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Flow Measurement and Instrumentation 16 (2005) 387–395

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The Joule–Thomson effect in natural gas flow-rate measurements


Ivan Marić∗
Rud̄er Bošković Institute, Division of Electronics, Laboratory for Information Systems, Bijenička c. 54, P.O.B. 180, 10002 Zagreb, Croatia

Received 26 January 2005; received in revised form 7 April 2005; accepted 15 April 2005

Abstract

A numerical procedure for the calculation of the Joule–Thomson (JT) coefficient of a natural gas is derived. The AGA-8 extended virial-
type characterization equation is used to calculate the rate of change of the compression factor with respect to the temperature at constant
pressure. The DIPPR/AIChE generic ideal heat capacity equations are used to derive the molar heat capacity of a natural gas mixture.
The accuracy of the natural gas flow-rate measurements, based on differential devices, is analysed with respect to the temperature drop,
characterized by the JT effect. The results obtained are illustrated graphically. The procedure derived enables compensation for the JT effect
in natural gas flow-rate measurements.
© 2005 Elsevier Ltd. All rights reserved.
Keywords: Joule–Thomson coefficient; Molar heat capacity; Natural gas; Compression; Flow rate

1. Introduction approximated by the following equation:


U2 − U1 = Q + W (1)
When a gas expands through a restriction from high
pressure to low pressure it changes its temperature. This where U2 and U1 denote the internal energy in the system
process occurs under conditions of constant enthalpy and at the beginning and at the end of the process, Q is the heat
is known as JT expansion [1]. It can also be considered added to the system and W is the work done by the system.
as an adiabatic effect because the pressure change occurs We assumed an insulated system and the heat added to the
too quickly for significant heat transfer to take place. The system can be neglected, i.e. Q = 0. The work done by the
temperature change is related to pressure change and is system is
characterized by the JT coefficient. The temperature drop
increases with the increase of the pressure drop and is W = p1 V1 − p2 V2 (2)
proportional to the JT coefficient. For each gas there exists and Eq. (1) becomes
an inversion point that depends on temperature and pressure,
below which it is cooled and above which it is heated. U1 + p1 V1 = U2 + p2 V2 (3)
Let us consider the gas flow through the orifice, shown
or
in Fig. 1, to be an insulated process so that no heat is
transferred during the process. The gas initially has a H1 = H 2 (4)
pressure p1 , temperature T1 and volume V1 . After it passes
through the orifice, its pressure is p2 and the volume is V2 . where H1 and H2 denote the corresponding enthalpy at
If the kinetic and potential energy change of the gas the beginning and at the end of the process. From the
is negligible, then the first law of thermodynamics can be above assumptions and Eq. (4) it follows that the gas-flow
through the orifice can be considered a constant enthalpy
(isenthalpic) process. Our objective is to find the temperature
∗ Tel.: +385 1 4561191; fax: +385 1 4680114. change T = T1 − T2 , given a particular gas and the
E-mail address: ivan.maric@irb.hr. conditions T1 , p1 , p2 and H1 = H2. To achieve this we need

0955-5986/$ - see front matter © 2005 Elsevier Ltd. All rights reserved.
doi:10.1016/j.flowmeasinst.2005.04.006
388 I. Marić / Flow Measurement and Instrumentation 16 (2005) 387–395

substituting (9) into (10) we obtain the total differential of h:


   
∂v
dh = c p dT + v − T d p. (11)
∂T p
If Eq. (11) is divided by d p while holding h constant (dh =
0; isenthalpic process) the following equation is obtained:
     
