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International Journal of Hydrogen Energy 29 (2004) 1173 – 1180

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E&ect of H2-injection on the thermodynamic and transportation

properties of natural gas
J.A. Schoutena;∗ , J.P.J. Michelsa , R. Janssen-van Rosmalenb
a University of Amsterdam, Van der Waals-Zeeman Institute, Valckenierstraat 67, Amsterdam 1018 XE, The Netherlands
b Energy+i:d , Boslaan 7, Roden 9301 KH, The Netherlands

Abstract
Condensation of hydrocarbons due to temperature and pressure changes in the pipelines plays an important role in the
transportation of natural gas. Injection of hydrogen might change this condensation behavior considerably. The in3uence of
hydrogen on the thermodynamics upon injection, on the Joule–Thomson e&ect at the pressure reduction stations, on the energy
density, on the Wobbe index, and on the pressure drop in the pipelines has been calculated. It has been shown that injection
of 25% hydrogen may lead to a temperature drop of several degrees, the temperature drop at the pressure reduction stations
reduces by 13 , and the pressure drop in the transport lines increases only slightly. Moreover, at 40 bar and 258 K the amount
of liquid condensate is slightly less in the case of hydrogen if the same amount of energy is transported.
? 2003 International Association for Hydrogen Energy. Published by Elsevier Ltd. All rights reserved.

Keywords: Hydrogen; Natural gas; Mixture; Thermodynamic properties; Transportation properties

1. Introduction Dutch universities and companies. One of the aspects is the

Hydrogen as an energy carrier has the potential to reduce
the impact of energy use on global climate change. The
use of hydrogen will enable the large-scale introduction of
durable energy, like hydro, solar and geothermal energy,
both for stationary and for transport systems. Also local
atmospheric pollutants, like NOx , CO, and particles, will be
reduced by the introduction of fuel cells.
However, in the transition period towards a hydrogen
economy, hydrogen will probably be obtained from other
sources, such as fossil fuels. Hydrogen production from
fossil fuels, particularly from natural gas, may prove to be
attractive. The wide availability of fossil fuels and the ma-
ture hydrogen production technologies for the conversion
of fossil fuels into hydrogen should permit hydrogen to be
produced at acceptable prices during this transition period.
The consequences of injecting hydrogen into the exist-
ing natural gas grid are being investigated by a number of
∗ Corresponding author. Fax: +31-20-5255788.
E-mail address: schouten@science.uva.nl (J.A. Schouten).
e&ect of the injected hydrogen on the behavior of the natural
gas in the transportation lines, in particular on the conden-
sation behavior of the heavy components. These e&ects are
related to both the temperature and pressure changes upon
hydrogen injection as well as to the change in composition.
This condensation requires continuous operational attention
of the gas companies and a positive e&ect of hydrogen might
a&ect the decision to introduce hydrogen.
First of all, there is a temperature e&ect at the point where
the hydrogen is injected in the gas stream. The e&ect is due
both to the mixing and to the expansion of the hydrogen. But
also the thermodynamic properties of mixtures of hydrogen
with natural gases may di&er considerably from those of the
natural gases. This will have consequences at various places
along the transportation lines. At the pressure reduction sta-
tions the temperature drop due to the Joule–Thomson e&ect
will be di&erent. As a consequence, the amount of energy
required to heat up the gas in order to avoid condensation
at the custody transfer stations will be di&erent. Secondly,
the energy density will decrease upon hydrogen injection so
that the pressure gradient along the pipelines should prob-
ably be higher in order to transport the same amount of

