picture & table: A83
Using the Joule-Thomson effect
 The main application of the J -T effect is the Linde process, later
also the Claude process, still later also natural gas processing:
gases with relatively high vapour pressure
 Initially used mainly for liquefaction of air, followed by
distillation to separate air into N2 + O2
 Water and CO2 can be removed
at ~ -50°C and -80°C, resp.
 Note: during vaporisation of Picture:
Ö96
liquid air, more N2 than O2 is
vaporised, enriching the
remaining liquid in O2, which
can lead to ignition of oil,
therefore cooling with liquid
nitrogen (by-product from O2
production !) is much safer T,x diagram for O2 + N2 at 1 atm
5.4 Linde-Hampson process

(for liquefaction of gases)

and MMW14: chapter 4..2.5
Linde-Hampson process – ideal /1
1-2 Compression at T = Tin
2-3 Heat exchange
3-4 Throttling
4-6 Liquid removal
4-5 Gas removal
5-7 Heat exchange heat
Liquefied gas exchange
Note: massin =
massliq @ 6 + massgas @ 5
1 and 7 can be open for

air (and p2 for cold gas = 1 bar); Picture: S90
closed loop for other gases
Data for several gases

Critical Temperatures, Critical Pressures, Boiling Points
Gas Tc(oC) Pc (atm) BP at 1 atm (oC)
He -267.96 2.261 -268.94
H2 -240.17 12.77 -252.76
Ne -228.71 26.86 -246.1
N2 -146.89 33.54 -195.81
CO -140.23 34.53 -191.49
Air -140 39 see data N2, O2, …
Ar -122.44 48.00 -185.87

O2 -118.38 50.14 -182.96
CH4 -82.60 45.44 -161.49
C2H6 32.27 48.16 -88.6
CO2 31.04 72.85 -78.44
C3H8 96.67 41.93 -42.02
NH3 132.4 111.3 -33.42
Cl2 144.0 78.1 -34.03
Mass balance: Note: ΔT23 < ΔT57
min = m4 = m6 + m5
Energy balance I:
h3= h4 = x· h5+(1-x)· h6 II
fraction of mass heat
liquefied = γ = 1-x Liquefied gas exchange
Energy balance II:

m2· h2 = m6· h6+m7· h7
h2 = γ· h6 + (1-γ)· h7
I
gives
Picture: S90
γ = (h2-h7)/(h6-h7)

 For example (see p,h
diagram on next page) 4
3’’
air 290 K, 1 bar → 200 bar 2 1
hair in = 290 kJ/kg = h4
Compressor
3
h1 = 255 kJ/kg Cooler after compressor
3’ Heat exhanger
h2 = - 40 kJ/kg = h3
Throttling and liquid removal
h3’ = -130 kJ/kg
Picture: Ö96
air mass fraction liquefied,

γ, from energy balance Some data for air:
min· h1= γ· min· h3’+ (1-γ)· min· h4 cp kJ/kg· K 1 bar 300 bar
gives γ = (h1-h4)/(h3’-h4) = 0°C 1.006 1.409
0.083 kg / kg -100°C 1.011 1.761
T2 = 120 K, T3’ = 80 K (see also Ö96 – example 6.4)

Linde-Hampson process: p,h diagram
Source: http://refrigerant.itri.org.tw/Refprop/air.gif
Linde-Hampson process – real states ”*”

1-2* Compression with
intercooling
2*-3* Heat exchange with
pressure drop
3*-4* Throttling
4*-6* Liquid removal
4*-5* Gas removal
5*-7* Heat exchange Liquefied gas
4* instead of 4: much less

liquid product !
Cooling inlet compression
with water can give 1-2
With air, if 7 ≠ 7* then cold Picture: S90
air is rejected.
Linde-Hampson process - improved
 Linde process
with pre-cooling
using a separate
refrigeration
process
 Linde process
with external pre-
cooling process
and high pressure to ~50 bar
to ~200 bar
circulation (for air)
Pictures: Ö96
Linde-Hampson initial cascade process

