MEASUREMENTS AND MODELLING OF HYDROCARBON DEW POINTS

FOR NATURAL GASES”

Background and objective

The knowledge of the hydrocarbon dew point (HCDP) is of great importance for the
oil & gas industry as it is one of the gas quality specifications used for ensuring safe
transport of natural gas.

Avoiding hydrocarbon condensation is crucial as the presence of liquids in the

pipelines increases the pressure drop and introduces operational problems in pipelines
designed for single phase transportation. Thus, accurate measurement and prediction
of hydrocarbon dew points are of great importance to obtain a safe and effective
utilization of the natural gas pipelines.

At the laboratory facilities of Sasol in Temane a new model Fluid Modelling Group
(FMG) for measuring hydrocarbon dew points for natural gases is available. We are
currently evaluating the effect of various factors, such as the filling procedure, the
chamber temperature and the conditioning of the gas samples in the accuracy of the
measurements.

Prediction of hydrocarbon dew point data in the oil & gas industry is usually done by
thermodynamic models, such as traditional equations of state (EoS), like SRK and PR.
Previous studies pointed out that classic EoS had difficulties in correctly representing
the dew point line for natural gases, while more advanced models, such as the Fluid
Modelling Group(FMG) significantly improve the predictions.

The following tasks are to be considered:

1. Literature review: Challenges with experimental determination and modelling of

the HCDP for natural gases

2. Measurement of HCDP in the FMG. Effect of various factors such as the filling
procedure and the chamber temperature.
3. Proposal of an operating procedure for reliable HCDP measurements in the FMG.

4. Modelling of hydrocarbon dew points with classic EoS and other models such the
Daniels GC.

Abstract

The knowledge of the hydrocarbon dew point (HCDP) is of great importance for the
oil and gas industry as it is one of the gas quality specifications used for ensuring safe
transport of natural gas. Avoiding hydrocarbon condensation is crucial as the presence
of liquids in the pipelines increases the pressure drop and introduces operational
problems in pipelines designed for single phase transportation.

Thus, accurate measurement and prediction of hydrocarbon dew points are of great
importance to obtain a safe and effective utilization of the natural gas pipelines.

At the laboratory facilities of Sasol in Temane new model (FMG) for measuring
hydrocarbon dew points for natural gases is available. Hydrocarbon dew points were
measured in order to study the effect of various factors on the accuracy of the HCDP
measurement and, therefore, perform the qualification of the GERG rig.

Hydrocarbon dew points are usually predicted using thermodynamic models, such as
traditional cubic equations of state, like Soave-Redlich-Kwong (SRK). Previous
studies have pointed out that classic EoS are not able to correctly represent the dew
point line for natural gases, while more advanced models, such as the FMG,which is
the Fluid Modelling Group give significantly improved predictions.

In this Master thesis, hydrocarbon dew point measurements have been performed for
two synthetic gases and one real gas. Several experiments have been conducted in
order to study the effect of the volume of the sample gas, the chamber’s temperature
and the sample conditioning. The results show that there is no volume effect or effect
of the sample conditioning. On the other hand, at 10°C difference of the chamber’s
temperature from 35 to 45 °C has an effect of approximately 0.9 °C on the measured
dew points. Given the fact that there is adsorption of heavy hydrocarbons inside the
rig, which is a known challenge in HCDP measurements, the effect is more
pronounced in gases consisting of heavier compounds, as in the case of the real gas.

The dew point experimental data are used to evaluate the reliability of three
thermodynamic models: Dalniels GC, Laboratory results and FMG. All three models
studied appear to yield satisfactory results. Daniels GC and Laboratory’s predictions
are very similar at low pressures up to the cricondentherm temperature, while Daniels
GC is better than Laboratory at higher pressures.

Both these models describe better the experimental data obtained from the synthetic
gases than FMG, except from the high pressures, and especially the cricondenbar
pressure, where FMG gives the best results.

Furthermore, the real gas’ dew point curve is adequately predicted by FMG, which
yields the best predictions than the other two models. Finally, an uncertainty analysis
is performed which further confirms the reliability of the FMG model.

1. Introduction
Natural gas is a hydrocarbon mixture consisting primarily of methane CH4 (70-90%
v/v) and other hydrocarbon such as ethane, propane and butane. Non-hydrocarbon
impurities such as H2O, CO2, N2, H2S can also be found in small amounts. Natural gas
is the cleanest fossil fuel and can be used everywhere, from households to energy
high-demanding industries. This is the reason why natural gas pipeline networks have
been developed for the transportation of the gas throughout the world [1].

The knowledge of the hydrocarbon dew point (HCDP) is of great importance for the
oil and gas industry. Natural gas pipelines are designed for single-phase transportation
and, therefore, hydrocarbon condensation could have severe consequences for the safe
transportation of the gas. In order to assure an effective utilization of the natural gas
pipelines, accurate measurement and prediction of hydrocarbon dew points is
necessary.

At the laboratory facilities of Sasol in Temane, an apparatus for measuring

hydrocarbon dew points, named FMG, is available. The objective of this Master thesis
is the study of various factors affecting the accuracy of the hydrocarbon dew points
and, therefore, the qualification of FMG for future measurements.

Adsorption phenomena are a known challenge in dew point measurements and have
been studied in order to determine their effect on the measured dew points [2]. This
study, which was performed using another dew point model, in the frame of a master
thesis also, showed the presence of adsorption and suggested the building of a dew
point rig with less adsorbing material (GERG rig). Adsorption of the heavy
compounds of the mixture leads to a change of the composition of the gas and,
therefore, inaccurate measurements. The presence of adsorption inside GERG rig is
investigated through the study of the parameters affecting the accuracy of the
measured dew points.