0360-3199/$ 30.00 ? 2003 International Association for Hydrogen Energy. Published by Elsevier Ltd. All rights reserved.
doi:10.1016/j.ijhydene.2003.11.003
1174 J.A. Schouten et al. / International Journal of Hydrogen Energy 29 (2004) 1173 – 1180
energy. On the other hand, the mixture may cause a pres-
sure drop in the pipeline di&erent from that in the case of
the natural gas since the properties are di&erent. Moreover,
the gas quality, characterized by the Wobbe index and the
caloriGc value, should be kept within rather narrow limits,
limiting the amount of hydrogen that can be injected. Fi-
nally, the phase envelope of the mixture will deviate from
that of the ‘pure’ natural gas and, therefore, the amount of
condensate at a particular temperature and pressure will be
di&erent.
2. Temperature change at injection of hydrogen
Injection of hydrogen in natural gas will probably be per-
formed in the same way as the usual injection of nitrogen in
natural gas, as is carried out by Gasunie (the Dutch trans-
portation company). Nitrogen is compressed to a pressure
that is several bars higher than the pressure of the natural gas
in the pipeline and is then injected in the natural gas stream.
This process is both an irreversible dynamical expansion of
the gas to be injected and a simultaneous irreversible mixing
of the gases.
It is assumed that the natural gas stream and the amount
of hydrogen to be injected are such that the process can be
considered to be adiabatic and that the pressure in the nat-
ural gas system will not change with injection of hydrogen.
As a model, consider a natural gas pipeline at a pressure
p1 and a temperature T (Fig. 1). A second pipeline is Glled
with hydrogen at the same temperature but at a pressure p2 ,
which is higher than p1 . Both gas volumes are connected
via a small hole and the whole system is in dynamical equi-
librium. The system is thermally isolated from the environ-
ment so that the process is adiabatic. One can imagine the
process to be separated into two processes. First, the hydro-
gen will expand. Work is done on the hydrogen system and
the system will do work on the environment. This is a Joule–
Thomson expansion but, since the system is far above the
inversion temperature of hydrogen, the temperature of the
system will slightly increase instead of the usual decrease.
So in this step both temperature and volume will increase.
Secondly, the hydrogen will mix with the natural gas. Since
it is not an ideal mixture, both the temperature and the vol-
ume will change during this process. In principle, the ef-
fect can be positive or negative, but, considering the inter-
molecular forces, a lowering of the temperature is expected.
Due to this temperature change the volume of the system
will decrease and the environment will do work on the
system.
The problem is to calculate the Gnal temperature because
only the Gnal pressure is known (p1 ) and not the Gnal vol-
ume. Therefore, an iteration procedure is needed. One has
to choose a relevant parameter set for the iteration and a
procedure to carry out the iteration. At Grst sight, it seems
logical to carry out Grst an irreversible adiabatic expansion
of the hydrogen from p2 to p1 and calculate the temperature
Fig. 1. Schematic representation of the mixing of hydrogen with
natural gas.
decrease of the hydrogen. Then, using the heat capacities of
both the natural gas and the hydrogen the equilibrium tem-
perature could be calculated. In the second step the gases
could be mixed at constant pressure. However, the second
step is the most complicated step and includes the iteration
procedure. Therefore, one can do the expansion and the mix-
ing in a single step as well.
The procedure we have developed is the following. The
choice for the iteration parameters is the set KV and KU ,
the change in total volume and total internal energy of the
system, respectively. These parameters are related by the
Grst law of thermodynamics, the conservation of energy.
First, the total internal energy and total volume of the system
at the starting conditions (Fig. 1) are calculated. A Grst
estimate is made of the change in total volume and in total
energy of the system by carrying out both the mixing of
the gases and the hydrogen expansion to p1 in one step at
constant temperature. A volume V2 of hydrogen (at p2 ) is
needed to bring a volume V1 of natural gas at the required
composition. According to the Grst law
KU = KQ + KW; (1)
where KW is the work done on the system. The process is
assumed to be adiabatic thus
KU = KW: (2)
The total work done on the system is
KW = (P2 − P1 ):V2 − P1 :KVtotal (3)
with KVtotal = KVexpansion + KVmixing :
The calculated values of KU and KW are, in general, not
equal in the Grst step. The temperature is then changed and
the procedure is repeated until the relative value of the dif-
ference between KW and KU is less than 10−3 . A computer
program for the above procedure has been developed. For
the equation of state of the natural gas and the hydrogen the
AGA8-DC92 equation has been taken [1].
The temperature e&ect has been calculated for 10 and
25 mol% H2 injection in a lean gas (82.5% CH4 , 11.7%
N2 , 1.1% CO2 , 3.5% C2 H6 , 0.75% C3 H8 , and balance C¿3 ),
which is commonly used in the households in the Nether-
lands, and a rich gas (85.5% CH4 , 0.5% N2 , 1.8% CO2 ,
