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HYDRATE PREVENTION IN SUBSEA NATURAL GAS

PRODUCTION

TPG4510 Petroleum Production Specialization Project

by
Moses Gideon Akpabio

Faculty of science and Technology


Institute of petroleum Technology (IPT)
Department of Petroleum Engineering and Applied Geophysics

NTNU
Norwegian University of
Science and Technology

JULY, 2012

Acknowledgement
This piece of work would not have been possible without the help and contributions of
others. I hereby seize this opportunity to appreciate these people for their assistance
whenever I found myself in doubt of what to do and how to do it.
My profound gratitude goes to my supervisor, Professor Jon Steinar Gudmundsson for his
understanding and assistance on defining this project work, his guidance, and all useful links
he sent to me while here in Nigeria that have make this final result possible. I also appreciate
the way he accepted me as his student, his advice and answers to all of my questions. I
equally acknowledge the support of Associate Professor Pal Skalle as well as the Norwegian
government for sponsoring the EnPE/NORAD programme.
I also appreciate my friends and colleagues, especially Mr. Samson Imoh, and others, whose
suggestions and inputs have enhanced my motivation in finishing this project work.
However, I acknowledge the works of several authors as well through which I have gained a
lot of new ideas for this project work.
I deeply appreciate the creator of the universe for His mercies, love and for this wonderful
opportunity. And, my Parent and siblings are well acknowledged for their respective
contributions to my life.

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Abstract
Subsea production of oil and gas is always faced with the potential problem of hydrates
formation which causes pipeline blockage, damage of pipeline fittings, and other related
problems. A reliable method that has the ability to predict hydrate formation conditions
during the production process, and transmission is thus needed. It is important to ensure
safe operations.
In this work, water concentration estimation for the conditions prevailing at the reservoir,
the wellhead and the receiving terminal on land are evaluated analytically based on
theoretical approach. As an example, a natural gas stream from Nigeria with pipeline as a
transmission medium is used. The temperature profile and pressure profile along this
pipeline have also been used as an input in the evaluation of hydrate formation. Also, a
hydrate inhibition strategy with MEG is considered. Results show that the flow is within the
hydrates forming region, since the temperature is below 20 oC and pressure, above 100 bara.
Water concentration estimation provides useful information which can assist in prevention
of hydrate formation as gas flows through a pipeline. The temperature profile and pressure
profile also provide useful information for the management or controlled of hydrates
formation as the temperature and pressure data can indicate the thermodynamic conditions
that favours hydrates formation.

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Table of Contents
Title

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Acknowledgement. .

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Abstract.

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Table of Contents.

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List of Tables. .

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List of Figures. .

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1. Introduction.

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2. Natural Gas: A Closer Look.


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2.1 Brief History of Natural Gas. .

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3. Natural Gas Hydrate.


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3.1 Structures of Gas Hydrates. .
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3.2 Conditions Necessary for Formation of Hydrates. .
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3.3 Gas Hydrate Prevention.
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3.3.1 Hydrates Prevention with Inhibitors.
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3.3.2 Selection of Hydrate Prevention and Remediation Strategies.
3.4 Hydrates Prevention Using MEG.
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4. Water Content of Natural Gas.

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5. Empirical Correlations and Calculation Methods.

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5.1 Water Content of gas stream .


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5.2 Temperature Profile. .
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5.2.1 Necessary Equations and Variables.
5.2.1.1 Heat Capacity Estimation. .
5.2.1.2 Mass Rate. .
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5.3 Pressure Profile.
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5.3.1 Necessary Parameters and Equations.
5.3.1.1 Reynolds Numbers. .
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5.3.1.2 Density.
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5.3.1.3 Velocity.
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5.3.1.4 Viscosity.
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5.3.1.5 Gas Compressibility Factor (Z).
5.3.1.6 Friction factor.
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5.4 MEG Estimation.
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6.1 Water Content of Natural Gas at different Conditions. .


6.2 Temperature Profile. .
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6. Result and Discussion.

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6.3 Pressure Profile. .


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6.4 Hydrate Inhibition using MEG. .

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7. Discussion of Project Work


7.1 Quality of Model.
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7.2 Quality of Input Data and Results.
7.3 Potential Improvements.
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8. Conclusion. .

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Nomenclatures.

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References.

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Appendix A: Tables & Figures.

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Appendix B: Calculation Procedures.

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List of Tables
Table 1: Typical Natural Gas Components. .
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Table 2: Three common hydrate unit crystal structures.
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Table 3: Summary of Applications, Benefits & Limitations of Chemical Inhibitors.
Table 4: Water Content of gas at different conditions.
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Table A1: Sour gas correction factor constants.
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Table A2: Constants in LGE equation. .
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Table A3: Natural Gas Reservoir, Production & Pipeline Parameters.
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Table A4: Natural Gas Stream Composition from Nigeria, with modification.
Table A5: Temperature Profile Data. .
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Table A6: Pressure Profile Data.
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List of Figures
Figure 1: Natural Gas Typical Molecule.
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Figure 2: Hydrate Plug Removed from a Gas Pipeline.
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Figure 3: Host molecules (water) and guests (Gas). .
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Figure 4: Schematics of Structure I, II and H Gas Hydrates. .
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Figure 5: Phase Diagram Showing the Conditions under which Hydrates form.
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Figure 6: Conceptual representation of hydrate formation in an oil-dominated system.
Figure 7: MEG Reclamation Process Schematics. .
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Figure 8: Temperature variation along pipeline.
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Figure 9: Steady-State flow (pressure) in gas pipeline.
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Figure 10: Steady-State Temperature Profile.
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Figure 11: Steady-State Pressure Profile.
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Figure A1: Water contents of natural gases. .
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Figure A2: Pressure-temperature Curves for Predicting Hydrate Formation
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Figure A3: Natural Gas Heat Capacity of 0.60 and 0.65 Specific Gravity.
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vi

1. Introduction
Natural gas is rapidly growing in global importance both as a primary energy source and as a
feedstock for the downstream industry. The increase of natural gas in the energy matrix all
over the world has posed a strong demand on offshore exploration and production. Natural
gas consumption has constantly continued to increase from 50 % of the oil consumption in
1950 to 98 % in 1998 (Chapoy 2004). This growth is being driven by a number of economical,
ecological and technological factors together with an overall increasing energy demand
because it is environmentally cleaner than oil and coal.
Natural gas demand is increasing steadily and considering pipeline among other means of
transporting oil and gas, there is guaranteed delivery from the wellhead to processing plant
and from there to the consumers and which also assures lower maintenance costs. It is
therefore important to operate an offshore pipeline system free of hydrate formation risks.
However, it is worthy to note that subsea pipelines represent at least 25 % of the total
project cost and this is one of the reasons for the flow assurance studies (Nava et al. 2011).
The past decade has seen the oil and gas industry moving towards deep-water exploration
and production, with over 10,000 feet of water depth (Mehta et al. 2001), where pressures
and temperatures are ideal for hydrate formation. This has brought new challenges for
hydrate prevention in transportation of natural gas in subsea environment.
Hydrate formation in offshore pipelines is a major problem that arises due to temperature
drop and other thermodynamic changes as hydrocarbons are produced. As temperature
drops or decreases, the solubility of water in gas decreases and the water vapour condense.
The precipitated water molecule causes hydrate to form with hydrocarbon molecules such
as methane. The formation of hydrates can lead to clogging of pipeline, higher pressure
losses, flow rate reduction, and other problems. The removal of hydrate plugs in subsea
production systems as well as transmission systems poses safety concern and can lead to
loss of time and costly repair work. For these reasons, the formation of hydrates in subsea
gas transmission pipelines should be prevented effectively and economically to guarantee
that the pipeline operates normally.