∂T 1 ∂v
= T −v . (12)
∂p h cp ∂T p
After substituting v = R T Z /(M p) into Eq. (12) and then
Fig. 1. Gas flow through the orifice can be considered as an isenthalpic
Eq. (12) in Eq. (5) we obtain
process.  
R T2 ∂Z
µJT = (13)
pcm, p ∂ T p
to calculate the thermodynamic quantity
  where M is a real gas molar mass, cm, p = c p /M is the
∂T
µJT = (5) molar heat capacity at constant pressure, R denotes the
∂p H universal gas constant and Z is the compression factor.
where µJT is known as the JT coefficient. The temperature Eq. (13) is adapted for the calculation of the JT coefficient
change can be calculated using of a natural gas based on the AGA-8 extended virial-type
characterization equation [3].
T = µJT ω (6) According to [5] the gas heat capacity is c p = c p I −
where ω denotes a pressure loss across the orifice plate. R T (T Φ  + 2Φ  ). The corresponding molar heat capacity
(cm, p = c p /M) is
1
2. Procedure cm, p = [c p I − R T (T Φ  + 2Φ  )], (14)
M
This section outlines the procedure used for the calcula- where Φ  and Φ  are the first and the second derivatives
tion of the JT coefficient of a natural gas based on an AGA-8 of the gas fugacity coefficient, R is the molar gas constant
extended virial-type characterization equation [2,3] and and c p I is the ideal molar heat capacity of a gas mixture at
DIPPR generic ideal heat capacity equations [4]. First, the flowing temperature T . The fugacity coefficient of a real gas
relation of the JT coefficient to the equation of state will be is defined by
derived. Then the relation will be adapted for the calculation  pf
dp
of the JT coefficient of natural gas using the AGA-8 natural Φ= (Z − 1) , (15)
0 p
gas compression factor equation [2,3].
Let us start with the fundamental differential equation where Z is the gas compression factor, p is pressure variable
and p f the flowing or operating pressure. The ideal molar
dh = T ds + vd p (7) heat capacity c p I is calculated using
relating the specific enthalpy h to the specific entropy s, 
N
temperature T , specific molar volume v and pressure p. If cpI =
j
y j c pi (16)
Eq. (7) is divided by d p at constant T the result is j =1
   
∂h ∂s where y j is the molar fraction of component j in the
=T + v. (8)
∂p T ∂p T j
gas mixture and c pi is the molar heat capacity of the
Using the Maxwell relation (∂s/∂ p)T = −(∂v/∂ T ) p , same component at the flowing temperature. The molar
Eq. (8) is transformed into heat capacities of the ideal gas mixture components can
    be approximated by polynomials, or using DIPPR/AIChE
∂h ∂v generic equations [4], i.e.
= −T + v. (9)
∂p T ∂T p  2  2
j c j /T e j /T
Consider the enthalpy to be a function of temperature and c pi = a j + b j + dj , (17)
sinh(c j /T ) cosh(e j /T )
pressure, or h(T, p). The total differential is
    j
where c pi is the molar heat capacity of the component j
∂h ∂h
dh = dT + dp (10) of the ideal gas mixture, a j , b j , c j , d j and e j are the
∂T p ∂p T
corresponding constants and T is the flowing temperature.
where (∂h/∂ T ) p is by definition the heat capacity at The constants a, b, c, d and e for some gases are shown in
constant pressure c p , while (∂h/∂ p)T is defined by (9). By Table 1.
I. Marić / Flow Measurement and Instrumentation 16 (2005) 387–395 389

Fig. 2. Interface to the software object, which implements the calculation of the Joule–Thomson coefficient and the natural gas properties in accordance with
AGA-8.

Table 1 
58
The DIPPR/AIChE gas heat capacity constants + K −3 ρr2 ρr−1 Cn∗ K 3 [bn2 − cn kn (2bn + kn
n=13
Natural gas DIPPR/AIChE ideal gas heat capacity constants kn
component a b c d e − cn kn ρrkn )ρrkn ]ρrbn −1 e−cn ρr (20)

Methane—CH4 33 298 79 933 2086.9 41 602 991.96 where


Ethane—C2 H6 40 326 134 220 1655.5 73 223 752.87 
18
Propane—C3 H8 51 920 192 450 1626.5 116 800 723.6 Z0 = B − K 3 Cn∗ , (21)
n=13