 J.A. Schouten et al. / International Journal of Hydrogen Energy 29 (2004) 1173 – 1180
Table 1
Temperature decrease at H2 -injection
Pressure (bar) 67 (77) 67 (67) 40 (50) 8 (18)
Lean gas
10 mol% 2:63 K 2:65 K 1:44 K 0:23 K
25 mol% 5:50 K 5:56 K 3:02 K 0:48 K
Rich gas
10 mol% 3:92 K 3:94 K 2:04 K 0:32 K
25 mol% 8:18 K 8:24 K 4:29 K 0:67 K
8.5% C2 H6 , 2.7% C3 H8 , and balance C¿3 ), often used in
industry. The calculations have been performed for 280 K
and three pressures corresponding with the pressures in the
main transportation lines, the regional net, and the low pres-
sure distribution net. In Table 1 some of the results are
presented. In the Grst row the pressure in the pipeline is
given, while the pressure of the hydrogen to be injected is
denoted in brackets. The temperature decrease varies from
a few degrees at the highest pressure to only a few tenths
of a degree at 8 bar. The e&ect is nearly proportional to
the H2 concentration for low concentrations (not shown in
Table 1) but slightly less than proportional for larger H2
fractions. To study the variation with temperature some cal-
culations have been performed at 300 K. The temperature
e&ect is less at higher temperatures: e.g. 5:5 K for the lean
gas with 25 mol% H2 at 280 K and 4:6 K at 300 K. A com-
parison of the results of the lean and the rich gas shows that
the e&ect is larger for the higher caloriGc gas. Calculations
have also been made for a hydrogen injection pressure equal
to that of the natural gas. In Table 1 the results are only
given for the highest pressure. It is shown that the result
is nearly independent of the (over) pressure of the injected
gas.
The results can be explained in the following way. Let
us assume that the natural gas is pure methane. If hydro-
gen is injected the hydrogen molecules will interact with
the methane molecules and destroy some of the methane–
methane interactions. Since the hydrogen–methane interac-
tion is relatively small the potential energy of the system
will increase and, therefore, the kinetic energy and thus the
temperature will decrease if the mixing is adiabatic. At low
pressures the number of collisions is much less and so is the
temperature decrease. The same holds for higher tempera-
tures because the density is less. In the rich gas the con-
centrations of the higher hydrocarbons, which have a more
negative interaction energy, is larger resulting in a larger
temperature e&ect.
At 280 K a Joule–Thomson expansion of hydrogen from
70 to 60 bar will result in a temperature increase of about
0:35 K. Since the heat capacity of the natural gas is much
larger than that of hydrogen, the e&ect will be very small
in the mixture. There is a small di&erence between the lean
and the rich gas due to the slightly higher heat capacity of
1175
the rich gas. Thus, the (over) pressure of the hydrogen is
not relevant for the temperature e&ect.
In some cases rich gas is mixed with lean gas. To keep
the Wobbe index, deGned as the ratio of the gross caloriGc
value to the square root of the relative density at 1.01325
bar and 273:15 K (STP), at the required value, nitrogen is
injected into the natural gas. Calculations have been made,
using the above procedure, for nitrogen injection into the
same natural gases and under the same conditions of tem-
perature and pressure. In general the tendency is the same
as in the case of hydrogen injection but the e&ect is about
45% that of hydrogen. The explanation is also similar with
one di&erence. For nitrogen a Joule–Thomson expansion re-
sults in a small temperature decrease, not an increase, e.g.,
expansion of nitrogen at 280 K from 70 to 60 bar gives a
temperature decrease of about 1:9 K.
3. Energy density
Since the heating value of a mole of hydrogen is about 13
that of a mole of methane, the energy density of natural gases
decreases if hydrogen is injected. As will be discussed later,
sometimes nitrogen might be injected simultaneously with
hydrogen to get a prescribed value for the Wobbe index. In
Table 2 results are presented for the lean gas at 40 bar and
280 K. The third column gives the energy density relative
to that of the lean gas. Since the objective is to reduce the
emission of CO2 , the last column gives the amount of carbon
dioxide produced per MJ. The second row gives the values
if the mole fraction of hydrogen is 0.1. To keep the Wobbe
index constant the amount of nitrogen should be reduced by
about 2.5%. The last row gives the values for the lean gas
mixed with hydrogen if the Wobbe index is not kept con-
stant by reducing the amount of nitrogen. The table shows
that in both cases the e&ect is non-negligible. Injection of
10 mol% hydrogen requires a 9% higher 3ow rate to trans-
port the same amount of energy. Therefore, the pressure in
the pipelines has to be increased. On the other hand, the vis-
cosity and, more important, the compression factor change
which also in3uence the pressure drop in the pipelines. The
overall e&ect will be discussed below in the section about
the pressure drop in the pipelines.
Table 2
E&ect on the energy density, N2 concentration, and CO2 emission
of 10% hydrogen in the lean gas at 40 bar and 280 K
Wobbe Energy N2 CO2
index density (%) (g/MJ)
Lean gas 45.55 1.00 11.73 50.86
10% H2 45.55 0.93 9.18 48.97
(Wobbe equal)
10% H2 44.61 0.92 10.55 48.96
1176 J.A. Schouten et al. / International Journal of Hydrogen Energy 29 (2004) 1173 – 1180