The main objective of this project is to study flow assurance of a natural gas produced from
a subsea environment. A pipeline transmission system of natural gas stream from subsea to
shore (receiving terminal on land) is considered, using a natural gas stream composition
from Nigeria as an example.
In order to avoid hydrate formation in the pipeline system during transmission, my focus is
on analyzing the temperature profile and pressure profile in a steady-state production
conditions along the pipeline. These will provide information on temperature and pressure
data along the pipeline as well as indicating if hydrates will form. Water vapour content of
natural gas is also analyzed for conditions prevailing at the reservoir, wellhead, and at the
receiving terminal. Hydrates formation prevention with Mono-Ethylene-Glycol (MEG), and
an inhibitors rate required to prevent hydrates formation are also analyzed. The inhibitor is
to reduce the dew point temperature of water vapour in the gas flow below operating
temperature and thus, decreasing the risk of hydrate formation.
These will be computed analytically based on the theoretical approach. This project is a case
study based on a specific steady-state defined production case. The production data is
provided in the Appendix, Table A3.
The results will be analysed to identify if the pipeline has the potentials of forming hydrates
as the temperature and pressure drop along the pipeline and to analyse the inhibitors that
could be used to prevent hydrates from blocking the pipeline.

2. Natural Gas: A Closer Look


Natural gas is a non-renewable resource that is expected to be widely expanded in the
decades to come. It is considered a very safe energy source when transported, stored and
used. It is a mixture consisting mainly (70 - 95 %) of methane (CH4, a covalent bond
composed of one carbon atom and four hydrogen atoms), as shown in the Figure 1. It also
contains other gaseous hydrocarbons such as ethane (C2H6), propane (C3H8), normal butane
(n-C4H10), isobutane (i-C4H10), and pentane (C5H12), among other higher molecular weight
hydrocarbons (Sanchez 2010).

Figure 1: Natural Gas Typical Molecule: Models of molecules of oxygen (O2), water (H2O), methane (CH4) and
carbon dioxide (CO2) (Sanchez 2010).

Natural gas also contains impurities or contaminants that have to be removed before it can
be used as a consumer fuel after its extraction from the reservoir. These impurities include
acid gases, such as hydrogen sulfide (H2S), carbon dioxide (CO2), mercaptans (methanethiol
CH3SH, and ethanethiol C2H5SH), nitrogen (N2), helium (He), and water vapor (H20).
Sometimes, mercaptans are kept or added for safety reasons (Sanchez 2010). However, a
typical composition of natural gas is given in Table 1.

Table 1: Typical Natural Gas Components, (Chapoy 2004).


Hydrocarbons

Non - Hydrocarbons

Components
Methane
Ethane
Propane

Mole %
70 - 98
1 -10
Trace - 5

Components
nitrogen
Carbon dioxide
Hydrogen sulphide

Mole %
Trace - 15
Trace - 20
Trace - 20

Butane

Trace - 2

Helium

Up to 5 (non usually)

Pentane

Trace - 1

Hexane

Trace - 0.5

Heptane+

Trace

In the reservoir, oil and natural gas normally coexist with water. Water comes as the wetted
phase and from the sub-adjacent aquifer. The presence of water also causes crystallization
of salts after hydration due to salt concentration increase (when water is consumed).
Furthermore, when gas is produced offshore, the separation of liquid fractions and the
removal of water are not always carried out before the production flow is sent into
pipelines. Consequently, the unprocessed well gas stream coming from a production field
can contain water and light hydrocarbon molecules (methane, ethane, propane and other
components). Given the correct temperature and pressure conditions (particularly large
temperature gradients which leads to higher pressure), can lead to hydrate formation during
transport through pipelines.

2.1 Brief History of Natural Gas


The history of natural gas can be traced back to the ancient Mesopotamia, or the cradle of
civilization that is known today as the Middle East. Natural gas has been observed since
ancient times (Ingersoll 1996). However, it was until a few centuries ago that countries such
as Great Britain, China, and USA, among others, started using natural gas as a means of
supplementing their need for energy (Mokhatab et al. 2006). Moreover, the construction of
a sustainable gas infrastructure, including storage, preprocessing and transport facilities
allows natural gas to become commercially available throughout the world (Sanchez 2010).
According to Mokhatab et al. (2006), Chinese drilled the first known natural gas well in 211
B.C. A few centuries later (around 500 B.C.), they employed crude bamboos as a means to
4

transport natural gas. In Europe, even though the British discovered natural gas in the
middle of the 17th century, it was until the late 18th century (around 1785) that they started
trading natural gas obtained from coal seams for lighting of houses and streets (Rojey et al.
1994).
An intriguing factor that caused a faster expansion of the use of natural gas around the
world in the last decade of the 19th century was the fact that many cities began replacing
their gas lamps with electric lamps. Thus, the gas industry was required to look for new
markets, perhaps far away from their usual customers (Sanchez 2010).
Natural gas had been clearly extinguished by electricity. However, at that time the real
problem was certainly the lack of a pipeline infrastructure to transport and distribute natural
gas, as well as the lack of facilities to store it (Chapoy 2004).

3. Natural Gas Hydrate


Gas hydrates were first identified in 1810 by Sir Humphrey Davy and their composition
established by Faraday, Koh (2002). They are crystalline compounds formed by chemical
combination of natural gas and water under pressure and temperature considerably above
the freezing point of water (Sloan 1998). Hammerschmidt, in 1934 determined that the
plugging of natural gas pipelines was not due to ice formation but to formation of clathrate
hydrates of natural gas (Gaillard et al. 1999). They had it that, this discovery was the
determining factor in causing a more pragmatic interest from oil and gas companies.
As said earlier, natural gas hydrate in oil and gas pipelines may block the pipelines, facilities
and instruments and cause flow and pressure monitoring errors, reducing gas transportation
volume, increasing pipeline pressure differences and damaging pipe fittings, as shown in
Figure 2.

Figure 2: Hydrate Plug Removed from a Gas Pipeline, Zarinabadi et al. 2011.

3.1 Structures of Gas Hydrates


The structures of the crystals fall into the class of clathrates with the water molecules
forming a hydrogen-bonded cage-like structure which is stabilized by guest molecules
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located within the lattice, Makogon (1997) and Sloan (1998). Gas hydrates which are
crystalline ice-like solids are formed from water and a range of lower molecular weight
molecules, typically methane, ethane, and propane. The water molecules are referred to as
the host molecules and the other compounds which stabilize the crystal are called, the
guest molecules. The hydrate crystals have complex, three-dimensional structures in which
the water molecules form a cage and the guest molecules are entrapped in the cages as
shown in Figure 3.

Figure 3: Host molecules (water) and guests (Gas), Zarinabadi et al. 2011.

There are three known hydrate structures referred to as structures I, II and H (abbreviated as
sI, sII and sH) as contained in Pickering et al. 2001. The schematics of the three different
structures are presented in Figure 4.

Figure 4: Schematics of Structure I, II, and H Gas Hydrates (source: www.feesa.net).

Structure I hydrates contain 46 water molecules per 8 gas molecules giving a hydrate
number of 5.75. The water molecules form two small dodecahedral voids and six large tetradecahedral voids. The sizes of the voids are relatively small meaning that the guest
molecules are restricted in size to essentially methane and ethane (Pickering et al. 2001).
Structure II hydrates contains 136 water molecules per 24 gas molecules giving a hydrate
number of 5.67. The water molecules form 16 small dodecahedral voids and 8 large
hexakaidecahedral voids. The larger voids are able to accommodate molecules including
propane, isobutane, cyclopentane, benzene and others. However, while the larger cavities
can accommodate larger molecules, the structure is only stable if small help molecules are
available to fill the smaller lattice cavities (Pickering et al. 2001).
Structure H hydrates contains 34 water molecules for every 6 gas molecules giving a hydrate
number of 5.67. The structure has three cavity sizes with the largest cavity able to
accommodate larger molecules than both sI and sII. Once again, stability is only possible in
the presence of smaller help molecules such as methane or nitrogen (Pickering et al. 2001).
Table 2 lists the properties of the three common unit crystals.

