International Journal of Advanced Biotechnology and Research (IJBR)

ISSN 0976-2612, Online ISSN 2278–599X,

Vol-7, Special Issue-Number5-July, 2016, pp1030-1036
http://www.bipublication.com

Research Article

Studying and simulating gas hydrate formation procedure in Kamyaran CGS

pressure reduction station

Ranjbar .Behnam1, Jafarbeigi. Ehsan2 and Kazemi .Maryam 3

1
Department of Chemical Engineering, kermanshah Branch,
Islamic Azad University kermanshah, Iran
2
Young Researchers and Elite Club, kermanshah Branch,
Islamic Azad University, kermanshah, Iran
3
Department of Chemical Engineering, kermanshah Branch,
Islamic Azad University kermanshah, Iran
ABSTRACT
Hydrate formation can naturally occur in gas pipes or industrial equipment, which in many cases is highly risky. Gas
hydrate formation brings about pressure reduction and occasionally pipe line blockage. In this study for data Peng –
Robinson method is used. Also using virial state equation and gas composition simulation is done with Hysys
software.Then using peng-robinson state equation CGS pressure reduction stasation is simulated. After that
considering the instrument in Hysys software the hydrate formation condition is studied. With use of the diagrams
analysis pressures and temperatures under which hydrate was formed is determined and studied. Using the results of
this project hydrate formation in other statins can be prevented.

Key words:gas hydrate, hydrate crystals, simulation, pressure reduction station.

