i-`: --=-i rJ

gjff-

The Role of Fluid Thermodyliamic Behavioui. in Natural Gas

Handling and Transportation

a report I,y

Luis F Ayala

As5istatlt Professor Of Pe[role.iiil alld Natllral Gas EIIgi[Ieeritig. The Pelmsylualitia State Uiiluersily

Hydrocarbon themrodynairics is an important tool on temperature during throtding or isenthalpic

for the analysis natural gas engineering systems. In expansion. As previously discussed, the effect of
general, natural gas engineering practice centres throtding has a number of inportant applications in
around understanding the interaction between natural gas .engineering and the temperature change
natural gas fluids and various environments, that results of letting a fluid freely expand fi:om a
including the I.eservoir, the pipeline, the separator, higher to a lower pressure is frequendy called the
Joule-Thomson effect. Natural gases are known to
i , ,\ compressors, etc. Understanding of fluid
themrodynanric behavior -i.e. the behaviour of all typicauy cool upon isenthalpic expansion, and this
possible fluid phases as a function of pressure, fact is comnorily used in the production of LNG Luis F Ayala is A!§i5lanl Profe§!or

temperature, and compo.sition - is essential for aiquid methane). The reduction in fluid temperature of Pelmleum and Waluul Gas

[ngifleering al The Pennrylvania

opdmal design and safe and efficient operation of needed in natural gas liquefacdon systems is typically
§lale University. He; hal alto been

engineering systerm dealing with fluids. In this achieved by throttling - the isenthalpic process of all ln!lruclor in lhe Chemical

article, we will inustrate the importance of fluid changing the temperature of a fluid by adiabatic Engineering and Petroleum

Engineering Deparlmenl! at
themodynairic behaviour in the analysis of natural expansion. For cooling upon isenthalpic 9xpansibn Uniyer]idad de Orienle rvenezuela).

gas handling and transportation. to be possible, the themrodymmic behaviour of the Pr6Ie!!or Ayala's research aclivitie]

rocu! on the amaaj of naluul gr

natural gas fluid has to be such that H should talfe •ngineen.ng, hydrocarbon pha!e
One remarkable difference between flow of oil and positive values within t:he region of operadon. While behaviour, mulliphase frow,

natural gases through engineering devices is that of Joule-Thomson coefficients for gases can take
mumerical modeling and arlificial

intelligence. He i§ a member of the

the effect of pressure drop on fluid temperature. This p6sidve or negative values, tb£|Qule-I_bQ_mJS!§gp §o{iety ol Petroleum EnginEerI

is especially tnie when heat losses to the environment cg9.gEsifp`!.£orJi.quidsisalvyays_negagivae,,_alb9iLs!nall. (§PE), Walional A!!o[ialion of

Engineers of Venezuela and the

are not inportant and the system does not exchapge In other woi-ds, in the isenthalpic expansion of Canadian Pelroleum Society.

heat with its surroundings. For instance, it is wen- liquids, there will generally be a small rise in Prole5ioJ Ayala holds PhD and M!

degrees in petroleum and natural

known that mquI3l n g£§._.P.inLe_fi£±£Sa±±Snal!3££QQ1.zwith temperature. To understarid this energetic
gas engineering from The
distance (effect._. cormionlym{.called=joule_Thomson behaviour, one needs to take a look at fluid Penn]y]vania 5!a!e University and

eooling'), while oil lines.`.ke€at. The reason for such theTodynarliic analysis. two tnginEering degree5. orie in

chemical Engineering (!rmm cHm

dissimilarity pertains to the different themlodynamif,
`oude) and one in p!lroleum

phase behaviour of both phases. Whether a gas cools Fluid themodynamic analysis typically employs the engineering (summa (urn `aude)

upon expansion or compression or not - that is, concept of the ideal gas as a benchmark behaviour of lrom llniver!idad de Orienle,

when subjected to pressure changes -depends on the
value of its Joule-Thomson coefficient. This is not
only inportant for natural gas pipeline flow, but also
for the recovery of condensate fi-oin wet natural
gases. In the cryogenic industry, turboexpanders are
used to shoject a wet gas to a sudden expansion (i.e.
sharp pressure drop) in order to cool the gas stream
weu below its dew point, and recover the riquid
dropout. Thermodynamically, the Joule-Thouson
coefficient is defined as the isenthalpic change in
temperature in a fluid caused by a unitary pressure
drop' i.e.
„=(i?A
The joule~Thomson coefficient dr) is the
mathematical measure of the effect of pressure di.op
Venezuela.
reference, and introduces the concept of the
compressibility fac.tor (Z) to a.ccount for deviations
fi.om the ideal gas model. The ideal gas model is the
simplest fonn of a fluid's equation of state (EOS). It
is well known that the ideal gas EOS works well at
low pressures and high temperatures - conditions at
which Z=1. More inportantly, it can be
demonstrated that changes of Z with presslire and
temperature can explain the most salient features of
fluid thermodynanic behaviour.
To illustrate this point, FI.gwrc 1 displays the
behaviour of the compressibility factor (Z) with
respect to pressure and temperature. FJgivlrg I is a v.Cry
useful visualisation of fluid vofumetric behaviour and
was generated using real volumetric data for methane
as predicted by the popular Peng-Robinson EOS - a
cubic EOS.