Table 2: The three common hydrates unit crystal structures. Nomenclature: 51264 indicate a water

cage composed of 12 pentagonal and four hexagonal faces. The numbers in squares indicate the
number of cage types. For example, the structure I unit crystal is composed of two 5 12 cages, six
51262 cages and 46 water molecules. (Sloan Jr., 2003)

Hydrate crystal structure

Cavity

Small

Large

Small

Large

Small

512

51262

512

51262

512

16

4.33

3.91

4.73

24

20

Description
Number of cavities per unit
cell
Average cavity radius ()

II

2
3.95

Coordination number

20

Number of waters per unit


cell

46

136

28

medium

Large

435663

51262

3.91

4.06

5.71

20

20

36

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3.2 Conditions Necessary for Formation of Hydrates


There are three major conditions necessary for hydrates formation (Zarinabadi et al. 2011).
These include:

Water as the liquid phase.


Hydrate formers. These are small gas molecules such as methane, ethane, and
propane.
The right combination of temperature and pressure. Hydrate formation is favoured
by low temperatures and high pressures typically 20C and 100 bara.

Figure 5 presents a hydrate formation diagram in the pressure-temperature plane. The right
hand region covers pressures and temperatures at which hydrates are thermodynamically
unstable and is therefore hydrate free as indicated. In the hydrates region, the degree of
sub-cooling is sufficient such that hydrates form spontaneously, Estefen et al. 2005.

Figure 5: Phase Diagram Showing the Conditions under which Hydrates will form (Estefen et al. 2005).

Gas hydrates form in the water phase from gas molecules dissolved in that phase.
Consequently, H2S and CO2 increase the temperature at which hydrates will form since they
are more soluble in water than most hydrocarbons. Turbulence producing conditions (for

example: orifice meters, reduced port valves) enhance the formation of hydrates during
flow. However, hydrates also form under static conditions.
Factors that contribute to the initiation of hydrate formation include:

Degree of sub-cooling hydrates may not begin to form immediately upon reaching
the hydrate point. As much as 5C to 10C of sub-cooling is needed to form the first
seed crystals of hydrates;

Presence of artificial nucleation sites rest, scale, sand, and

Degree of mixing system geometry and flow regime (CAPP 2007)

Furthermore, once crystallization has begun, time is needed for the crystals to agglomerate
(clump) and actually block the flow (CAPP 2007). In other word, hydrates formation is a
transient process. Also, the exact hydrate formation point depends on the composition of
the fluids involved; gas composition and water as well as brine composition. In Figure 6, the
conceptual representation of hydrate formation is shown schematically as temperature
drops along a pipeline with time in oil dominated system, though this project focuses on gas
system. It starts with a shell and then grows up to a hydrate plug (Sloan et al. 2009).

Figure 6: Conceptual representation of hydrate formation in an oil-dominated system. Sloan et al. 2009.

3.3 Gas Hydrate Prevention


Hydrates can be prevented and should not be accepted as normal operating routine. A
hydrate prevention program is more effective than remedial removal measures (CAPP
2007).
The industry has developed several techniques to prevent the formation of gas hydrates.
These methods together with design considerations are extensively discussed in the
literature: Hammerschmidt (1939); Campbell (1998); Makogon (1981); Nielsen and Bucklin
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(1983); Robinson and Ng (1986); and Ng et al. (1987). The following are the thermodynamic
ways to prevent the hydrate formation:
1. Reducing the water concentration from the system.
2. Operating at temperatures above the hydrate-formation temperature for a given
pressure by insulating the pipelines or applying heat.
3. Operating at pressures below the hydrate-formation pressure for a fixed
temperature.
4. Adding inhibitors such as salts, methanol, and glycols to inhibit the hydrate formation
conditions and shift the equilibrium curve to higher pressure and lower temperature.

3.3.1 Hydrates Prevention with Inhibitors


Inhibitors are added into processing lines to inhibit the formation of hydrates. There are two
kinds of inhibitors: thermodynamic hydrate inhibitors (THI), and low-dosage hydrate
inhibitors (LDHI), Paez et al. 2001.
The thermodynamic hydrate inhibitors (THIs) have been used for a long time in the industry
and they act as antifreeze. The main benefits of the thermodynamic hydrate inhibitors (THIs)
are their effectiveness, reliability (provided sufficient quantities are injected) and proven
track-records (Pickering et al. 2001). However, he observed that these benefits are
outweighed by significant limitations, including high volumes, high associated costs (both
CAPEX and OPEX), toxicity and flammability. He added that, they are harmful to the
environment and significant disposal into the environment is as well prohibited.
Low-dosage hydrate inhibitors have recently been developed and their usage modifies the
rheology of the system rather than changing its thermodynamic states. These inhibitors
work at low concentrations, lower than or equal to one (1) weight percent; therefore, the
use of this technique reduces the environmental concerns and since no regeneration units
are required, it results in reduction of capital cost, Pickering et al. 2001. The low-dosage
hydrate inhibitor is divided into kinetic hydrate inhibitors (KHIs), and anti-agglomerants
(AAs).
The kinetic inhibitors (KHIs) are commonly water-soluble polymers which delays the
nucleation and growth of hydrate crystals. Kinetic hydrate inhibitors are injected in much

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smaller quantities compared to thermodynamic inhibitors and therefore offer significant


potential costs savings, depending on the pricing policies of major chemical suppliers
(Pickering et al. 2001). They are also typically non-toxic and environmentally friendly. In
addition, the effectiveness of KHIs appears to be system specific, meaning that testing
programmes are required prior to implementation. Unfortunately, adequate testing can
require appreciable quantities of production fluids which may not be available, particularly
for new field developments. Furthermore, KHIs can interact with other chemical inhibitors
(for example corrosion inhibitors) and testing programmes need to account for this also
(Graham et al. 2001). They concluded that there are no established models for predicting
the effectiveness of KHIs which presents difficulties for field developers considering the
application of these chemicals.
Anti-agglomerants are usually surfactants and miscible in both hydrocarbon and water, so
they impede the agglomeration of hydrate crystals for a period of time without interfering
with crystal formation (Sharareh 2005). The benefits and limitations of Anti-Agglomerants
(AAs) are largely similar to those for KHIs, although AAs do not have the same sub-cooling
limitations. However, there is uncertainty about the effectiveness of AAs under shutdown or
low flow rate conditions and it is postulated that agglomeration may still proceed. In
addition, the one major limitation of AAs compared to KHIs or THIs is that they are limited to
lower water-cuts due the requirement for a continuous hydrocarbon liquid phase. Finally,
compared to both THIs and KHIs, Anti-Agglomerants lacks field application experience,
Pickering et al. 2001.

3.3.2 Selection of Hydrate Prevention and Remediation Strategies


The selection of hydrate mitigation and remediation strategies is based on technical and
economic considerations and the decision is not always clear-cut, Pickering et al. 2001. In
their report, for example, they cited that, in a deepwater development with a significantly
higher reserves base, the operator may elect for a higher cost strategy (example: electrical
heating) in order to minimize risks. In Table 2, a summary of the applications, benefits and
limitations of the three classes of chemical inhibitors are presented.

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Table 3: Summary of Applications, Benefits & Limitations of Chemical Inhibitors (Pickering et al. 2001)

Thermodynamic Hydrate
Inhibitors

Kinetic Hydrate Inhibitors

Anti-Agglomerants
Inhibitors

1. Multiphase
2. Gas & Condensate
3. Crude oil?

1. Multiphase
2. Condensate
3. Crude oil

1.
2.
3.
4.
5.