58
Z1 = Z0 + Cn∗ K 3 [bn2 − cn kn (2bn + kn − cn kn ρrkn )
The calculation of partial derivative of the AGA-8 n=13
compression factor with respect to the temperature at kn
× ρrkn ]ρrbn −1 e−cn ρr (22)
constant pressure (∂ Z /∂ T ) p as well as the calculation
of first (∂Φ/∂ T ) and second derivatives (∂ 2 Φ/∂ T 2 ) of and B, Cn∗ , K , ρm , ρr , bn , cn and kn are the parameters of the
the fugacity coefficient with respect to the temperature is AGA-8 equation of state [3] and are described in Table 2.
elaborated in [6]. Here we provide only the final equations, The above procedure is implemented using Object
i.e. Oriented Programming (OOP) approach. Fig. 2 illustrates
the interface to a software object S, which calculates the JT

58 kn coefficient, compression factor and other related parameters
R(T Z )2 C n∗ (bn − cn kn ρrkn )ρrbn e−cn ρr + p Z (T Z 0 − Z 1 )
 n=13 on the basis of the AGA-8 natural gas equation of state
Z = , (18)
R(T Z )2 + pT Z 1 [2,3]. The object function Calculate maps the input
  
1 58 kn parameters to the output results.
Φ = Z 1 − + ρm Z 0 + Z 0 ρm + C n∗ ρrbn e−cn ρr
Z n=13
ρr 
58 kn
+ C ∗ (bn − cn kn ρrkn )ρrbn e−cn ρr (19) 3. Experimental flow measurement system model for JT
ρr n=13 n
effect analysis
and
  In order to analyze the JT effect in flow measurements,
1 Z 2
Φ  = Z  1 − + 2 + 2Z 0 ρm + ρm Z 0 + Z 0 ρm based on pressure differential devices, the measuring section
Z Z shown in Fig. 1 was simulated. We assumed a natural
58 kn gas [3] flowing in a pipeline (D = 200 mm) through
+ Cn∗ ρrbn e−cn ρr an orifice plate (d = 120 mm) with corner taps in
n=13 accordance with ISO-5167-2 [7]. According to [8], the

58 kn temperature of the fluid should preferably be measured
+ 2ρr ρr−1 Cn∗ (bn − cn kn ρrkn )ρrbn e−cn ρr downstream of the primary device, but upstream temperature
n=13 should be used for the calculation of the flow rate. Within

58
the limits of application of ISO-5167 [8] it is generally
+ ρr−2 (ρr ρr − ρr2 ) Cn∗ (bn − cn kn ρrkn ) assumed that the temperature drop across the differential
n=13
device can be neglected but it is also suggested that one
bn −cn ρrkn
× ρr e should take it into account if higher accuracies are required.
390 I. Marić / Flow Measurement and Instrumentation 16 (2005) 387–395

Table 2
Symbols and units

Symbols and units


Symbol Description Unit

bn AGA-8 equation of state parameter –


C Coefficient of discharge –
cm, p Molar heat capacity at constant pressure J/(mol K)
Cn∗ Temperature and composition dependent coefficients –
cn AGA-8 equation of state parameter –
cp Specific heat capacity at constant pressure J/(kg K)
cpI Ideal molar heat capacity of the natural gas mixture J/(mol K)
j
c pi Ideal molar heat capacity of the gas component j J/(mol K)
D Upstream internal pipe diameter m
d Diameter of orifice m
H Enthalpy J
h Specific enthalpy J/kg
K Size parameter –
kn AGA-8 equation of state parameter –
M Gas mixture molar mass kg/(kmol)
p Pressure MPa
Q Heat added to the system J
qm Mass flow rate kg/s
R Molar gas constant 8314.51 J/(kmol K)
s Specific entropy J/(kg K)
T Temperature K
U Internal energy of the system J
v Specific volume m3 /kg
V Volume m3
W Work done by the system J
yi Molar fraction of i-th component in gas mixture –
Z Compression factor –
β Diameter ratio d/D –
p Differential pressure Pa
ω Pressure loss Pa
µJT Joule–Thomson coefficient K/Pa
Φ Fugacity coefficient –
ρm Molar density kmol/m3
ρr Reduced density –