Compressor
 Until 1895 the most Condenser
important process,
used only for Evaporator
Condenser
liquefaction of air
Evaporator
 Uses 4 cooling cycles Condenser
in series
Evaporator
 Relatively small Condenser
pressure &
temperature ranges
per stage Linde’s 4-stage cascade
process (here for N2)
 Medium is liquefied in
4th stage
Picture: Ö96

5.5 Claude process

(for liquefaction of gases)
See also MMW14: chapter 4..2.6
Claude process - ideal

Similar to Linde process Heat exchange
except for: I
2-3 heat exchange I II
and then partially: III
3-4 expansion turbine;
+ 3-5 heat exchange II + III
5-6 throttling Lique-
fied
6-8 liquid product gas
6-7 gas product

turbine
A mix of a Linde process
(all flow to throttle) and a
gas expansion process
(no flow to throttle)
Picture: S90
If 4 = 7 then heat
exchange III is not needed
Claude process – real states ”*”
1-2* Compression with
intercooling
2*-3* Heat exchange I with
pressure drop
3*-4* Expansion with losses$
3*-5* Heat exchange II with
pressure drop Lique-
5*-6* Throttling fied
gas
6*-8* Liquid removal
6*-7* Gas removal
7*-9* Heat exchange with
pressure drop
6* instead of 6: much less

liquid product !
Cooling inlet compression Picture: S90

with water can give 2=2* $ depends on expansion device
Linde-Hampson vs. Claude process

 For the Claude process the optimisation of the mass streams
and heat exchange is very important Picture: http://en.wikipedia.org/wiki/Liquid_oxygen (Feb. 2017)
 The Claude process is more complicated, requires less energy

input as a result of the expansion machine, nonetheless
efficiencies can be as low as ~ 4-6 %.
 For liquid air the production is ~ 0.05 - 0.07 kg/kg input air,
can be improved to 0.1 - 0.2 kg/kg input air when using pre-
cooling to -30 ~ -50°C
 The temperature after the compression
is very important for overall efficiency
 The choice between a Linde or Claude
process depends on size and costs
 For air, pre-cooling to ~ -50°C for H2O
removal, to ~-80°C for CO2 removal
Liquid O2
Process energy use
 The energy input can be Heat Power
Q P
evaluated from an energy balance
for liquid product
. . 0
γ· m· h0 + P = Q + γ· m· h3’
.
with fresh gas feed
.
γ· m at
enthalpy h0 and m = mass flow
to be compressed.
 Power input per kg product:
. .
P/(γ· m) = Q/(γ· m) + h3’ – h0 Table and picture after Ö96
Energy input for producing liquefied air at 80 Theoretical In practice

K at 290 K ambient temperature kWh / kg kWh / kg
Linde cascade process (4 stages) 0.32 0.54
Simple Linde process 1.21 2.1
Linde process + pre-cooling 0.70 1.2
Linde process + high pressure circulation 0.45 0.63
Claude process 0.35 0.85
5.6 Liquefied hydrocarbons

(LNG / methane, LPG) and CO2
See also MMW14: chapter 4..2.4
LNG processing /1
See:: http://www.khi.co.jp/english/rd/tech/154/ne154ts00a.html (Oct. 2012)

 Liquefied natural gas (LNG) is becoming increasing important, as a
substitute for oil and other fossil fuels; liquefaction facilitates long-
distance transport
 Methane (CH4) with higher C:H molar ratio than other hydrocarbon
fuels, gives less CO2 /kWh power
 Typical composition:
CH4 87 - 91 mole-%; C2H6 4 - 11 mole-%; C3H8 < 3 mole-%;
C4H10 < 1.5 mole-%; C5H12 < 0.05 mole-%
 The gas is delivered for processing at ~ 90 bar and after removal of
H2S / CO2, H2O, Hg (!), and heavy
components (C5+), it is completely
liquefied at ~ - 160°C,
pressures between 1 and 60 bar
 LNG can be used to produce CNG
(compressed natural gas, 100-250 bar)
LNG processing /2
LNG processing
Typical ”train” unit size