1. INTRODUCTION
Hydrate, a natural gas, is an ice like compound of
water and natural gas which is formed in low
temperature. This compound is part of Klatryt
family including two heterogeneous molecules
which are combined mechanically but in fact they
are connected without any chemical bond and
form one molecule or construction which traps the
other molecules. Natural gas hydrates have a semi
ice structure which surround methane and other
hydrocarbons and melt in temperature higher than
ice melting point [1]. The gas hydrate history is
divided into three periods: First period started
when it was discovered by Sir Humphery Davy in
1810 and continued up to now, it is interesting
because of the scientific process of hydrate
formation, since the water and gas combination in
a solid phase (hydrate) is scientifically The
second phase started almost since 1934 with
describing the fact that hydrate formation causes
blockage in pipe lines. This phase also continued
up to now. After Hammer Schmidt’s discover
about the reason of pipe lines blockage, the first
ones who did the experiments on the hydrate
formation conditions and reported some data from
it were Frost and Deaton. In this period hydrate
was considered as a problem for producers and
processors of natural gas. In other words this
period of hydrate history appertain to the
developing industries and its problems. The third
period: this period started in the mid-70s, when it
was found that the nature has created hydrates
millions of years before human beings. These
hydrates exist in the glacier areas of deep oceans
and also out of the atmosphere in other planets
such as mars [2].
As a result the recent period is historically the
meeting point of these three periods. Generally
hydrate formation is possible when decreasing the
 Studying and simulating gas hydrate formation procedure in Kamyaran CGS pressure reduction station
temperature or increasing the pressure [3, 4]. In
fact gas hydrate can be both a threat for pipelines
blockage and a way for gas transmission [5].
For designing industrial units of gas hydrate
production it is very important to have reliable
thermodynamic models for predicting the
operational conditions of hydrate formation and
its structure and composition. as one of the most
important as well as first models offered in this
field we can mention Ping Robinson and Van der
waals – Platteeuw models which were proposed in
1959 [6]. In 2002 Balard and Eslone, proposed a
model based on water fugacity in hydrate phase
and in other phases (water or ice). In this model
they try to omit van der waals and platteeuw’s
model two existing theories that are: hydrate
phase being ideal and equality of conditions for
standard state hydrate for all gas compounds in a
special structure [7].
In 2003 Clada and Sandler proposed a model
based on waals and platteeuw’s which is capable
of predicting hydrate formation conditions for gas
mixtures. In this model water equality fugacity
theory is used [8].
Anderson and colleagues in 2005 proposed a
model based on waals and platteeuw’s model
which can predict the conditions of gas mixture
hydrate formation. In this model Vant Hoof’s
function is used for calculating the Longmuir
constant [9].
The methods for preventing the hydrate formation
are divided into 5 groups: pressure controlling
methods, temperature controlling, removing
water, removing guest molecules and injecting
chemical inhibitors [10,11].
In pressure controlling method system is designed
in a way that operational pressure is
thermodynamically less than hydrate formation
pressure. This method is not efficient in most of
the cases because high pressure is necessary for
gas transmission. And also high pressure in many
procedures like gas absorption and moisture
removal can increase the system efficiency. But
this method can be used for removing the formed
Jafarbeigi Ehsan, et al.
hydrates. So it is rather a way to omit the hydrate
than to prevent its formation. In temperature
controlling method, for increasing the temperature
the pipe is heated by steam or electricity. Using
thermal insulants can also be useful. In some
procedures gas should be kept cool. In the third
method water removal is carried out with surface
absorption method by alumina silica gel, molecule
sieve or using the ethylene glycol battery
absorption methods. Removing the guest
molecules as they are in most cases the main fluid
of the process, it is defeating the purpose and
impossible. In chemical method for hydrate
formation preventing or removing the formed
hydrates, adding chemicals to the pipelines brings
about hydrate formation phase diagram change or
hydrate formation kinetics change. Inhibitors
include thermodynamic and kinetic inhibitors.
Adding thermodynamic inhibitors causes the
inhibiting molecule or ion to compete with water
molecules and to change water and hydrocarbon
thermodynamic balance. These materials change
the curve of hydrate phase balance to lower
temperatures and higher pressures and in this state
hydrate crystals are not
formed. Methanol, and glycols such as ethylene
glycol (MEG) and electrolyte solutions containing
inorganic salts such as sodium chloride, calcium
chloride and lithium chloride act as
thermodynamic inhibitors. Kinetic inhibitors can
affect the hydrate formation kinetics. These
materials can prevent hydrate crystal nucleation
the amount of these materials injection is very low
about 0.01% to 0.5 % weight percent [12, 13].
The other factors affecting the hydrate formation
are: mixing amount (turbulence), kinetics, crystal
formation, nucleation place, the accumulation
amount, and system salinity. These phenomena
can increase the hydrate formation but are not
essential for the formation procedure [14]. In the
recent years it is determined that ion liquids can
act as dual purpose inhibitors. Ion liquids are
organic salts which are known as green solvents
and are in form of liquid in a wide temperature
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 Studying and simulating gas hydrate formation procedure in Kamyaran CGS pressure reduction station
span, they are inflammable , have a low steam
pressure , and are accessible [15,16].
The purpose of this research is simulation of
hydrate crystal formation using Hysys software.
2. MATERIALAND METHODS
In this study, the way of hydrate formation in
Kamyaran cgc pressure reduction station was
studied.
2.1 REASONS OF GAS HYDRATE
SIGNIFICANCE
Nowadays paying attention to gas hydrate
phenomena and its useful and practical aspects
clarifies the necessity of more researches in the
following fields:
1-Since a few decades ago so far, the existence of
large amounts of natural gas stored in the gas
hydrates in the ocean’s bed and poles is proven.
Considering the finite resources of fossils fuels
discovering gas hydrate resources for recycling
energy can be noticed in future.
2-The gas hydrate capacity for storing the natural
gas, has absorbed attentions for using it for
storing and transporting the natural gas and other
gases as an alternative to liquefaction and
compression.
3-Gas hydrates can also be used in separation
processes. Gas hydrates are formable just with a
few number of materials. If we want to separate a
material from a mixture including non-formable
hydrate formation, using hydrate formation is
considered an opportunity. As example we can
mention condensing water-rich streams, making
drinking water from the sea, and separating gas
streams. The noticeable point is that about natural
resources of gas hydrates there are some worries
about their stability when changing pressure and
temperature. In some researcher’s belief when the
earth temperature increases because of Green
House effect, the hydrates may become instable
and decompose and therefore a large amount of
methane can enter the atmosphere and intensify
the green house effect, because the effect of
methane on these phenomena is more than carbon
Jafarbeigi Ehsan, et al.
dioxide. The scientists believe that at the end of
the ice age on earth and melting of ice resources,
the gas hydrate sources decomposition will occur.
In our country also this research in considered
very important and in oil industry institute a plan
is under study in which different practical and
theoretical aspects of gas hydrates are studied.
The formation of hydrate crystals in different
parts of oil and gas industry and subsidiary
procedures can cause the stop or decrease of the
products and for this reason there are good
information about their formation situation and
conditions, but as their production has not been
noticed, fewer studies have been carried out on
the growing speed of hydrate crystals. However
the advent of new theories about natural gas
transport in form of hydrate crystals in accordance
to the decrease of the expenses and final price of
the product has made more studies carried out in
this case.
2.2 METHODS FOR PREVENTING THE
HYDRATE FORMATION IN PRESSURE
REDUCTION STATIONS
Four methods are offered for stimulation of
preventing the hydrate formation. The first
method is common and used in pressure reduction
stations but the three other methods are offered as
alternatives. These four methods are:
A-Using indirect water bath heaters
B-Replacing the expansion turbines with pressure
relief valve
C-Using indirect water bath heaters and generator
D-Using electric heaters and generator
E-Replacing vortex pipes with pressure relief
valve
F-Replacing the CWT heater with indirect water
bath heaters
These cases are for preventing the simulated
hydrate[17].
3. GETTING TO KHOW THE CGS
PRESSURE REDUCATION STATION
CGS station: the cities entrance gas stations for
reducing the pipeline pressure from 1050 to 250
psi
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 Studying and simulating gas hydrate formation procedure in Kamyaran CGS pressure reduction station
As obvious from its name it occurs at the entrance
of the cities. Of course pressure reduction stations
of big industries and powerhouses are considered
of these kind of stations. The equipment in these
stations can be described as follow:
 Insulation joint
 Odorizer
 Scubber
 Filter separator
 Dry gas filter
 Isolating valves
 Indirect water bath heater
 Safety shut off valve
 Pressure reducing and control valve
 Metering system
 Safety Valves
 Sound attenuator
 Indicator units such as thermometer and
barometer
 Sensing line
 Drain valves
 supports
 fencing and environment
 Lighting system and protection
But the main parts of the station can be more
generally introduced as: Filtration, heating,
pressure reduction and control, measurement and
odorizing.
1-Gas filtration
In all gas pipelines there are usually especial
particles and contaminations which include: rust
particles of pipes, sediments, gas condensates, and
tiny solid particles which should be separated
from the inputting gas and should finally be
omitted from the consumed gas because of two
main reasons:
 For preventing the damage to the station
instrumentations such as counter, regulator and …
 Following gas standards to deliver to the
consumers
In filtration station filter separators are used, in
these kind of separators, the gas flow first enter
the plant and because of much speed reduction ,
Jafarbeigi Ehsan, et al.
water and mud sediment and after passing through
the filter elements the particle in them is taken up
to 5 micron.
2-Heatting
To prevent the hydrate formation and frizzing the
regulator parts and gas flow directions during the
pressure reduction, the gas is heated to some
extent.
3-pressure reduction and control
In the third stage in CGS station which is the most
important stage, two inlet pressures are reduced.
The inlet pressure of 1000psi is reduced to 400psi
and in the second stage to 250psi and proportional
to the outlet pressure is regulated by the regulator.
4-Measurement
The measurement of consumed gas in this station
is done by turbine type counters. On each of the
main lines a counter is installed. As seen in Fig
(1) CGS station is visible with its heaters, filters
and equipment.
Fig (2) shows the hydrate formation in pipelines.
Fig (1):cgs station
Fig (2):shows the hydrate formation in pipelines
4.STUDING THE HYDRATE SIMULATION
BY HYSYS
As you know gas does not normally freeze, but
when the temperature is low or when the pressure
is high and line has impurities like water, the
water molecules surround the gas molecules and
bring about gas hydration and following that
reduction of molecular movement which is very
important in pressure reduction stations. In this
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 Studying and simulating gas hydrate formation procedure in Kamyaran CGS pressure reduction station