1.
2.
3.
4.
5.

Applications
1. Multiphase
2. Gas & Condensate
3. Crude oil
Benefits
1.
2.
3.
4.

Robust & effective


Well understood
Predictive
Proven track-record

Lower OPEX/CAPEX
Lower volume (<1wt. %)
Environmentally friendly
Non toxic
Tested in gas system

Lower OPEX/CAPEX
Lower volume (<1wt. %)
Environmentally friendly
Non toxic
Wide range of subcooling

Limitations
1.
2.
3.
4.
5.
6.

Higher OPEX/CAPEX
High volumes (10-60wt. %)
Toxic / hazardous
Environmentally harmful
Volatile losses to vapour
Salting out

1.
2.
3.
4.
5.
6.

Limited subcooling (<10%)


Time dependency
Shutdowns
System specific testing
Compatibility
Precipitation at higher
temperature
7. Limited exp in gas systems
8. No predictive models

1. Time dependency?
2. Shutdowns?
3. Restricted to lower water
cuts
4. System specific testing
5. Compatibility
6. Limited experience
7. No predictive models

3.4 Hydrates Prevention Using MEG


A typical hydrate mitigation strategy is based on continuous injection of a thermodynamic
hydrate inhibitor (typically mono ethylene glycol [MEG]) with little or no insulation of the
subsea system. Today, Mono Ethylene Glycol is the state of the art hydrate control method
(Estefen et al. 2005). They also had it that besides preventing hydrates, MEG reduces the
corrosion rate in the carbon steel pipelines normally used and is well suited as carrier of
corrosion inhibitors and pH-stabilizers. Glycol is also considered to be regeneratable and
considered being environmentally friendly, because of its chemical properties and the use
within a closed loop system where the losses are relatively small (Estefen et al. 2005).
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The main benefits of a MEG solution include:

Reliable solution;
Closed loop;
Corrosion protective;
No gas plant or refinery contamination;
Environmentally friendly, non-toxic, non-flammable;
Qualified technology.

In a closed loop system, Rich MEG arriving at the production unit must be regenerated to
Lean MEG quality, 90-95 weight % MEG, before being re-injected at the subsea producers
(Estefen et al. 2005). The full reclamation of MEG process is illustrated in Figure 7.

Figure 7: MEG Reclamation Process Schematics. (Estefen et al. 2005)

14

4. Water Content of Natural Gas


Water is associated with natural gas from the reservoir, through production and processing
and is a major concern in transmission of natural gas. Natural gas leaving a gas reservoir is
saturated with water, and when it expands at wellheads or into separators, as the
temperature drops, solid gas hydrates may be formed and plugs the pipeline and other
processing equipment (Carroll 2002). The water content of natural gases is thus, an
important quantity to know, especially in connection with gas hydrate formation (Sloan
1990; Song et al. 1987).
In the transmission of natural gas, another problem is further condensation of water. It can
increase pressure drop in the line and often leads to corrosion problems. Thus, the water
content of sour natural gases is an important parameter in the design of facilities for the
natural gas production, transmission, and processing (Bahadori et al. 2009).
The water content of a natural gas in saturated condition is mainly dependent on pressure
and temperature conditions. The water content in a hydrocarbon gas phase decreases with
pressure and temperature, Chapoy (2004). He asserts that, a system containing carbon
dioxide and hydrogen sulphide contains more water at saturation than sweet natural gases,
and its even more pronounced if the pressure is above 5MPa.
Accurate knowledge of phase behaviour in water sour gas system is essential to the design
and operation of natural gas pipelines and production / processing facilities as much natural
gas contain acid gases and water (Mohammadi et al. 2005). He had it that, since the
acid/sour gases are normally saturated with water, it is necessary to estimate the
equilibrium water contents of sour gases as a function of system temperature, pressure, and
composition. This enables the calculation of amount of water condensed as a result of
changes in the system conditions.
There are many predictive methods developed for estimating water contents of gases. These
methods can be divided into two categories (Mohammadi et al. 2005):

Empirical or semi empirical correlations and charts


Thermodynamic models, which is based on equality of chemical potenetials.

15

He also asserts that the main advantage of empirical or semi empirical correlations and
charts is the availability of data input and the simplicity of the calculations, while most of the
available thermodynamic models could be installed on laptop computers.
Using empirical or semi empirical correlations and charts, Mohammadi et al. 2005 puts
that, as long as the gas gravity of the mixture is closed to that of methane, and temperature
is not too high, the effect of gas composition (in other word, gas gravity) can be ignored. He
added that for lean and sweet natural gases containing over 70 mol percent methane and
small amounts of heavy hydrocarbons, the effect of composition can be ignored and the
water content can be assumed as a function of temperature and pressure.
However, a detailed discussion on different methods with some conditions on which they
provide high accuracy can be found in the some of these literatures: Mohammadi et al.
(2005), Carroll (2002), Song et al. (1982), and others. In addition, accurate determination of
water content of sour natural gases therefore requires a careful study of the existing
literature information and available experimental data. In most cases, using additional
experimental data is the best way to verify the model based predictions (Bahadori et al.
2009).

16

5. Empirical Correlations and Calculation Methods


In order to evaluate hydrate formation and prevention along a pipeline system, the various
parameters described earlier in the introduction was computed analytically based on
theoretical approach. Empirical correlations and charts were adopted; therefore this section
will describe as well as discuss the various empirical correlations / models and methods
employed in solving these problems.

5.1 Water Content of gas stream


One of the major tasks of this work was to compute analytically the water content of a
natural gas stream at the reservoir, wellhead, and the receiving terminal conditions. The
composition of the natural gas is provided in the Appendix, Table A4.
To solve this problem, it was pertinent to find a suitable but simple model based on existing
scientific principles, or by adapting equations to experimental results for possible estimation.
Literature such as Mohammadi et al. (2005) indicates that there are several methods of
estimating water content of natural gas.
In this work, Robinson et al.s definition of equivalent hydrogen sulfide mol fraction was
used in determining the equivalent hydrogen sulfide mol fraction and, it is given in the
expression below:
(1)
where,

= equivalent mol fraction of hydrogen sulfide,


= hydrogen mol fraction, and
= carbon dioxide mol fraction. (Mohammadi et al. 2005)

He noted that this method is applicable for

< 0.4 (mol fraction), temperature in the

range of 283.15 to 450.15 K and pressure in the range of 2.07 to 69 MPa.


The equivalent mol fraction of hydrogen sulfide was then used in the new correction factor
developed by Mohammadi et al. (2005) to account for the effect of the acid gases. The
correction factor expression is given as:
[

( )

( )( )

( )]

(2)

where C1 to C3 = Mohammadi et als constant.


17

Fsour = correction factor for the sour content,


T and P = system temperature and pressure respectively.
To and Po = absolute temperature and pressure respectively.
This is based on the fact that water content of an acid/sour gas is a function of temperature,
pressure and acid gas equivalent H2S mol fraction. The constants used are provided in the
Appendix, Table A1.
However, the water content of the gas stream was then computed using the WichertWichert correlation which is given in equation (3) by the expression below:
(3)
where yw_sour and yw_sweet = water content of sour and sweet gas respectively.
The water content of sweet gas was estimated using McKetta-Wehe chart provided in the
Appendix, Figure A1, in that it is highly recommended, though it requires interpolation.
However, the water vapour content that will be precipitated out of the gas stream was
estimated as the difference between the water vapour content at the reservoir conditions
and the water vapour content at the receiving terminal.

5.2 Temperature Profile


The steady-state temperature profile of a subsea natural gas pipeline was analyzed based on
the following assumptions:

Steady-state flow and heat exchange (no problem variable is dependent on time);
Physical properties for the mixture and the structure are independent on
temperature and pressure;
Only mixture temperature variation in the longitudinal direction is considered;
Mixture is idealized homogeneous, that is, single phase flow;
One dimensional heat transfer.