up to 8 MTPA
(million tons per annum)
LNG composition
More detail:
MMVW14
Chapter 2
Often,
ethane
and/or
propane/butane
are (partly)
removed Source: WE09
Source: http://christophe.lauverjat.pagesperso-orange.fr/mava/index.html
p,h diagram methane CH4 (R-50)
Åbo Akademi Univ - Thermal and Flow Engineering Piispankatu 8, 20500 Turku 12.2.2017 31
LPG
 Liquefied petroleum gas (LPG) is a liquefied mixture of mainly
(>95%) propane plus some similar boiling point hydrocarbons, Picture ftp://ftp.eia.doe.gov/brochures/propane05/propane.htm (Oct 2012)
mainly butanes.
 LPG is produced during processing of natural gas and in crude oil
refining
Propane Production
 The atmospheric boiling point & Distribution System
of propane is ~ -42°C; LPG
can be liquefied by
compression and cooling
to ~ 12 bar at low
emperatures, and can be
stored at ~ 15 bar, 40°C

Wobbe index
https://en.wikipedia.org/wiki/Wobbe_index
(Feb. 2017)
For LNG: 35 ... 55 MJ/Nm3
Acetylene, ethylene, CO2, ....

Similar to LNG and
methane, Picture: D03
a cascade of
compression / heat
exchange / expansion
processes
can be used for
liquefication of
other hydrocarbons with
high vapour pressure
(ethane, ethylene, ....)
and CO2, using
hydrocarbons, ammonia,
CO2, ....... as refrigerants

5.7 LNG supply chain and processing
See also MMW14: chapter 1
Natural /LNG gas supply chain
Depending on transport distance and amount, transport of NG by pipeline, as

LNG or after conversion (Fisher Tropsch GTL fuels, MeOH, DME)
Picture:
2014: ~70% NG transport by pipeline, ~30% as LNG MMVW14
Small LNG terminals: 0.01 – 0.3 Mt/a (MTPA), large > 1.5 Mt/a.
Qatar: > 7 Mt/a, Australia > 8 Mt/a Global LNG trade 2016 ~ 250 Mt/a
http://www.nt.ntnu.no/users/skoge/prost/proceedings/gas-processing-doha-2009/fscommand/d01.pdf
LNG processing before transport
 Pre-chilling and removal of heavy fractions (C2-C5, C6+),
bringing CH4 content from ~90% to ~98-99%
 Liquid LNG from flash (to ambinient pressure) to storage
tanks, flash gas + BOG from storage and ship is compressed
and sold e.g. as fuel BOG =
 Gas turbines Boil-Off Gas
replaced steam
turbines for LNG
refrigeration,
 less attactive
to use flash gas
(recompression
(Nov. 2014)
needed)
Picture:
LNG production from raw NG
N2 removal:
1.quality
2. boiling point
3. roll-over
Picture:
MMVW14
 LNG: atm. boiling point ~ -162°C, 87-99% methane, density 430 ~

470 kg/m3, NG flammibility limits in air LFL ~ 5%-vol, UFL ~15%-vol
Picture: http://www.ccj-online.com/4q-2012/plant-reports-ecoelectrica-lp/sidebars/ (Nov. 2014)
LNG processing: special features
 Gas composition, purification needs: water, Hg, CO2, N2, ”heavy
hydrocarbons”, H2S
 Water removal: glycols (DEG or TEG), or adsorbents that also remove
CO2 and H2S, using molecular sieves, or alkanol amines (MEA, DEA, ....)
 Storage of LNG at ~ -160°C, 1 atm, at 1/600th of the NTP volume
requires, of course, insulation, and removing boil-off
 Pre-stressed concrete, Al and 9%Ni steel are suitable
 A serious challenge is stratification, caused by free convective flow of
heated liquid along the walls,
towards the upper,
liquid-vapour interface.
Roll-over can then give
sudden and rapid flashing.
 ”Aging” and varying LNG
input increase the risk
 More detail / source: F05 (e.g. Section 6.4)
5.8 Liquefied gas, LNG transport
Liquified gas transport
Picture: http://www.kommersant.com/photo/300/DAILY/2005/237/KP_55007_008_18_l.jpg (Oct. 2012)