Hydrocarbon dew point measurements have been conducted for two synthetic natural
gases and one real. The first synthetic gas is a binary mixture of methane and
n-heptane whereas the second consists of nitrogen, carbon dioxide and hydrocarbons
from methane up to n-octane. The real gas is actually a rich gas that contains nitrogen
and carbon dioxide as well as hydrocarbons up to n-decane.

In the oil and gas industry, thermodynamic models are used for the prediction of the
phase envelope. Such models are both traditional cubic equations of state (EoS) and
more advanced models. To evaluate the accuracy of these models, experimental data
are required.

In this work, the measured hydrocarbon dew points are used to evaluate three models:
SRK and PC-SAFT equations of state as well as the UMR-PRU model that belong to
the class of the so-called EoS/GE models.

In order to study the effect of the adsorption phenomena on the dew point
measurements various operational parameters of the rig, related to adsorption, were
examined. The parameters examined are:

 the volume of the gas used for each measurement,

 the temperature applied inside the chamber of the rig and
 the gas sample conditioning.
First, the theoretical background regarding the phase envelopes and the methods of
measuring and determining the HCDP will be presented. Chapter 3 consists of the
experimental work performed. The dew point measurements will be presented and
discussed. The results from modelling work together with an uncertainty analysis are
presented in Chapter 4. Finally, some concluding remarks and proposals for future
work will be given.

2. Theoretical Background

This chapter present the theoretical basis required for the study of natural gas’
thermodynamic behavior and its depiction on phase envelopes. In addition, a brief
overview of the methods used in order to measure or determine the dew point of
multi-component systems, such as natural gas, is performed, emphasizing to the
methods being used in this work. Adsorption is a known challenge in dew point
measurements and, therefore, adsorption theory is also presented.

2.1. Phase Envelope – HCDP

The thermodynamic behavior of natural gas is depicted on phase envelopes. A phase

envelope indicates the thermodynamic behavior of a multi-component system, such as
natural gas, and the conditions (pressure and temperature) where the different phases
of the mixture occur. A typical phase envelope of natural gas is presented on Figure
2.1.
P-T diagram for a typical natural gas

The critical point for a multi-component system is the common point between the
bubble point curve (the line of saturated liquid-100% liquid with a trace of vapor, on
the left of the critical point) and the dew point curve (the line of saturated vapor-100%
vapor with a trace of liquid, on the right of the critical point). It is the point for which
liquid and vapor phases are indistinguishable. Outside the curve, there is a singlephase
behavior: a liquid phase above the bubble point curve, a vapor phase above the dew
point curve and a dense phase above critical point.

Inside the curves, there is a two-phase region. The highest temperature and pressure at
which liquid and vapor coexist are called cricondentherm (CCT) and cricondenbar
(CCB) respectively [7]. The knowledge of the CCT and CCB and the dew point curve
is crucial for the natural gas’ safe transportation. The hydrocarbon dew point is
universally used in the natural gas industry as an important quality parameter,
stipulated in contractual specifications and enforced throughout the natural gas supply
chain, from producers through processing, transmission and distribution companies to
final end users.

The two-phase region to the right of the critical point is called retrograde region as a
different behavior of the mixture is met. Inside the curve, each one of the existing
lines represents a stable percentage of the liquid phase by volume. The critical point is
the boundary of the two phases where their thermodynamic properties are the same.
Consider we are in the vapor phase and in a temperature greater than the critical and
lower than the cricondentherm. As we are entering the two-phase region, with a
pressure decrease, we will start to produce some liquid. But, there will be a point (of
maximum liquid quota) where that liquid will start to vaporize. In other words, even
though we are compressing the system, liquid will vaporize and not condense. The
dotted line AB in Figure 1 inside the retrograde region indicates the maximum
volume ratio liquid/vapor met at a specific temperature. As the pressure drops the
mixture becomes richer in liquid phase until the horizontal dotted line – from then on,
the vapor phase becomes richer until 100% vapor is reached.
Figure 2.2 illustrates a typical vapor-pressure-liquid (VPL) diagram for
multi-component mixtures which shows how the liquid volume of the mixture
changes with pressure. As it can be noticed, for an isothermal increase of the pressure,
the percentage of the liquid phase increases until a maximum quota. From then on, the
liquid that has been formed starts to vaporize, thus the curve declines.

The shape of the phase envelope is defined by the composition of the mixture as it is
the one that defines its thermodynamic behavior. In order to study the effect of the
composition on phase envelopes, the composition of natural gas is theoretically
divided into two main categories: the light fraction (methane to hexane) and the
heptanes plus (C7+) fraction (heavy). Certainly, the non-hydrocarbons (carbon
dioxide, nitrogen etc) form another fraction [9]. The C7+ fraction is very important
for the dew point measurements since they are the heavy hydrocarbons that are
adsorbed inside the dew point apparatus.

The heptanes plus fraction is used to simplify the composition of natural gas in case
there is significant number of heavy components. The characterization of C7+ fraction
is essential when using equations of state. According to the properties of all the heavy
components as a whole, usually several heptane plus components are used, called
pseudo-components to best describe the behavior of the C7+ fraction [10].

The amount and properties of the C7+ fraction has significant effect on the phase
envelope of natural gas and especially in the dew point line. By using Peng-Robinson
Equation of state, the impact of the C7+ fraction on the phase envelope of natural gas
has been studied. The composition of the natural gas used for characterization in this
case is shown in Table 2.1.
 Composition of natural gas used to study the effect of C7+ fraction

Figure 2.3 shows the calculated with PR EoS phase envelopes for different
characterizations of C7+ fraction. It is noticed that as the molecular weight of the C7+
fraction increases, the shape of the phase envelope extends. Specifically, the critical
point moves slightly to the left while the cricondenbar and cricondentherm increases.