HYI)ROC^RI}ON WORLD 2007

F,'gl,re I : Z~factor Behaviour with Respect to Pressure arid Teinperatuce_
0,5 I,0 I.5 2.0 2.5 3.0 }.5 4.a 4.5 5.0
Tr
Cubic EOSs are based on the ideas of vari der
Waals, the first physicist to introduce meaningful
pressure and volume corrections to therideal model
and who enunciated the principle of the
corresponding states (PCS). According to the PCS,
all fluids have the sane compressibhity factor when
they are found at corresponding states. Two fluids
are said to be in corresponding states when they
have same reduced conditions (i.e. same pr. Tr, and
same acentric factor, for. the case of the thi-ee-
parameter PCS). Most hydrocarbons and thus
natural gases would then reveal approximately the and at high temperatures if pressures are not too
same volumetric behaviour, in t:emus of z, shown in high. It should be noted that for pl.essures pr >> 7,
FI'g#rc 1 as long as the appropriate reduced Z-factors are always greater than one, which
conditions are considered. indicates that the ideal model consistently
underpredicts volume at those conditions.
In FI*#rc 1, regions where Z takes the value of one
(or close to one) coiistitut:e all possible
combinations of pressure and temperature for
which the ideal EOS genei.aces reliable volurnetric
predictions. This reston is highlighted in light blue
in Flg#rc 1. Since liquid-solid transitions ai.e not
predicted by the Peng Robinson EOS (or any other
cubic EOS for that matter), the solid region and
solid/liquid line presented in Flg!irc I has been
supeliniposed on the figure based on the methane
experimental data. The predicted vapour/liquid
transition or vapour pressure curve (which starts at
the triple point and ends at the critical point
pr=Tl.=1) is also highlighted. The lower end of the
vapour pressure curve (inethane's triple point) is
found at Pr=0.0025 and Tr=0.4759, a condition
which cannot be predicted by cubic EOSs. It
should be noted that any cubic EOS would still
generate liquid -volumetric values for the 1.egion Tr
< Trtriple, where no liquid is present.
Liquid states, found to the left of the critical point
and above vapour pressure coiiditions, have
compressibhity factors that can range from Z=0.01
or below (at low pressures and temperatures) up to
Z=1.50 or inore (at high pressui.es). It is important
to indicate that liquids can exhibit compressibility
factors equal to one (Z=1). Note t:hat Z=1 isoline
extends well into the ]iqui.d region and up to the
solid/liquid transition and this is a consequence of
repulsion forces dominating the behaviour of the
liquid. At the same time, and if all conditions found
to the right of the vapour pressure curve ai.e
considered to be `gaseous' states, it could be said
that the smallest possible gaseous Z-factors are
found around the critical point conditic)ns tor = Tr
= 1). Cubic EOSs predict the same critical
compressibility factor (Zc, Z at pr=Tr=1) for all
fluids - which is a direct consequence of the
principle of corresponding states.
As Fi*#r€ I indicates, the Peng Robinson EOS ,i
predicts a universal Zc = 0.307 for an fluids. In \
reality, Zc-values are not exactly the same for all `-
fluids and they range between 0.23 and 0.31. For
methane, for example, Zc is actually equal to 0.2863.
In contrast, the region where mininum deviations
from ideality take place, i.e. the region where fluid
volunietric behaviour is exacdy predicted by the
ideal EOS (Z=1) and its vicinity (0.99 < Z < 1.01),
is shown in blue in FI£#r€ 1. The figure corroborates
that fluids can be said to behave `ideally' at low
pressures (i.e. pr < 0.25, regal.dless of tempei.ature)
AIL important link between fluid volumetric
behavior and its energeti'c behaviour can be
established by realising that Joule-Thomson „\\
coefficient and Z-factor behaviour can be
thermodynairically related through the fonowing
e#x:ri;;:=##|,,(h`IT=#(-3=;-,p
where cp = constant pressure hea.t capacity. Since
all other coefficients are always positive, this
equation demonstrates that the derivative (dz/dT)p
controls the energetic behaviour of fluids and
natural gases during isenthalpic processes. In other.
words, (dz/dT)p defines whether a fluid would
exhibit positive Joule-Thomson coefficients or not.
When the ten (dz/dT)p is positive, the free
expansion of the fluid would lead to its cooling -
such as what happens when na.tural gas enters
separators or when it crosses chokes or valves.
HYDROC:ATIBON WORLD 2007
 Tlie Role of Fluid Thermodynamic Behavioui. in Natui.al Gas +landling and Ti.ansportation