 Liquefied gases can be transported while being
refrigerated on ships, trains and trucks (and in
principle also on aeroplanes)
 One option is to use part of the boil-off as fuel for
Picture: http://www.vpsr.cz/lpg-road-tankers (oct. 2012)

the vehicle (and to
drive the compressor
for the refrigerator)
 Traffic and public safety
may be an issue
 See also http://liquefiedgascarrier.com/ (Nov. 2014)

LNG transport by ship
Pictures:
MMVW14
 Typically 30 000 – 300 000 m3, mostly ~ 130 000 m3 ~ 65 000 tons.
T = approx. -169 °C, p = 1.3 ~ 1.7 bar, BOG = 0.05 ~ 0.15 %/day
LNG transport by ship
Pictures:
MMVW14
LNG receiving terminal : model
Picture:
MMVW14
LNG receiving terminal: processing
Picture:
MMVW14
5.9 Natural gas liquefaction

and WE09: chapter 6
NG cooling curve
Pictures: http://scialert.net/fulltext/?doi=jas.2011.3541.3546&org=11
from article: http://scialert.net/qredirect.php?doi=jas.2011.3541.3546&linkid=pdf
and
https://www.researchgate.net/figure/289496479_fig1_Fig-1-Pure-and-MR-cooling-curve-in-
comparison-to-natural-gas-Helgestad-2009
LNG liquefaction /1 -35 °C -161°C

~ 0.07 bar
 LNG liquefaction is based on succesive

MAGAZINE_DETAIL.asp?ART_ID=2808&MONTH_YEAR=Feb-2006
compression, heat exchange and
expansion
 Currently the propane pre-cooled
mixed refrigerant (PPMR / C3MR)
process* → covers ~75% of the
market needs since the late1970s
Picture: http://www.worldoil.com/Magazine/
 A mixed refrigerant (MR) is used for

minimal irreversibility losses; the PPMR
process uses a mixture of nitrogen,
methane, ethane and propane →
 The first steps cool to ~ -35°C to
remove heavy components (natural gas
liquids, NGL), followed by Joule-
Thomson cooling to ~ -160°C
* APCI (Air Products & Chemicals Int)
LNG liquefaction /2
Methane circuit
An important alternative process for LNG liquefaction is the
optimised cascade LNG process (OCLP)* based on three
refrigerants: propane, ethylene circuits and methane (flash) circuit.
* Phillips Petroleum Co.
LNG liquefaction /3
Another important, more recent alternative, process for LNG liquefaction

is the the more recent dual mixed refrigerant process (DMR)* based
on pre-cooling to -50°C in the (P)PMR cycle (refrigerant propane) and
further cooling and liquefaction in the MR cycle (refrigerant mainly ethane
+ propane). Advantages: high efficiency, lowest specific costs. * Shell
LNG liquefaction /4 Others
Single mixed refrigerant (SMR) loop process Liquefin™ process

Mixed fluid cascade process
Source: WE09
NG liquefaction power consumption
Table:
MMVW14
5.10 Liquefied gas, LNG storage
See also MMW14: chapter 1.4.6
Liquefied gas storage spheres

Liquid level
 Storage of liquefied gases can be
accomplished at pressures near
1 atm using a spherical tank with a Power
free liquid surface STORAGE
 Isolation materials minimise the Throttle