4. Joule–Thomson e ect at pressure reduction stations
In the Netherlands Gasunie transports the gas in the main
transport lines under high pressure, from 70 to 40 bar. Via
pressure reduction stations it is distributed to the regional
pipelines where the pressure varies from 40 to 16 bar. Fi-
nally, it is transferred to the local net at a pressure less than
8 bar. At the pressure reduction stations the temperature of
the gas drops due to the expansion and, in many cases, heat
must be supplied to prevent condensation of the heavy hy-
drocarbons. To heat at constant pressure one cubic meter
of lean gas (at STP) 1:84 kJ=K is needed and for rich gas
2:07 kJ=K. The pressure drop from the main transport lines
to the regional pipelines may be as large as 20 bar, e.g., from
60 to 40 bar. In some cases even the pressure drops from
65 to 8 bar. In Table 3 a few examples are given for the
in3uence of hydrogen on the temperature drop. The mole
fraction of hydrogen is taken to be 0.25
The table shows that the addition of hydrogen has a
considerable e&ect on the temperature drop and thus on
the amount of heat needed to avoid condensation. If the
gas contains 25 mol% hydrogen, the temperature decrease
is about two-third the temperature drop in the gas without
Table 3
E&ect of 25% hydrogen in the lean gas on the temperature drop
KT at pressure reduction stations
hydrogen. Although the temperature drop in the rich gas is
clearly larger, there is no essential di&erence between the
lean and the rich gas with respect to the relative change.
Also some values for 290 K are presented. The results are
similar.
5. Wobbe index
Injection of hydrogen into the natural gas a&ects the
Wobbe index. The Wobbe index of hydrogen (48.3) is
higher than that of lean gas (45.5) but lower than that of
the rich gas (54.4). One might expect that adding hydrogen
would increase the index of lean gas but this is not the case
for small mole fractions of hydrogen. In Fig. 2 the Wobbe
index is presented as a function of mole percent of hydro-
gen. The curve shows a minimum at about 75 –80 mol%.
Injecting 10 mol% hydrogen in the lean gas lowers the
Wobbe index from 45.5 to 44.6. Since the curve is very
steep at the hydrogen rich side, the index for hydrogen
is very sensitive to impurities. The behavior of the curve
for rich gas is similar. The shape of the curves can be ex-
plained as follows. Both the gross caloriGc value and the
relative density are linear functions of the mole fraction of
hydrogen. However, the Wobbe index is inversely propor-
tional to the square root of the density and this produces the
curvature.