Considering Figure 8; as a representative of a pipeline transporting fluid from point A to


point B. The pipeline was discretized or divided into equal segments and analyzing a short
segment of length, L (from T1 to T2), and then the gas temperature variation along the
pipeline was determined by applying the principle of heat transfer. That is, equation (11) was
applied to each segment of the pipeline.
18

Figure 8: Temperature variation along pipeline.

5.2.1 Necessary Equations and Variables


To compute the steady state temperature profile of a subsea pipeline, the important
variables and equations were surveyed. In steady-state conditions, the flowing fluid is cooled
from the outside due to the cold seawater surrounding it. Assuming the cold seawater has a
constant temperature, the following variables are used:
Mass flow rate (m) inside pipeline [kg/s];
Constant outside temperature, (Tsea)[K];
Pipeline inlet fluid temperature, (T1)[K];
Pipeline outlet fluid temperature, (T2)[K];
pipeline length, (L) [m];
pipeline internal diameter, (din) [m]
Joule-Thomson cooling is not included in the derivation. (Gudmundsson 2011).
The pipeline was envisioned as a long heat exchanger tube with cooling from the outside
and the heat transferred is expressed as:
(4)
where q = heat transferred,
U = overall heat transfer coefficient,
A =heat transfer area, and
TLMTD = logarithmic mean temperature difference.
The cooling of the flowing fluid inside a pipeline can be expressed by the equation:
(

(5)

where Cp = heat capacity of the flowing fluid (fluid mixture).


Based on the definition of the logarithmic mean temperature difference which is expressed
as:
(

) (

(6)

19

where Tu = Tsea, and setting in for constant outside temperature, this result in the following
simplification:
(7)
The cooling from outside of the pipeline corresponds to the cooling of the fluid flowing
inside the pipeline, thus resulting in the relationship:
(

( )

(8)

where the heat transfer area is expressed by A = *d*L, (Gudmundsson 2011).


The relationship can be rewritten as:
( )

(9)

and
( )

(10)

Therefore, to determine the outlet temperature in each of the segment, the equation can be
re-arranged thus:
(

(11)

The temperature, T2 is the outlet temperature for each pipeline segment with an inlet
(wellhead) temperature T1. Equation (11) was then used in computation of temperature
variation along this pipeline.

5.2.1.1 Heat Capacity Estimation


Heat capacity depends on temperature but is practically independent of pressure,
Gudmundsson (2011). The heat capacity of a mixture of fluid (oil, gas and water well mixed)
can be estimated from the relationship:
(12)
where x-values = the mass fractions of the oil, gas, and water phases respectively,
CpM = heat capacity of the mixture.
In this study, a homogeneous single phase (gas) flow was assumed, and the heat capacity
correlation was reduced to:
(13)
where xg = mass fraction of the gas phase and Cpg = specific heat capacity of gas.
Cp = heat capacity of gas
20

The specific heat capacity Cpg was estimated by interpolating through the heat capacity chart
(Moshfeghian 2009), as a function of temperature and specific gravity and at constant
pressure. The heat capacity chart is provided in the Appendix, Figure A3.

5.2.1.2 Mass Rate


The mass rate of the system was computed using the expression below:
(14)

where qg = gas flow rate and


= gas density.
From the assumption that the physical properties of the mixture are independent upon
temperature and pressure, the gas density was estimated from the correlation given below
in equation (15). In other word, the density was determined at standard conditions. Recall
that an ideal gas law is given by:
and density:
.
Thus, combining the two relationships, density can also be expressed as:
(15)

where Ps, = pressure,


Ts = temperature,
Zs = compressibililty at standard conditions.
Mw = gas molecular weight, and
R = gas constant.

5.3 Pressure Profile


The total pressure drop in pipelines and wells consists of pressure drop due gravity (p g),
acceleration (pa), and frictional forces (pf), Gudmundsson (2011). This can be expressed
mathematically as:
pT = pg + pa + pf

(16)

21

Figure 9: Steady-State flow in gas pipeline.

Assuming that there is no elevation (that is, the pipeline is horizontal), then the pressure
drop is mainly due to friction losses between the pipe wall and the fluid. Then, total pressure
drop of compressible fluids (gas) due to friction in horizontal pipe was surveyed from the
expression given below, Gudmundsson (2011):
(

( )

(17)

The natural logarithm term is quite small and can be ignored, Gudmundsson (2011).
Simplifying for P2 yields:

(18)

where f = friction factor,


m = mass rate,
z = gas compressibility factor,
L = pipeline length,
T = system temperature,
d = pipes diameter,
R = gas constant,
M = gas molecular weight, and
A = pipeline cross sectional area.
The pressure at the end of each pipeline segment was then computed using equation (18)
and the pressure drop was then computed as the difference between the inlet pressure (P 1)
and outlet pressure (P2) which can be expressed as:
PT = P1 P2

(19)

5.3.1 Necessary Parameters and Equations


The pipeline throughput (flow rate) depends on the gas properties, pipe diameter and
length, initial gas pressure and flowing temperature, and the pressure drop due to friction.

22

Considering flow through a horizontal pipe segment of length, L, in Figure 9, the upstream
pressure P1 and a downstream pressure P2, (P1 P2) represents the driving force that causes
the flow and the longer the pipe length for a given pressure the larger the pressure drop.
However, iteration was performed on the pipeline diameter to obtain a reasonable pipe
diameter that will ensure flow with less pressure drop. Thus, subsequent sub-sections
discuss these important dependent parameters and variables.

5.3.1.1 Reynolds Numbers


Reynolds number is a dimensionless parameter used to characterize the type of flow such as
laminar, turbulent, or critical flow in a pipe. It is a function of fluid properties (such as
density, gas flow rate, and viscosity) and pipe internal diameter. It is expressed
mathematically as:
(20)
where = fluid density,
v = fluid velocity in the pipe,
d = pipeline internal diameter,
= fluid viscosity.
Laminar flow occurs in a pipeline when the Reynolds number is below a value of
approximately 2000. Turbulent flow occurs when the Reynolds number is greater than 4000.
For Reynolds numbers between 2000 and 4000, the flow is undefined and is referred to as
critical flow (Menon 2005).

5.3.1.2 Density
This is dependent upon the system pressure, gas compressibility and temperature. Recall
that an ideal gas law is given by:
And, density:
.
Therefore, density relationship can also be mathematically expressed as:
(21)
where p, T, and z = system pressure, temperature, and compressibility respectively,
Mw = gas molecular weight, and
23

R = gas constant.

5.3.1.3 Velocity
Considering a pipe segment; the velocity of the flowing gas changes with density and the
pipes internal diameter. It is also a function of fluid rate (q) along the pipe which is given as:
;
and,
And, combining these equations and simplifying for velocity, gas velocity was then
determined using the expression below:
(22)
where m = mass flow rate of the fluid,
A = pipeline cross sectional area.

5.3.1.4 Viscosity
The dynamic viscosity of a fluid is a unique function of fluid composition, pressure and
temperature. As the gas flows in the pipeline, the viscosity changes with change in
temperature and pressure.
In this work, the Lee-Gonzales-Eakins (LGE) correlation was used, (Gudmundsson 2011 and
Jeje et al. 2004), and it has the following form:
(

(23)

where:

where k1 to k5, and x1 to x3 = constants.


These constants are provided in the Appendix, Table A2.