”boil-off” gas, BOG typically
~ 0.05 % per day Condenser
 The tank can be considered to be the evaporator of a vapour-
compression cycle: the boil-off is extracted, compressed,
condensed and throttled to the tank pressure
 The two-phase mixture returned to the tank gives a cooling effect
that exactly compensates for heat leaking in during steady-state
operation
 For very low-temperature boiling gases like methane, a cascade
refrigeration process can be used with propane, freons, water, ..
Picture:http://newsimg.bbc.co.uk/media/images/38726000/jpg/_38726631_pancevo_300_ak.jpg (Oct. 2012)
Liquefied gas storage
Picture: http://scifun.chem.wisc.edu/chemweek/CO2/CO2_phase_diagram.gif (Oct. 2012)

 Many liquefied gases can be
stored in gas storage spheres
at atmospheric pressures, for
example air, O2, N2 at ~ -190°C
 CO2 is stored at ~ -20°C at
20 bar (triple point at 5.1 bar;
if de-pressurised below that it
will give a solid : dry ice! )
 Ammonia can stored at
atmospheric pressure at -33°C
 Alternatively, gases can be
stored without refrigeration in
pressurised gas bottles.
LNG storage tanks,

roll-over
 Heat transfer inside LNG

storage tank, roll-over
Pictures:
MMVW14
5.11 LNG off-loading, regasification
See also MMW14: chapter 1.4.6
LNG regasification /1
 At the destination, LNG must be returned to the gaseous state for
transport and distribution, gradual warming from -163°C to > 0°C at
60 ~ 100 bar or more.
 Also, to recover energy: ~ 8% of LNG energy is used for liquefaction!
 If possible, sea-water
trickle-type heat
exchangers (made of
wood, or Ti-based metal)
are used; if needed
some of the gas is
burned to produce heat.
 In some cases, contents of
N2 and/or C2+ are adjusted.
 See: http://www.saggas.com/en/proceso-de-regasificacion/
LNG regasification /2
Pictures: http://www.saggas.com/en/proceso-de-regasificacion/
Port of Sagunto ,
(East coast of Spain)
Installed capacity
1.150.000 Nm3/h
Vaporisers (4x seawater,
1x submerged combustor)
 Status Finland (Feb. 2017):
– Pori: operational September 2016 (storage capacity 0.015 Mt)
– Tornio Manga project (to be available 2018)

– Porvoo: LNG production operational 2010 (0.02 Mt/a)
Off-loading: LP compression, BOG

condensation, HP compression /1
 LP sendout
pumps:
~ 1.3  ~ 9 bar
typical
Pictures:
MMVW14
Picture:
MMVW14
 After LP pump 1.3  9 bar, BOG recondenser at

~ 9 bar, followed by HP pump  120 bar

 LP sendout
pumps:
~ 9  ~ 120 bar
typical
Pictures:
MMVW14
Regasification / vaporisation /1
Pictures:
 Open Rack Vaporisation (ORV) : ~ 70% MMVW14
water
 Submerged Combustion Vaporizer (SCV): ~20% Pictures:

MMVW14
 Shell-and-tube  Intermediate fluid Pictures:

vaporiser vaporiser process MMVW14
 Hydrocarbon
heat transfer
fluid process
Pictures:
MMVW14
 Ambient air Pictures:

vaporizer MMVW14
As for yet another option
for recovery of LNG cold
energy:
Stirling engines !
 Use of cold with organic Rankine cycle (ORC) Pictures:

closed (left) or open (right) MMVW14
5.12 FPSO: floating production,

storage and off-loading for LNG
FPSO floating production, storage and offloading

 For example, the Lithuanian Picture: http://en.delfi.lt/lithuania/energy/floating-lng-terminal-
floating storage and

regasification unit (FSRU),
independence-sails-into-klaipeda.d?id=66226156
built for Lithuania’s liquefied

natural gas (LNG) terminal
at Klaipéda; storage
capacity 170 000 m3. (27.10.2014)
 Compared to on-shore equipment,
besides energy efficiency
extra attention to compactness
and safety
 Mixed refrigerant (MR) processes
need less equipment, while pure Single Mixed Refrigerant (SMR)
refrigerant cycles need more stages Process (see L11)
NG liquefaction for FPSO
 LNG liquefaction processes for FPSO studied by Lee et al. (2011)