The temperature change for the orifice plate is defined The temperature drop is calculated using Eq. (6), i.e. T =
by Eq. (6). The JT coefficient strongly depends on the T1 − T2 = µJT ω.
temperature, pressure and natural gas composition and may
vary significantly. The pressure loss is the difference in
static pressure of the fluid measured approximately one 4. Results and discussion
pipe diameter upstream and at least six pipe diameters
downstream of the orifice plate. The pressure loss ω in The magnitude of the JT coefficient of a natural gas
Eq. (6) for an orifice plate with corner taps [7] can be depends on the natural gas composition and varies with
approximately calculated using the following equation: temperature and pressure. The temperature drop due to
 the JT effect is proportional to the product of the JT
1 − β 4 (1 − C 2 ) − Cβ 2 coefficient and the pressure loss. In orifice-based flow-
ω =  p (23)
1 − β 4 (1 − C 2 ) + Cβ 2 rate measurements [7] the upstream temperature is used
for the calculation of the flow rate but the temperature
where p denotes the differential pressure, C is the
should preferably be measured downstream of the primary
coefficient of discharge and β is the ratio of the inner
device. The density, viscosity and isentropic exponent of
diameters of the orifice and the pipe. A detailed description
a gas are dependent on the temperature and consequently
of the pressure loss for orifice plates is given in [9]. Another
the uncompensated effect of a temperature drop may cause
approximate equation for pressure loss calculations [8] is
an error in the flow-rate measurements. The impact of the
ω = (1 − β 1.9 )p. (24) temperature drop on the accuracy of real-time flow-rate
I. Marić / Flow Measurement and Instrumentation 16 (2005) 387–395 391