Gas Temperature (K) p1 (bar) p2 (bar) KT

Lean 280 60 40 9.5

30 8 11.3
8 1 3.6
60 8 27.6

290 60 40 8.8
30 8 10.5
8 1 3.3
60 8 25.3

Lean+H2 280 60 40 5.8

30 8 7.0
8 1 2.3
60 8 16.5
290 60 40 5.4

Rich 280 60 40 12.1

30 8 14.2
8 1 4.4
60 8 35.9

290 60 40 11.1

Rich+H2 280 60 40 7.2

30 8 8.8
8 1 2.8
Fig. 2. The Wobbe index as a function of the hydrogen mole
60 8 20.8
fraction for a rich and a lean gas.
 J.A. Schouten et al. / International Journal of Hydrogen Energy 29 (2004) 1173 – 1180 1177

Table 4
Pressure decrease Kp over 90 km and velocity of the gas (at the
end of the pipeline) in a pipeline with a diameter of 1:04 m

T (K) p Kr :106 :106 Q Kp v

(bar) (m) (Pa.s) (m3 =s) (bar) (m/s)

Lean gas
280 65 12 12 425 11.9 8.7
15 12 12.3 8.8
12 24 12.3 8.8
290 12 12 12.7 9.3

Lean+25%H2
280 65 12 12 508 14.6 11.7
425 9.9 8.9
67.1 508 14.0 11.1

Rich gas
280 65 12 12 425 11.3 8.1

Rich+25%H2
280 65 12 12 518 15.1 11.8
425 9.8 8.7
67.9 518 14.2 10.9

Kr is the roughness,  the dynamic viscosity, Q the 3ow rate

Fig. 3. The nitrogen mole fraction, needed to keep the Wobbe index
at 43.7, as a function of the amount of hydrogen for three gases.
In the Netherlands the Wobbe index has to be maintained
within the limits 43.4 and 44.4 for the households. Most of
the gases have a much higher Wobbe index and have to be
mixed with nitrogen to satisfy these limits. If hydrogen is
injected less nitrogen is needed, thus in that case the Wobbe
index can be kept constant by adding nitrogen simultane-
ously with the hydrogen. In this way, a substantial reduction
of the production of nitrogen is possible, saving also en-
ergy. For a few gases the nitrogen mole fraction (including
the nitrogen already present in the gas), needed to keep the
Wobbe index at 43.7, is given as a function of the amount
of hydrogen in Fig. 3.
6. Pressure drop in the pipelines
The 3ow of a 3uid in a pipeline is governed by the
well-known Navier–Stokes equation. If we consider a sta-
tionary state and neglect the in3uence of gravitation on the
3ow, the equation reduces to an equation which is usually
used for the calculation of the pressure drop dp along a
length d x of the pipeline of internal diameter D [2]:
dp = −0:5:v2 ::d x=D; (4)
where  is the mass density of the gas at the pressure and
temperature in the pipeline, v is the average velocity of the
gas (at the prevailing conditions) and  is the friction factor.
(referred to STP) and p the pressure at the starting point.
Integration of the above equation gives the pressure drop
over a Gnite length of the pipeline. The friction factor de-
pends on the Reynolds number deGned by
Re = :v:D=; (5)
where  is the dynamic viscosity at the pressure and tem-
perature in the pipeline. Note that if  is taken constant, Re
is also constant along the pipeline. One also needs the value
for the roughness Kr , the average height of the protrusions,
of the pipeline. For highly turbulent 3ows (Re ¿ 106 ) the
friction factor  can then be calculated from the equation:
1=0:5 = −2 log[2:51=(Re:0:5 ) + Kr =(3:71D)]: (6)
It is further assumed that the temperature is constant along
the pipeline. In Table 4 results are presented for a practical
example. The gas is transported over a distance of 90 km
with an initial pressure of 65 bar. The 3ow rate is 425 m3 =s
(STP) and the diameter of the pipe is 1:04 m. This results in a
very high Reynolds number, accounting for highly turbulent
3ow. The calculations have been performed for a lean and a
rich gas and for these gases with 10 and 25 mol% hydrogen.
The e&ect of temperature, viscosity and friction factor has
also been determined. The Grst and second row give the
temperature of the pipeline and the initial pressure, the third,
fourth and Gfth rows the roughness, the viscosity, and the
3ow rate (referred to STP), the sixth row gives the pressure
drop over 90 km and the last row the velocity of the gas at
the end point.
1178 J.A. Schouten et al. / International Journal of Hydrogen Energy 29 (2004) 1173 – 1180
As mentioned before, the energy=m3 is less for the hydro-
gen containing gases than for the natural gas. At 273:15 K
and 1:10325 bar the energy of the lean gas is 36:56 MJ=m3 ,
with 25 mol% H2 30:58 MJ=m3 . As a result, to transport the
same amount of energy the 3ow rate for gas with hydro-
gen should be 508 m3 =s. For the rich gas the energy at STP
is 44:22 MJ=m3 , with 25 mol% 36:31 MJ=m3 . Therefore, in
the last case the 3ow rate should be 518 m3 =s.
The table shows that an uncertainty in the viscosity of
100% results in an uncertainty of the pressure drop of about
3%. It turns out that this change is almost independent of
the composition of the gas, which is generally the case for
turbulent 3ow. It should be noted, that at lower Reynolds
numbers (lower 3ow rates), the dependency on the viscosity
is larger. In that case, however, pressure drops along the
pipelines are insigniGcant as compared to those of the highly
turbulent 3ows. Therefore, the e&ect of the viscosity can be
neglected. Increase of the temperature by 10 K increases the
pressure drop by about 6% also for the gases with hydrogen.