See also:
 http://www.mustangeng.com/NewsandIndustryEvents/Publications/Publications/ midstream_LNG_Journal_Feb08.pdf (2008)
 http://www.airproducts.com/~/media/Files/PDF/industries/lng/en-lean-gas-article.pdf (2013)
5.13 Hydrogen
See also http://www.hydrogen.energy.gov (Feb. 2017)
Hydrogen production
Picture: http://www.partstrain.com/images/The_Auto_Blog/BMW_hydrogen_new.jpg (Oct. 2012)

 Hydrogen is (was?) seen, especially by politicians, as a ”solution” to
the ”energy production” and greenhouse effect problems
 However, hydrogen is not a fuel that can be extracted from
a natural resource but must be produced
 Options for hydrogen production are
– From natural gas or bio-gas by reforming
with steam and/or oxygen
– From coal (or peat or wood or .....) by gasification
– By electrolysis of water, using electricity from nuclear power or a
renewable source (wind, solar, ...)
– Fermentative and other micro-organism systems
 Separation of H2 from syngas (CO/H2/...) or other gas mixture can
be accomplished with for example pressure swing absorption (PSA)
methods or membranes
 Often concentrated CO2 is a by-product → CO2 sequestration
Picture: http://www.astro.uwo.ca/~jlandstr/planets/webfigs/matter/slide6.html (Oct. 2012)

Hydrogen liquefaction /1
Source & picture: http://www.oilcrash.com/articles/h2_eco.htm#5.2 (Oct. 2012)
 The energy content per volume
of gaseous hydrogen is low;
even in liquefied form it is less
than that of for example
gasoline
 Compression of H2 is very
energy consuming; for example
compression to 20 bar can cost
10% of the heating value energy
 Liquefaction requires
temperatures below 33 K
(Tcrit), for atmospheric
pressure 20 K.
 For the Joule-Thomson effect a
temperature < 200 K is needed
Picture: http://www-pub.iaea.org/MTCD/Publications/PDF/te_1085_prn.pdf (Oct. 2012)

 Cooling of H2 is accomplished by  Current energy requirements for
multi-stage compression and H2 liquefaction are in the order of
expansion coupled with counter- 30 – 60 MJ (8-17 kWh)/kg liquid
flow heat exchange and energy H2 (theory : 14.1 MJ/kg) for a
recovery by expansion turbines, plant producing > 100 kg/h
based on the Claude process:
 I. Compression to ~ 50 bar,
removal of compression heat
 II. Pre-cooling with liquid nitrogen
to ~ 80 K / ~ - 196°C
 III. Expanding and further cooling
of the H2 (80 → 30 K)
 IV. Expanding in a throttling valve
→ 20 K
 Liquid H2 is then stored at low
pressure and T ~ 20 K
(sources: BET04, IAEA99 )
Picture: http://www.hydrogen.energy.gov/pdfs/progress05/v_e_1_shimko.pdf (Oct. 2012)

 Work in the US under the
DOE hydrogen program aims at
liquefied H2 production at
13-18 MJ/kg, corresponding to
~ 0.5 US$/kg.
 The process is based on the
hydrogen Claude process, and is
referred to as the Combined
Reverse-Brayton Joule-
Thomson (CRBJT) expansion
Simplified CRBJT cycle
cycle
K-101 & E-100: compression and cooling
 The efficiency of the hydrogen LNG-101 and LNG-102: heat exchange
Claude process may be improved TEE-100: flow divider
by using He, He/Ne or Ne instead Q-102: turbo-expander
of H2 in the gas compression / VLV-100: throttling valve
expansion cycle (He-Brayton; MIX-100: mixes gas from turbo-expander
Ne-Brayton cycle) and from flash separator
P, h diagram for hydrogen
Source: http://refrigerant.itri.org.tw/Refprop/Normal%20hydrogen.gif (dead link)