When (dz/dT)p is negative, the adiabatic Figure 2: The Ei\ei.getic lnvei.sion of Natural Gases

expansion would result in an increase of fluid

temperature, which is the case of liquids.
Pr
Consequently, the equality (az/aT)p=O defines an
15
energetic inversion locus or condition for which
#=0. All transition points where H=O describe the 14

energetic invei.sion curve, which can be readily 13

delineated in Flkitrg 1 by identifying all conditions

12
where (dz/dT)p takes a zero value.
I
Based on the information a.vai]able in Figivrc I, the
10

energetic inversion curve has been delineated in

FI.g#re 2. In this figure, it is clear that cooling 9

occurs inside the inversion dome (i.e. dz/dT takes 8

positive values and thus # > a). while heating

7
occurs outside the inversion envelope because
dz/dT is negative. 6

i An interesting observation is that the Joule-

4
Thomson coefficient of an ideal gas must be
identically equal to zero. Even though t:he `ideal )

region' for the fluid (i.e. the light blue in F!.gijrc I)

2
is contained inside the inversion envelope, tmly
ideal gases neither cool nor heat upon isenthalpic I

expansion because Z=1 = const:ant for ideal gases. 0

Only real fluids can take positive or negative Joule-

0 0.5 I.0 I.5 I.0 2.5 I.0
Thomson values. However, real fluids can
Tr
approach such ideal behaviour at high temperatures

OUR COMPETITORS WERE NOT TOO PLEASED WHEN WE LAUNCHED THE

11 LASER DEWP0lNT METER

\-
 hi
EF=

(Tr > 3) and pressures below pr=10, because iso-Z
curves become approxima.tely flat and changes in Z
with temperature are much less significant. In
summary, fluids found within the left `half' of the
inversion dome (close to the critical point of the
fluid) will experience iiiuch larger temperature
drops during throttling-such as when natural gases
this behaviour is controlled by the value of the
derivadve (dz/dT)p. In contrast, 1iquids have p-v-T
properties that cause them to elevate their in
temperature when adiabatically expanded. Liquid
systems typically operate above the vapour-pressure
curve and below critical conditions, i.e. within the
region that is found to the left and outside of the

Understanding Of f luid thermodynamic bchavio¥ :,i§,,\ diseutial

for aptinal design and saife and egivi.ehi ope;qfron Of

engineering systems di;ting u7ith -fruits.

expand into separators or at chokes in wellheads-
than fluids found within the `right' half of the
inversion dome. The location of the inversion
curve shown in F!±itrc 2 should be regarded as
approximate, since different equations of state
would predict slightly different locations.
FI±#re 2 demonstrated the importance of. fluid
thennodynamic behaviour in t:he analysis of natural
gas handling and transportation. Natural gases wifl
typically reduce their temperature when undergoing
adiabatic expansion, and it has been established that
inversion curve. Therefore, liquid hydrocarbon
systems would typically heat upon adiaba.tic
expansion - because (dz/dT)p is negative for such
conditions. The ti.ansition from cooling to heating,
-\
represented by the inversion envelope, starts around
0.80 < Tr < 0.90 and can be used to distinguish
liquid-like from gas-like thennodymmic behavior.
when fluids are single phase, especially around
critical conditions tor = Tr =- 1). Foi. most
conditions of engiveering interest, natural gases are
found inside the inversion dome and thus they will
be expected to cool upon expansion. rl

Advel.tiser's Index Flexim GmbH 43 Neptune oceanographics Ltd

~.flexim.com www.neptune.gb.com
A d v e I.I i s a T Page
H6egh LNG 29 0utokumpu stainless Tubular
www.hoeghlng.com
Products
Adolf Schnorr GmbH & www.outokumpu.com
Co. KG 35 |unLtd 63
www. `schnon.de Rosen
w~.ima.co.uk www.Rosenlnspection.net/fachity
API 11
International Petroleum Industry Scientific Environmental
www.api.org
Environmental Conservation Instruments Inc
Association (II'IECA) 25 www.sciengr.com
ARUI) 31
www.ipieca.org
www.amp.com/energy SKF ReliabELty System

Burgmann Industries GmbH Meteo Consult 17 W~.Skf.com/reliabflity

& Co. KG 13
www.meteo.nl
Voith Turbo GmbH & Co. KG 49
www.eadebulgmann.com www.va.riable-speed.com
Mubea Tellerfedern und
Christian Bauer GmbH + Sparmelemente GmbH 37 Whessoe s.a
Co. KG 51 www.mubea.com www.whessoe.fr
www.christianbauer.com
National petrochemical & Refiners Wood Mackenzie
CCR Technologies 21 Association (NPRA) mc www.woodmac.com/globalrefining
~.reclin.com -.npm.Org
World Refifling Association
Fire Protection Engineering as 39 NDTsystems&ServicesAG 41 (WRA)
www.fee.no www.wraconferences.com
www.ndt-ag.de