This is due to the fact that to transport the same amount
of energy a larger volume is needed at higher temperatures.
The e&ect of the Kr factor is also relatively small, although
it must be noted that this factor can change in time. An
increase of Kr by 25% gives an increase of the pressure drop
of about 3%.
The table also shows that the pressure drop in the rich
gas is less than in the lean gas. Given an equal 3ow rate,
with the amount of m3 =s referred to STP, the density of the
rich gas is higher at the prevailing conditions in the pipeline
but the velocity is smaller than that of lean gas. Moreover,
in the equation for the pressure drop (4) the velocity is
squared.
If we like to discuss the e&ect of hydrogen on the pressure
drop, there are several possibilities. Do we compare the lean
gas with, e.g., the lean gas mixed with 25% hydrogen at
the same 3ow rate, at the same end pressure, with the same
energy 3ow, with the same pressure drop, or a combination?
Probably the best comparison is to keep the energy 3ow
and the pressure at the end of the pipe the same. Table 4
shows that, starting at 65 bar, the pressure drop of the lean
gas increases by 2:7 bar over 90 km if 25 mol% hydrogen
is added. In the case of the rich gas it is 3:6 bar. It can be
noted that if one likes to have the same pressure at the end
of a pipeline with a length of 90 km, the initial pressure
should be 2.1 or 2:9 bar higher, respectively.
In all cases the mean velocity of the gas in the pipeline
is far below the maximum accepted value of 20 m=s.
7. Vapor–liquid equilibrium
Intuitively one would expect vaporization of the liquid
phase of a mixture if the pressure is decreased or the tem-
perature is increased. However, under special circumstances
the reverse might happen. This phenomenon is called retro-
grade condensation and occurs at temperatures (far) above
the critical temperature of the mixture. Retrograde conden-
sation is an important cause of hydrocarbon liquid dropout
in the transport lines at pressure drops.
Calculation of the phase behavior of natural gases is very
complicated due to the presence of the heavy hydrocarbons,
in particular those with a carbon number between eight and
12, as shown by Voulgaris [3]. Experiments have been per-
formed to get information about the solubility of the light
component of a natural gas in the heavy hydrocarbons [3,4].
It turned out that the in3uence of N2 , C2 H6 and CO2 on the
solubility of CH4 in decane is within experimental accuracy
the same for all these gases in the retrograde region and
at lower pressures. Calculations with the Peng–Robinson
equation of state were in good agreement with these
results [3].
Injection of hydrogen increases the complexity because
of the highly asymmetric nature of hydrocarbon–hydrogen
mixtures. In recent years several e&orts have been made to
model these mixtures with a cubic equation of state [5–11].
Except near the critical temperature of the mixture, good re-
sults were obtained for the vapor–liquid equilibria curves of
binary systems. One of the problems is that the  function
in the well-known Soave–Redlich–Kwong and the Peng–
Robinson equations of state (EOS) is not constructed for
temperatures far above the critical temperature. Some inves-
tigators tried to avoid this problem by constructing other 
functions [5,6,11] and/or mixing rules [5,7,8,10,11]. Others
developed correlative methods relating the interaction coef-
Gcients kij of the various hydrogen–hydrocarbon mixtures
[8,9,11]. It turns out that the results for the vapor–liquid
equilibrium of binary hydrogen–hydrocarbon mixtures are
not very sensitive to the values of kij [9,11]. They are more
sensitive to the repulsion parameter, but calculations showed
that the results did not improve substantially by introducing
new complicated mixing rules for the repulsion parameters
[9].
Therefore, it seems reasonable to expect that calculations
with the PR-EOS will give a good approximation for the
in3uence of hydrogen on the phase behavior of a natural gas.
The well-known Aspen program has been used. Since we
are interested in the change in phase behavior of a natural
gas if hydrogen is added, calculations have been made both
for a natural gas and this natural gas mixed with hydrogen.
The natural gas is a lean gas (CH4 81%, N2 14%, C2 H6 3%,
CO2 1%, C3 H8 0.4%, C4 ::C12 ). The amount of hydrogen
added is 20 mol% so that the mole fraction of hydrogen is
0.167 and the mole fractions of the other components are
all reduced by 16.7%. The calculations of the vapor–liquid
equilibrium have been performed for a pressure of 40 bar
and at a temperature of 258 K. To get a suQcient amount
of liquid the temperature has been assumed rather low. This
makes a more detailed analysis of the compositions of the
liquid and gas phase possible.
The Aspen program has built-in a number of interaction
parameters kij for hydrogen with the components of the nat-
ural gas. These parameters are given in Table 5.
 J.A. Schouten et al. / International Journal of Hydrogen Energy 29 (2004) 1173 – 1180 1179