Also known as refrigerant R-702; Note: temperatures up to 100 K only
Pictures: http://naftcenews.wvu.edu/naftc_enews/2005/08/07/advances-in-hydrogen-storage (Oct. 2012)

H2 transport and storage /1
 Hydrogen can be stored as a compressed gas,
in liquefied form or as solid hydrides. For large
amounts, underground storage in aquifers and
depleted oil/gas reservoirs can be considered.
 Metal hydride (MH) storage devices (as High pressure H2 transport
developed by Ovonics) can store up to three
times as much hydrogen in the same volume as
can be stored using high pressure methods
Liquefied H2 transport
H2 storage as metal hydrides (≈ 340 bar)
H2 transport and storage /2
Pictures: http://www.innovation-brennstoffzelle.de/e/h2/haupt3e.html (Oct. 2012)

Picture http://www.apollomissionphotos.com/index_apollo_saturn2.html (Oct. 2012)
 Liquefied hydrogen pipeline
(a few 100 m) at Cape Canaveral (FL);
several 1000 km of pressurised H2
pipeline exist worldwide
An LH2 vessel
LH2 storage at NASA

5.14 Dry ice
Picture: http://i.ebayimg.com/00/s/NTY2WDg0OQ==/z/nuMAAOSwcnpTqrYg/$_32.JPG?set_id=880000500F
Dry ice (solid CO2) production /1
Throttling
of a
saturated
liquid:
AB
below
triple sublimation
point line at 1 atm
only at –78.5 °C
gas
+ solid
Picture:
A11
Dry ice (solid CO2) production /2
Here, heat rejection in condenser

at 25°C to an NH3 v-c cycle
Picture:
A11
Sources #5 /1
 A83: P.W. Atkins ”Physical chemistry”, 2nd ed., Oxford Univ. Press (1983)
 A11: R. C. Arora ”Refrigeration and air conditioning”, 2nd. Ed. PHI
Learning Private Limited, New Delhi (2011) Chapter 2.30, 6.8, 13.10-11,
 BET04: U Bossel, B. Eliasson, G. Taylor ”The future of the hydrogen economy:
bright or bleak?” (2003, 2004) http://www.oilcrash.com/articles/h2_eco.htm#nota_01
 D03: İ. Dinçer “Refrigeration systems and applications” Wiley (2003)
 F05: T.M. Flynn “Cryogenic engineering” 2nd Ed. Marcel Dekker (2005)
 IAEA99: “Hydrogen as an energy carrier and its production by nuclear power”
IAEA-TECDOC--1085 IAEA, Vienna (Austria) (1999)
 L11: S Lee et al., “The study on a new liquefaction cycle development for LNG
plant” Int. Gas Union Res. Conf. 2011 (15 p.)
http://members.igu.org/IGU%20Events/igrc/igrc2011/igrc-2011-proceedings-and-presentations/poster-
papers-session-4/P4-22_Sanggyu%20Lee.pdf/@@download/file/P4-22_Sanggyu%20Lee.pdf
For some p,h diagrams:

http://www2.dupont.com/Refrigerants/en_US/products/literature.html (accessed Feb. 2016)
http://christophe.lauverjat.pagesperso-orange.fr/mava/index.html (accessed Feb. 2016)
Picture http://www.eq.uc.pt/~abel/gifs/Kol24lg.JPG (Feb. 2017)