24

5.3.1.6 Gas Compressibility Factor (Z)


The compressibility factor is a measure of how close a real gas is to an ideal gas. The
compressibility factor is a dimensionless number and its a function of the gas gravity,
temperature, pressure, and the critical properties of the gas. For a natural gas mixture,
reduced temperature and reduced pressure is used in determining gas compressibility,
Gudmundsson (2011).
There are several approaches to calculating the compressibility factor for a particular gas
temperature (T) and pressure (P). Hall and Yarborough equation fitted to standing-Katz chart
was used in this work (Whitson et al. 2000). This is based on the reduced pressure and
reduced temperature and it is expressed as:
(24)
(

where:

) )

y = reduced-density parameter, (it is the product of a van der Waals co-volume and
density), was obtained by solving the expression below:
( )

with
( )

(
(
)
)(
)
where Tpr and Ppr = pseudo reduced temperature and pressure respectively.

5.3.1.6 Friction factor


There are various correlations for estimating friction factor of pipes. But in this work,
Haalands friction factor correlation for pipes with rough walls was used as expressed in
equation (25). It is dependent upon Reynolds number and the relative pipe roughness,
Gudmundsson 2011. The relative pipe roughness is given as the ratio of pipe roughness to
the diameter of the pipe.

[( )

(25)
25

where n = 1 for liquids, and n = 3 for gases.


Haalands equation is especially suited for gas pipelines if n=3, Sletfjerding et al. 2001.

5.4 MEG Estimation


The formation of hydrates in gas pipeline systems can be addressed by using thermodynamic
inhibitors which alter the fluids composition. Chemical inhibitor considered in this study is
the mono ethylene glycol (MEG). This is based on the information obtained from the
literature such as Estefen et al. (2005).
Hammerschmidts correlation, the simplest correlation was used to estimate the amount of
inhibitor required to lower hydrate formation temperature (Gudmundsson 2011).
(

(26)

where K = Inhibitors constant,


Mw = Inhibitors molecular weight,
T = hydrate depression temperature, and
x = inhibitors mass concentration.
The required inhibitors concentration (MEG) was obtained by solving equation (26) and it is
expressed as:
(

(27)

The inhibitors constant of MEG used in this analysis was 1222, and molecular weight of the
MEG was 62.00 kg/kmol, (Gudmundsson 2010).
The following assumptions were however made that:

The gas is saturated at wellhead conditions,


The water is pure (in other word, effect of salt is not considered),
Flow is at steady state conditions, and
that hydrates form at 20C. A safety factor of 5oC was also included in this analysis.

The dew point depression is given as the difference between the hydrate formation
temperature and the final terminal temperature. Hydrate formation temperature was
determined using the pressure-temperature curve (GPA Handbook). This chart is provided in
the Appendix, Figure A2.
Water mass rate was determined as the product of gas mass rate and mol fraction of water
condensed expressed as:
26

(28)
Where mg = mass rate of gas and
xw = mol fraction of water.
However, the mass rate of hydrate inhibitor required was estimated as the product of mass
rate of water and the mol fraction of the inhibitor. This is expressed as:
mMEG = mwxMEG

(29)

where mw = mass rate of water and


xMEG = mol fraction of inhibitor.

27

6. Results and Discussion


The main objective of this work was to study flow assurance of a natural gas produced
offshore and transmitted through a pipeline to shore. Analyzes done as described in the
introduction, were based on the fact that hydrates formation are favoured by low
temperature, high pressure and presence of water. A typical natural gas composition from
Nigeria was used in this study. The natural gas composition obtained is provided in the
Appendix, Table A4, with slight modification by this author to account for some
compositions that were not present, just for purpose of this analysis. However, this section
will present the results for the different analyzes that were considered in this work.

6.1 Water Content of Natural Gas at different Conditions


In this work, empirical correlations and charts were used as described in the methods. Water
content of natural gas stream containing acid/sour gas was estimated with the contribution
of the acid/sour gases accounted for by the correction factor. It is obvious that acid gas
correction factor increases as temperature and pressure decreases (that is, from the
reservoir to the receiving terminal). The result also shows that the gas holds less water in the
gas phase at these different conditions. This is summarized in Table 3 below:
Table 4: Water Content of Gas at different conditions

Water
Content
mg/Sm3

Pressure
bara

Temperature
o
C

Sour Gas
Correction
Factor

Reservoir

290.00

90.00

0.9785

3495

Wellhead

200.00

80.00

0.9855

3063

Terminal

113.34

17.59

0.9932

374

Conditions

The water vapour condensed out of the gas phase at the wellhead is 432.67 mg/Sm3 and at
the receiving terminal at shore, it is 2689.04 mg/Sm3. However, the difference between the
water content at reservoir condition and the water condensed at the receiving terminal,
amounts to the quantity of water that needs to be removed or prevented from forming
hydrates. The total value of condensed water at the receiving terminal is approximately 806
mg/Sm3 which is high enough to cause hydrates formation with the presence of other
28

favourable conditions. It is necessary to control the water content of gas to ensure safe
operation of gas pipeline.

6.2 Temperature Profile


From the given rate of gas (35106 Sm3/day), the arrival temperature of this system is
approximately 18 oC. This indicates that in steady state thermal analysis, with constant mass
rate, heat capacity, the overall heat transfer coefficient and the pipelines internal diameter
(600 mm), the gas temperature along the pipeline tends towards the constant sea (ambient)
temperature (10 oC). This is shown in Figure 11.

Steady state temperature profile


80.0

70.0

60.0

Temperature, T(oC)

50.0

40.0

30.0

20.0

10.0

0.0
0

20000

40000

60000

80000

100000

120000

Distance, L(m)
Figure 10: Steady-State Temperature Profile

The result of this analyzes points out that the fluid is within hydrate forming region
(temperature) when compared to the theoretical or necessary conditions (less than 21 oC)
29

that favours hydrate formation. The pipeline is exposed to the cooling sea current, thus the
gas inside the pipeline is cooled down to temperatures that favour hydrate formation.
In steady state operation, the production fluid temperature decreases as it flows along the
pipeline due to heat transfer through pipe walls. This steady state temperature profile from
the produced fluid can be used to identify the flow rates and insulation preference that can
keep the system above the critical minimum temperature during production.
Thermal analysis of a typical subsea production system, which predicts the temperature
profile along the flowline, is one of the most important steps in the subsea layout design
(Vianna et al. 2009). However, heat transfer analysis of the pipeline systems is of great
importance for the prediction and prevention of hydrate formations. Accurate knowledge of
the temperature field in the equipment combined with the knowledge of the critical
temperature values for solid deposit formations must be adequately evaluated in order to
ensure continued production at desired levels for profitability.

6.3 Pressure Profile


The analysis of steady state pressure drop in a gas pipeline in this study was evaluated using
a correlation published in Pressure drop in Gas Pipeline, TPG 4140 (Gudmundsson 2010). The
initial wellhead pressure which is the pipelines inlet pressure was 200 bara and the arrival
terminal pressure estimated is approximately 113 bara. This gives a total pressure drop (PT)
of approximately 87 bara for a flow rate of 35106 Sm3/day, and a pipeline diameter of 600
mm. It was observed that the velocity of gas changes due to changes in gas compressibility
which is a function of pressure, temperature and gas composition.
However, from this result, it can be said that this flow is not out of hydrate forming region,
based on theoretical conditions that high pressures favours hydrate formation in a gas
pipeline (usually 100 bara and above). The steady-state pressure profile along the pipeline is
presented in Figure 11.

30

Steady State Pressure Profile


200.0
180.0
160.0

Pressure, P (bara)

140.0
120.0
100.0
80.0
60.0
40.0
20.0
0.0
0

20000

40000

60000

80000

100000

120000

Distance, L (m)
Figure 11: Steady-State Pressure Profile

6.4 Hydrate Inhibition Using MEG


The formation of hydrates in gas pipeline systems can be addressed by using thermodynamic
inhibitors which alter the fluids composition. In this study, MEG was considered and the
Hammerschmidts correlation was used in estimating the required concentration of inhibitor
to prevent hydrates from forming.
From the result, the required amount of MEG estimated was 27.32 %, with an upstream
(wellhead) rate of 9.24 kg/s (798.350 tonne/day). The estimated quantity of vapour
condensed out of the gas phase at the terminal to be inhibited from forming hydrates was
806.23 mg/Sm3. The increased amount of produced water will require an increased amount
of MEG to maintain the correct concentration to prevent hydrate formation.