Table 5 As shown, the energy density of a natural gas mixed with

Values for the unlike interaction parameters kij for binary mixtures hydrogen is smaller than that of the natural gas. To transport
of hydrogen with the components of a natural gas the same amount of energy about 18% more cubic meters
System kij System kij must be transported in the above example (40 bar; 258 K).
Therefore, the di&erence in the amount of condensate in the
H2 –CH4 0.0156 H2 –C7 H8 −0.510 transport line is only a few percent in favor of the gas with
–C2 H6 −0.0667 –C7 H16 −0.1167 hydrogen. One should realize, however, that the exact value
–C3 H8 −0.0833 –N2 0.103 depends not only on the temperature and pressure but also
–C4 H10 −0.397 –CO2 −0.1622
on the speciGc composition of the gas.
–C6 H14 −0.0300
It is also interesting to compare the mole fractions of the
gas phase in the two cases. It turns out that the mole fraction
of the light components reduce to about 83% by adding the
hydrogen. A deviation occurs with the heavy hydrocarbons:
Table 6
Amount of the natural gas components dissolved in the liquid phase C8 80%, C9 77%, C10 73%, C11 69% and C12 65%.
for the hydrogen-natural gas mixture relative to that in the case of
the natural gas without hydrogen
8. Conclusions
Component (%) Component (%)