project, Hysys software is used. This software has Table (1) Stream composition
tools with which we can determine the points Mole Mass Volume
component
where hydrate is formed. And after that the fractions fraction fraction
operator will know that in these temperatures and Methane 0.8776 0.08028 0.08921
Ethane 0.0273 0.0468 0.0438
pressures these condition occurs, and noticing that
Propane 0.0063 0.0158 0.0103
regulates the station heater temperature to prevent 0.0023 0.0077 0.0044
n-Butane
hydrate forming condition. First the state equation Nitrogen 0.0405 0.0647 0.0267
should be determined, it is very important. Co2 0.0080 0.0201 0.0081
Knowing that in the gas systems are made mainly Oxygen 0.0000 0.0001 0.0000
from hydrocarbons , hence the suitable state H2S 0.0033 0.0064 0.0027
H2O 0.0347 0.0357 0.0119
equation is Peng- Robinson equation .This
equation is applicable in a wide range of
temperature and pressure in one, two ,or three
phase systems and is suggested for petro chemical
gas-oil systems and has a good accuracy in hydro
carbon systems. After inserting the percent of
table (1) components into the simulation
environment , we define the data of the intended
state equation and after the end of these stages we
choose hydrate in the simulation environment and
after determining the hydrate, simulator will
determine the hydrate formation conditions in the
intended station fig (3). Next it gives us the
temperatures and pressures under which hydrate is
formed table (2). In table (3) the results from
simulation in hydrate formation condition is
Figure(3) hydrate formation curve in pressure
shown in the highest pressure and temperature. reduction station
The dew and bubble points are also determined. Table(2) Hydrate curve table
Tables (4and5) show the outlet results of the Pressure(psig) Temperature(c)
simulator in dew and bubble pressure. The 249.5 1.920
generalized form of the Peng-robinson state 463.0 6.852
equation is as follow: 537.5 8.012
699.2 9.995
758.2 10.59
793.5 10.91
814.3 11.10
826.2 11.20
833.5 11.26
836.8 11.29
833.7 11.26
Table(3) Connections
CONNECTIONS
Critical temperature -72.82c
Critical Pressure 808.7psig
Cricondentherm -58.10psig
Cricondenbar 837.4psig