31

7. Discussion of Project Work


7.1 Quality of Model
The mathematical model presented showed a bit complex approach to estimating
parameters such as water content of sweet gas, the heat capacity of gas, and hydrate
depression temperature. They all require interpolations through a chart.

7.2 Quality of Input Data and Results


The natural gas composition data from Nigeria was scarce. The quality of the gas
compositions was not as obtainable at the reservoir (that is, some compositions like
Hydrogen sulfide, Carbon dioxide, and Nitrogen were not included), thus, an adjustment was
made and this can affect the results. However, economic analysis, extra quantity of inhibitor
considered in this work that could be stored in the tank during production operation was not
done, as well as transient analysis for this system was not also done.

7.3 Potential Improvements


There are plans to improve on the quality of the input data and the results. These plans
include: making of transient analysis of this flow along the pipeline analytically for both the
temperature and pressure profiles, economic analysis of the inhibitor and estimation of the
extra quantity of inhibitor in the storage tank. For the gas composition data, the quality
would be improved by searching for another data that will contain the necessary
compositions as obtainable at the reservoir. However, sensitivity analysis would be
performed on some important parameters like price of inhibitors, pipelines internal
diameter, etc. to observe their possible effects in managing or controlling hydrates
formation.

32

8. Conclusion
Produced natural gas stream from the reservoir is always saturated with water. One of the
problems associated with the transmission of this fluid especially in offshore / subsea
environments to shore through pipeline is the formation of hydrates. Thus, the important
parameters and factors that favour hydrate formation must be understood if hydrates are to
be controlled or managed.
Water content estimation of a natural gas stream at the reservoir, wellhead and the
receiving terminal conditions is one of the important parameters that must be understood if
successful operations of pipeline transmission systems are to be ensured. The estimated
amount of water vapour condensed was 803.23 mg/Sm3.
In the thermal analyzes, the initial wellhead temperature was 80 oC and the arrival
temperature is 17.59 oC giving rise to a total temperature drop of 62.41 oC. Thus, the gas
flow is not out of hydrate forming region as the terminal arrival temperature was below 20
o

C.

The pressure profile analyzes also results in a total pressure drop of 86.66 bara, with the
arrival pressure of 113.34 bara. The initial wellhead pressure was 200 bara, thus arrival
pressure also reflects pressure above 100 bara, a condition which also favours hydrates
formation.
Based on the fact that this flow is not out of hydrate forming conditions, MEG was
considered for the prevention of hydrate plug formation. The total amount of hydrate
inhibitor (MEG) required to prevent hydrate formation was estimated to be 798.35
tonne/day. Consequently, it is important to identify first the potentials of hydrate formation
in a pipeline system and then plan on the necessary prevention strategy for safe operations.

33

Nomenclature
MEG
CAPEX
OPEX
P1
P2
A
f
z
R
T1
T2
din
Tf
QMEG
L
g
Tr
Pr
g
Tc
Pc
CO2
Mw
m
Cp
H2S
TLMTD
U
xg
THIs
KHIs

Fsour
To
Po
yw_sour
yw_sweet

=
=
=
=
=
=
=
=
=
=
=
=
=
=
=
=
=
=
=
=
=
=
=
=
=
=
=
=
=
=
=

Mono-Ethylene-Glycol
Capital Expenditure
Operational Expenditure
Upstream or Inlet Pressure (bara)
Downstream or outlet Pressure (bara)
Cross sectional Area of pipeline (m2)
Friction factor
Gas compressibility factor
Gas constant (J/kmol.K)
Upstream or Inlet temperature ( oC)
Downstream or outlet temperature (oC)
Pipeline internal diameter (m)
Gas flowing temperature (oC)
MEG flow rate (tonne/day)
Pipeline Length (m)
Gas viscosity (cp)
Reduced temperature
Reduced pressure
Gas density (kg/m3)
Critical temperature (K)
Critical pressure (MPa)
Carbon dioxide
Molecular weight (kg/kmol)
Mass rate (kg/s)
Heat capacity (J/kg.K)
Hydrogen Sulfide
Logarithmic mean temperature difference (K)
Overall heat transfer coefficient (W/m2.K)
Gas mass fraction (kg/kmol)
Thermodynamic hydrate inhibitors
Kinematics hydrate inhibitors

Equivalent hydrogen sulfide (mol)

=
=

Mole fraction hydrogen sulfide (mol)


Mole fraction carbon dioxide (mol)

=
=
=
=
=

Sour gas correction factor


Absolute temperature (oC)
Absolute pressure (bara)
Sour gas water content (mg/Sm3)
Sweet gas water content (mg/Sm3)
34

L
BC
q
K

=
=
=
=

Change in pipes length (m)


Before Christ
Heat transfer (W)
Inhibitors constant

35

References
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Natural Gases, 2009. Journal of the Japan Petroleum Institute, 52, (5), 270-274.
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Series, Vol. 1, and Vol. 2.
Canadian Association of Petroleum Producers Guideline (CAPP), Calgary, Alberta, 2007.
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http://www.capp.ca/library/publications/healthSafety/pages/pubInfo.aspx?DocId=6710
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to 10,000 Psia, 2002. Gas Liquids Engineering, Ltd. Calgary, Alberta, CANADA. Paper
Presented at the 81st Annual GPA Convention. Dallas, Texas. March 11-13.
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Systems, 2004. Prsente et soutenue publiquement par de lEcole des Mines de Paris
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13th December, 2011). P.19-34
Estefen, T.P., Werneck, D.S., Amante, D.A., Jorge, J.P.C., and Trovoado, L.C. Subsea
Production System for Gas Field Offshore Brazil, 2005. International Student Offshore
Design Competition, Federal University of Rio de Janeiro Naval Architecture and Ocean
Engineering Department. p.28, 40 & 41. http://www.isodc.com/1st_ISODC05ufrj%20team.pdf (accessed November, 2011).
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40

Appendix A
Table A1: Sour gas correction factor constants, (Mohammadi et al. 2005)

Mohammadi et al.
Constants
C1

0.03185

C2
C3

0.01538
-0.02772

Table A2: Constants in LGE equation (Jeje et al. 2004)

Lee, Gonzales & Eakin (LGE) Method


LGE Constants
k1
9.379
k2
0.01607
k3
1.5
k4
209.2
k5
19.26
x1
3.448
x2
986.4
x3
0.01009
y1
2.447
y2
0.2224

Table A3: Natural Gas Reservoir, Production & Pipeline Parameters

Reservoir Pressure

PR

290

bara

Wellhead Pressure

Pwh

200

bara

Reservoir Temperature

TR

90

Wellhead Temperature

Twh

80

Seawater temperature

Tsea

10

Wellhead (template) Depth

Dwh

150

Total Natural Gas Rate

3.50E+07

Sm3/day

Pipeline Internal Diameter ID

din

600

mm

Pipeline Length
Pipeline Overall Heat Transfer Coefficient

L
U

120
10

km
W/m2.k

Pipeline Roughness

35.10

microns

C
C
C

41

Figure A1: Water contents of natural gases, Mcketta and Wehe Chart (GPA Handbook).

42

Figure A2: Pressure-temperature Curves for Predicting Hydrate Formation Temperature (GPA
Handbook).