measurements and the way in which it can be compensated qm ( p1 , T2 , p) − qm ( p1, T1 , p)
Er =
are discussed in this section. qm ( p1 , T1 , p)
qm2 − qm1
= (25)
qm1
4.1. JT coefficient
are calculated, where qm ( p, T, p) denotes the mass
flow rate at the specified pressure p, temperature T and
Figs. 3 and 4 illustrate the corresponding JT coefficients
differential pressure p. Prior to computing the flow rate,
for methane and for a natural gas mixture (ISO-12213-
the corresponding calculation of a natural gas density [3],
2/Annex C/Table C.1/Gas 3/mole percentages: methane
viscosity (residual viscosity function) [11] and isentropic
85.90, ethane 8.50, propane 2.30, carbon dioxide 1.50, nitro-
exponent [6] is performed. Fig. 7 shows a relative flow-
gen 1.00, i -butane 0.35, n-butane 0.35, i -pentane 0.05 and
rate error for methane flowing through the orifice plate with
n-pentane 0.05) calculated for the range of pressure from
corner taps [7] shown in Fig. 1. The results are shown for
0 to 60 MPa in 1 MPa steps and for six discrete tempera-
two discrete differential pressures (20 and 100 kPa) and for
tures in the range from 245 to 345 K. From Figs. 3 and 4
absolute upstream pressure ranging from 0 to 60 MPa in 1
it can be seen that for each temperature there exists a cor-
MPa steps and for six equidistant upstream temperatures in
responding pressure (inversion point) at which the JT coef-
the range from 245 to 345 K. Fig. 8 shows a relative flow-
ficient changes its sign. The calculations are shown up to a
rate error for a natural gas mixture (ISO-12213-2/Annex
pressure of 60 MPa, which lies within the ‘Wider Ranges of
C/Table C.1/Gas 3/mole percentages: methane 85.90, ethane
Application’ given in ISO12213-2, of 0–65 MPa. However,
8.50, propane 2.30, carbon dioxide 1.50, nitrogen 1.00,
the lowest uncertainty for compressibility is for pressures up
i -butane 0.35, n-butane 0.35, i -pentane 0.05 and n-pentane
to 12 MPa and no uncertainty is quoted in Ref. [3] for pres-
0.05) obtained over the same pressure and temperature
sures above 30 MPa. Above this pressure, it would therefore
ranges as in Fig. 7. From Figs. 7 and 8 it can be seen that
seem sensible for the results of the JT calculations to be used
the maximum relative flow-rate error increases with the
with caution.
increase of the differential pressure at constant temperature.
Also the maximum error decreases with the increase of the
4.2. Temperature drop temperature at constant differential pressure. It is interesting
that Figs. 7 and 8 show that orifice metering is most sensitive
Fig. 5 shows the temperature drop for methane flowing to the JT effect in the range 5–12 MPa, which is the
through the orifice plate with corner taps [7]. The results range over which most natural gas transmission metering
are shown for two discrete differential pressures (20 and occurs. This is due to a combination of the JT temperature
100 kPa) and for absolute upstream pressure ranging from drop across the plate combined with the sensitivity of the
0 to 60 MPa in 1 MPa steps and for six equidistant gas density to the temperature value used for the density
upstream temperatures in the range from 245 to 345 K. calculation. Beginning with low pressure and holding the
Fig. 6 shows the temperature drop for a natural gas mixture temperature and differential pressure constant, the error
(ISO-12213-2/Annex C/Table C.1/Gas 3/mole percentages: first increases with the increase of pressure, reaches a
methane 85.90, ethane 8.50, propane 2.30, carbon dioxide maximum and then decreases with further increase of
1.50, nitrogen 1.00, i -butane 0.35, n-butane 0.35, i -pentane pressure. At very low differential pressures the JT effect
0.05 and n-pentane 0.05) obtained over the same pressure can be ignored with negligible effect on the flow-rate error,
and temperature ranges as in Fig. 5. but at higher differential pressures and lower temperatures
the error increases significantly and the temperature drop
must be compensated in order to reduce the corresponding
4.3. Flow-rate error measurement error. The flow-rate error due to the JT
effect also depends on the natural gas composition because
To simulate a natural gas flow-rate error caused by the density and viscosity are changing with temperature.
the temperature drop at a particular pressure, temperature The calculation of upstream temperature from downstream
and differential pressure (Fig. 1), the flow rate of a temperature is an iterative procedure because JT coefficients
natural gas is calculated first by using the real upstream at upstream and downstream temperatures are not linearly
temperature and then by using the calculated downstream related. It is, however, reasonable to assume the JT
temperature as measured upstream. The flow-rate error is coefficients at upstream and downstream temperatures to
calculated by using a measurement system model with be approximately the same for differential pressures below
measurement procedures embedded in the OOP mode [10]. 100 kPa. The upstream temperature can then be calculated
For the corresponding natural gas composition, upstream using
temperature T1 , upstream pressure p1 and differential
T1 ≈ T2 + µJT ω, (26)
pressure p, the corresponding JT coefficient µJT , pressure
loss ω, downstream temperature T2 = T1 − µJT ω and where µJT denotes the JT coefficient computed at
the relative error downstream temperature T2 and upstream pressure p1 .
392 I. Marić / Flow Measurement and Instrumentation 16 (2005) 387–395

Fig. 3. Joule–Thomson coefficient µJT for methane for pressures from 0 to 60 MPa and temperatures from 245 to 345 K.

Fig. 4. Joule–Thomson coefficient µJT for a natural gas mixture (mole percentages: methane 85.90, ethane 8.50, propane 2.30, carbon dioxide 1.50, nitrogen
1.00, i-butane 0.35, n-butane 0.35, i-pentane 0.05 and n-pentane 0.05) and for pressures from 0 to 60 MPa and temperatures from 245 to 345 K.
I. Marić / Flow Measurement and Instrumentation 16 (2005) 387–395 393

Fig. 5. Temperature drop due to the JT effect T = µJT ω when measuring the flow rate of methane through the orifice plate with corner taps (ISO-5167-2).
The pressure p varies from 1 to 60 MPa in 1 MPa steps, temperature T from 245 to 305 K in 20 K steps, for each of two differential pressures p (20 and
100 kPa).