Sources #5 /2
 ME06: S. Mokhatab, M.J. Economides, World Oil Magazine 227(2) (Feb
2006) http://www.worldoil.com/February-2006-Process-selection-is-critical-to-onshore-LNG-
economics.html
 MMVW14: S. Mokhatab, J.Y. Mak, J.V. Valappil, D.A. Wood, Handbook of
Liquefied Natural Gas, Elsevier / Gulf Profess. Publ. (2014) Chapter 1,(2),3,4
see https://abo.finna.fi/Record/alma.1238231 incl. E-book
 WE09: X. Wang, M. Economides, ”Advanced natural gas engineering,” Gulf
Publ. Co. (2009)
 S90: A.L. Stolk ”Koudetechniek A1”, Delft Univ. of Technol. (1990)
 TV08: D,G. Thombare, S.K. Verma. ”Technological developments in the
Stirling cycle engines”, Renew. Sustain, Energy Rev. 12 (2008) 1-38
 Ö96: G. Öhman ”Kylteknik”, Åbo Akademi Univ. (1996)
http://users.abo.fi/rzevenho/Kylteknik%20_Ohman%2019962000.pdf
 See also: Martinez, I. ”Lectures on Thermodynamics” – lecture 18
(English or Spanish) http://webserver.dmt.upm.es/~isidoro/bk3/index.html
updated and based on “Termodinámica básica y aplicada", Ed. Dossat,
Madrid (1992) ISBN 84-237-0810-1 Kamerlingh Onnes Lab Leiden (1924)

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Refrigeration (Kylteknik)

course # 424519.0 v. 2017

5. Low temperatures, liquefied gases,

ÅA 424519 Refrigeration / Kylteknik

5.1 Gas refrigeration and

ÅA 424519 Refrigeration / Kylteknik

5.2 Stirling cycles

See also A11: chapter 13.10

Stirling cycle, Stirling engine

 Heat is temporarily stored in the

12.2.2017 Åbo Akademi Univ - Thermal and Flow Engineering 7/84

Stirling refrigeration cycles /1

See also: http://www.stirlingcryogenics.com/ (Feb 2017)

With repeated strokes,

ÅA 424519 Refrigeration / Kylteknik

5.3 Joule-Thomson effect

See also A11: chapter 2.30

Gas expansion: Joule-Thomson effect /2

 Some tabelised data:

ÅA 424519 Refrigeration / Kylteknik

5.4 Linde-Hampson process

See also A11: chapter 13.11

1 and 7 can be open for

Data for several gases

Ar -122.44 48.00 -185.87

Energy balance II:

Linde-Hampson process – ideal /3

air mass fraction liquefied,

T2 = 120 K, T3’ = 80 K (see also Ö96 – example 6.4)

Linde-Hampson process – real states ”*”

4* instead of 4: much less

Linde-Hampson initial cascade process

12.2.2017 Åbo Akademi Univ - Thermal and Flow Engineering 22/84

5.5 Claude process

See also MMW14: chapter 4..2.6

Claude process - ideal

6-7 gas product

6* instead of 6: much less

Cooling inlet compression Picture: S90

Linde-Hampson vs. Claude process

 The Claude process is more complicated, requires less energy

Energy input for producing liquefied air at 80 Theoretical In practice

ÅA 424519 Refrigeration / Kylteknik

5.6 Liquefied hydrocarbons

See also MMW14: chapter 4..2.4

See:: http://www.khi.co.jp/english/rd/tech/154/ne154ts00a.html (Oct. 2012)

Typical ”train” unit size

12.2.2017 Åbo Akademi Univ - Thermal and Flow Engineering 32/84

For LNG: 35 ... 55 MJ/Nm3

Acetylene, ethylene, CO2, ....

12.2.2017 Åbo Akademi Univ - Thermal and Flow Engineering 34/84

5.7 LNG supply chain and processing

See also MMW14: chapter 1

Natural /LNG gas supply chain

Depending on transport distance and amount, transport of NG by pipeline, as

LNG production from raw NG

 LNG: atm. boiling point ~ -162°C, 87-99% methane, density 430 ~

ÅA 424519 Refrigeration / Kylteknik

5.8 Liquefied gas, LNG transport

See also MMW14: chapter 3

Picture: http://www.kommersant.com/photo/300/DAILY/2005/237/KP_55007_008_18_l.jpg (Oct. 2012)

Picture: http://www.vpsr.cz/lpg-road-tankers (oct. 2012)

 See also http://liquefiedgascarrier.com/ (Nov. 2014)

12.2.2017 Åbo Akademi Univ - Thermal and Flow Engineering 41/84