43

Figure A3: Natural Gas Heat Capacity of 0.60 and 0.65 Specific Gravity (Moshfeghian, 2008)

44

Table A4: Natural Gas Stream Composition from Nigeria, with slight modification
Source: Development of petrochemicals from natural gas (methane), Maina, N.S., 2005 (Dept. of
Chemical Engineering, Ahmadu Bello University, Nigeria)
(Original)

(Modified)

Component Symbol

Mol
Percent

Mol
fraction

Component Symbol

Mol %

Mol
fraction, zi

Methane

C1

91.25

0.9125

Methane

C1

90.01

0.9001

Ethane

C2

3.61

0.0361

Ethane

C2

5.35

0.0535

Propane

C3

1.37

0.0137

Propane

C3

2.46

0.0246

i-Butane

i-C4

0.31

0.0031

i-Butane

i-C4

0.31

0.0031

n-Butane

n-C4

0.44

0.0044

n-Butane

n-C4

0.38

0.0038

i-Pentane

i-C5

0.16

0.0016

i-Pentane

i-C5

0.21

0.0021

n-Pentane

n-C5

0.17

0.0017

n-Pentane

n-C5

0.2

0.002

Hexane

C6

0.27

0.0027

C6

0.05

0.0005

Heptane+

C7+

2.42

0.0242

Hexane
Heptane
plus

C7+

0.57

0.0057

CO2

Nitrogen

N2

0.04

0.0004

H2S

CO2

0.14

0.0014

N2

H2S

0.28

0.0028

100

100

Carbon
dioxide
Hydrogen
Sulphide
Nitrogen
Total

Carbon
dioxide
Hydrogen
Sulphide
Total

45

Table A5: Temperature Profile Data

Segment Pipeline
Number Segment
dL
#
m
1
0
2
100
3
200
4
300
5
400
6
500
7
600
8
700
9
800
10
900
11
1000
12
1100
13
1200
14
1300
15
1400
16
1500
17
1600
18
1700
19
1800
20
1900
21
2000
43
4200
1190
118900
1191
119000
1192
119100
1193
119200
1194
119300
1195
119400
1196
119500
1197
119600
1198
119700
1199
119800
1200
119900
1201
120000

Pipeline
Temperature
Ti
o

C
80.000
79.871
79.741
79.612
79.484
79.355
79.227
79.099
78.971
78.843
78.716
78.589
78.462
78.335
78.209
78.083
77.957
77.831
77.706
77.581
77.456
74.763
17.747
17.733
17.718
17.704
17.690
17.676
17.661
17.647
17.633
17.619
17.605
17.591

46

Table A6: Pressure Profile Data

Pressure Profile Determination


Segment Pipeline Pipeline Compressibi
Serial Segment Temperature lity factor Density Velocity
Number
g
dL
Ti
U
Z
o
#
C
m
kg/m3
m/s
1
0
80.000
0.8835 143.473
7.8485
2
100
79.871
0.8833 143.559
7.8438
3
200
79.741
0.8831 143.591
7.8420
4
300
79.612
0.8829 143.624
7.8402
5
400
79.484
0.8826 143.657
7.8384
6
500
79.355
0.8824 143.690
7.8367
7
600
79.227
0.8822 143.722
7.8349
8
700
79.099
0.8819 143.755
7.8331
9
800
78.971
0.8817 143.787
7.8313
10
900
78.843
0.8815 143.820
7.8296
11 1000
78.716
0.8812 143.852
7.8278
12 1100
78.589
0.8810 143.885
7.8261
13 1200
78.462
0.8808 143.917
7.8243
14 1300
78.335
0.8806 143.949
7.8225
15 1400
78.209
0.8803 143.981
7.8208
1193
1194
1195
1196
1197
1198
1199
1200
1201

119200
119300
119400
119500
119600
119700
119800
119900
120000

17.704
17.690
17.676
17.661
17.647
17.633
17.619
17.605
17.591

0.7597
0.7598
0.7599
0.7600
0.7600
0.7601
0.7602
0.7603
0.7604

115.775
115.662
115.549
115.435
115.321
115.207
115.093
114.978
114.862

9.7262
9.7357
9.7452
9.7548
9.7644
9.7741
9.7838
9.7936
9.8034

Constants

5.188
5.188
5.189
5.189
5.190
5.190
5.191
5.191
5.192
5.193
5.193
5.194
5.194
5.195
5.195

1.293
1.293
1.293
1.293
1.293
1.293
1.293
1.292
1.292
1.292
1.292
1.292
1.292
1.292
1.292

128.905
128.859
128.813
128.767
128.721
128.676
128.630
128.585
128.539
128.494
128.449
128.404
128.359
128.314
128.269

5.520
5.520
5.520
5.520
5.520
5.520
5.520
5.521
5.521

1.219
1.219
1.219
1.219
1.219
1.219
1.219
1.219
1.219

106.249
106.244
106.239
106.233
106.228
106.223
106.217
106.212
106.207

Haaland's
Total
Outlet
Reynolds Friction
Pressure
Pressure
Drop
Viscosity Number Factor
P2
dPT

Re
fH
mPa.s
bara bara
0.0196 34399147 0.0108 200.00 0.00
0.0196 34395012 0.0108 199.92 0.08
0.0196 34397808 0.0108 199.84 0.16
0.0196 34400597 0.0108 199.76 0.24
0.0196 34403379 0.0108 199.68 0.32
0.0196 34406153 0.0108 199.60 0.40
0.0196 34408921 0.0108 199.52 0.48
0.0196 34411681 0.0108 199.44 0.56
0.0196 34414434 0.0108 199.36 0.64
0.0196 34417180 0.0108 199.28 0.72
0.0196 34419919 0.0108 199.20 0.80
0.0196 34422650 0.0108 199.13 0.87
0.0196 34425375 0.0108 199.05 0.95
0.0196 34428094 0.0108 198.97 1.03
0.0196 34430805 0.0108 198.89 1.11
0.0158
0.0158
0.0158
0.0158
0.0158
0.0158
0.0158
0.0158
0.0158

42701098
42722431
42743828
42765288
42786813
42808401
42830054
42851772
42873556

0.0108
0.0108
0.0108
0.0108
0.0108
0.0108
0.0108
0.0108
0.0108

114.19
114.08
113.98
113.87
113.77
113.66
113.55
113.45
113.34

47

85.81
85.92
86.02
86.13
86.23
86.34
86.45
86.55
86.66

B. Calculation Procedure
I present here the calculation procedures of the various inputs used in this work for the
evaluation of hydrates formation and prevention, but the equations with the important
parameters are discussed in the empirical correlations and calculation methods section. The
natural gas composition data was first obtained and other necessary data provided in
Appendix A, and then the formulas to be used was decided for the calculations of the
needed values.
For water vapour estimation at different conditions, the equivalent hydrogen sulfide was
first determined and it was used for the calculation of the sour gas correction factor. Sweet
gas water content was determined using Mcketta-Wehe chart, and the water content of the
gas was then estimated as the product of the sweet gas water content and the sour gas
correction factor.
For temperature drop, I needed to calculate the specific gravity of the gas using the
molecular weight and the pseudocritical properties of the gas compositions. I further on to
calculate the mass rate of the gas at standard conditions and the temperature profile along
the pipeline was then calculated.
I continued on the pressure drop along the pipeline. The gas compressibility was calculated
using reduced temperature and pressure, and it is highly dependent on pressure and
temperature of the system. I further calculate the density, velocity, viscosity, Reynolds
number, friction factor, and then outlet pressure for each pipes segments. And, finally the
total pressure drop along the pipeline.
Finally, for the prevention of hydrate formation using MEG, I first determined hydrate
depression point. From the percentage of water condensed, water mass rate was
determined, and with the estimated amount of MEG, the required quanity of inhibitor (MEG)
at the wellhead to prevent hydrate formation and blockage of pipeline during transmission
was estimated.

48