Fig. 6. Temperature drop due to the JT effect T = µJT ω when measuring the flow rate of a natural gas mixture (mole percentages: methane 85.90, ethane
8.50, propane 2.30, carbon dioxide 1.50, nitrogen 1.00, i-butane 0.35, n-butane 0.35, i-pentane 0.05 and n-pentane 0.05) through the orifice plate with corner
taps (ISO-5167-2). The pressure p varies from 1 to 60 MPa in 1 MPa steps, temperature T from 245 to 305 K in 20 K steps, for each of two differential
pressures p (20 and 100 kPa).
394 I. Marić / Flow Measurement and Instrumentation 16 (2005) 387–395

Fig. 7. Relative error Er = (qm2 − qm1 )/qm1 in the flow rate of methane measured by an orifice plate with corner taps (ISO-5167-2) when using downstream
temperature measurement with no compensation for the JT effect (qm2 ) instead of upstream temperature (qm1 ). The pressure p varies from 1 to 60 MPa in 1
MPa steps, temperature T from 245 to 305 K in 20 K steps, for each of two differential pressures p (20 and 100 kPa).

Fig. 8. Relative error Er = (qm2 − qm1 )/qm1 in the flow rate of a natural gas mixture (mole percentages: methane 85.90, ethane 8.50, propane 2.30, carbon
dioxide 1.50, nitrogen 1.00, i-butane 0.35, n-butane 0.35, i-pentane 0.05 and n-pentane 0.05) measured by an orifice plate with corner taps (ISO-5167-2) when
using downstream temperature measurement with no compensation for the JT effect (qm2 ) instead of upstream temperature (qm1 ). The pressure p varies from
1 to 60 MPa in 1 MPa steps, temperature T from 245 to 305 K in 20 K steps, for each of two differential pressures p (20 and 100 kPa).
I. Marić / Flow Measurement and Instrumentation 16 (2005) 387–395 395

4.4. Compensation for the effect of the temperature drop in the calculation of the natural gas molar heat capacity and
flow-rate measurements the partial derivative of a natural gas compression factor
with respect to the temperature at constant pressure. The
Whilst modern flow computers have provision for procedure enables the calculation of the JT coefficient of
applying a JT correction to measured temperatures, this natural gas over a wide range of pressures and temperatures
usually takes the form of a fixed value supplied by the user. and can be applied in flow-rate measurements based on
The calculations in this paper show that any initial error pressure differential devices.
in choosing this value, or subsequent operational changes
in temperature, pressure or gas composition, could lead to
significant systematic metering errors. Acknowledgement
In order to compensate for the effects of temperature
drop due to JT expansion through an orifice plate the The author would like to express his thanks to
temperature correction procedure could be implemented in Dr. Roger Norman, Advanced Engineering Solutions Ltd,
the flow computer. For the given gas mixture analysis it Cramlington, UK, for critically reviewing this paper and for
is possible to precalculate the two-dimensional array of JT his valuable comments and suggestions.
coefficients by varying the pressure p and the temperature
T : {µJT ( pi , T j ); i = 1, . . . , M, j = 1, . . . , N; PL ≤ pi ≤
PH , TL ≤ T j ≤ TH }, where PL , PH and TL , TH denote References
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Chemistry, 6th ed., McGraw-Hill, New York, 1996.
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13–20.
Eq. (23) in order to avoid iterative computation of the [7] ISO-51671-2, Measurement of fluid flow by means of pressure
discharge coefficient C. differential devices inserted in circular-cross section conduits running
(2) Interpolate the JT coefficient (e.g. piecewise lin- full – Part 2: Orifice plates, ISO, Ref. No. ISO-51671-2:2003(E), (ISO
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{µJT ( pi , T j ); i = 1, . . . , M, j = 1, . . . , N}. [8] ISO-51671-1, Measurement of fluid flow by means of pressure
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