C1 65 Toluene 82 When adding hydrogen to a natural gas, a number of

C2 69 C8
C3 72 C9
Benzene 81 C10
C7 84 C11
Based on the amount of hydrogen in the gas phase
(16.7%), a Grst rough estimate of the amount of the natural
gas components in the liquid phase would be 83.3% of that
in the case of the natural gas without hydrogen. In Table 6
the results of the calculation are given for the ten largest
contributions.
In addition it can be noted that hydrogen hardly dissolves
in the liquid phase, that the contributions of N2 and CO2 to
the amount of liquid are small, and that the numbers for ni-
trogen and carbon dioxide are 65% and 68%, respectively
(not in the table). In this respect nitrogen and carbon diox-
ide behave similar to methane. The experimental results for
binary systems of Refs. [12,13] are conGrmed in the sense
that the solubility of methane in the liquid is much higher
than that of hydrogen and nitrogen, but much smaller than
that of carbon dioxide. The solubility of hydrogen in the
liquid is less than that of nitrogen. The experimental results
also show that the solubility does not depend very much on
the length of the hydrocarbon chain.
The calculations show that the number of condensed
moles per cubic meter of gas of all the components de-
creases if hydrogen is added. The reduction is larger than
16.7% for the light natural gas components, in particular
methane, and only slightly less than 16.7% for the heavy
hydrocarbons (see Table 6). On the average the reduction
of the amount of liquid is 22%, more than the concentration
of hydrogen. Since the mole fraction of methane in the gas
phase is large, this is largely due to methane. As a result
the density of the liquid is slightly higher. The reduction in
the weight of the liquid is 21%.
88 changes take place in the thermodynamic properties that are
86 of interest for the transportation of the gas.
84 At the injection of hydrogen in the main transportation
84 lines the temperature drops several degrees. The e&ect is
twice as large as with the injection of nitrogen. The tem-
perature drop in the pipelines at the pressure reduction sta-
tions is reduced by about 13 if the natural gas contains 25%
hydrogen, thus reducing substantially the amount of energy
needed at the custody transfer stations to heat up the gas.
Of course, the energy density decreases if hydrogen is
added and this should be taken into account in all calcula-
tions. It is also shown that, although the Wobbe index of
hydrogen is higher than that of the lean gas, injection of hy-
drogen up to about 75% reduces the Wobbe index, as in the
case of the rich gas. This e&ect of hydrogen on the Wobbe
index also implies that the injection of nitrogen, as is gen-
erally applied in the Netherlands for obtaining a gas with
a low Wobbe index, can be partially replaced by injecting
hydrogen.
The pressure gradient in the pipelines is larger in the case
of the natural gas than in the mixture containing hydrogen
if the same amount of gas is transported on a volumetric
basis but less on an energy basis. On an energy basis the
pressure decrease in the main transport lines over a distance
of 100 km is a few bars more for the natural gas containing
25% hydrogen.
Calculations of the vapor–liquid equilibrium at 40 bar and
258 K show that the amount of condensate in the transporta-
tion lines is a few percent less in the hydrogen mixture if the
same amount of energy is transported. This is mainly due to
a reduction of the amount of methane dissolved in the liquid.
Acknowledgements
This project is supported with a grant of the Dutch Pro-
gram EET (Economy, Ecology and Technology) a joint
1180 J.A. Schouten et al. / International Journal of Hydrogen Energy 29 (2004) 1173 – 1180
initiative of the Ministries of Economic A&airs, Education,
Culture and Sciences and of Housing, Spatial Planning and
the Environment. We thank Prof. Boesten for teaching us
the use of the Aspen program.
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