Jafarbeigi Ehsan, et al. 1034

 Studying and simulating gas hydrate formation procedure in Kamyaran CGS pressure reduction station

Table (4) Bubble Point curve table.

Pressure Temperature Volume Enthalpy
(psig) (c) (m3/kg mol) (kJ/kgmol)
11.32 -163.7 3.363 -8.987
19.40 159.3- 3.416 -8.962
30.15 -154.5 3. 478 -8.935
44.43 -149.4 3.550 -8.905
63.31 -143.9 3.637 -8.873
88.08 -138.0 3.740 -8.838
120.2 -131.9 3.865 -8.799
161.1 -125.4 4.016 -8.758
212.1 -118.7 4.201 -8.713
273.8 -112.0 4.429 -8.664
345.9 -105.2 4.712 -8.613
426.6 -98.65 5.065 -8.559
512.5 -92.45 5.505 -8.502
598.3 -86.78 6.057 -8.444
677.8 -81.77 6.747 -8.386
738.8 -77.90 7.511 -8.334
772.1 -75.66 8.109 -8.300
790.6 -74.31 8.552 -8.278
801.2 -73.46 8.868 -8.263
808.7 -72.82 9.133 -8.252
Table (5) Dew Point curve table
Pressure Temperature Volume Enthalpy
(psig) (c) (m3/kg mol) (kJ/kgmol)
836.8 -67.48 0.1237 -8.145
837.4 -68.14 0.1186 -8.159
837.3 -68.40 0.1166 -8.164
833.7 -69.76 0.1074 -8.192
824.7 -71.16 9.928 -8.220
810.4 -72.66 9.202 -8.249
808.7 -72.82 9.133 -8.252
5. DISCUSSION percentage and the type of the equation in the
In this study first by predicting the hydrate simulation environment (Peng-robinson state
formation condition in pressure reduction station equation) pressures and temperatures under which
it was tried to do the simulation for hydrate hydrate was formed were determined. In continue
formation and to prevent it. Putting the compound the highest pressures and temperatures and dew

Jafarbeigi Ehsan, et al. 1035

 Studying and simulating gas hydrate formation procedure in Kamyaran CGS pressure reduction station
and bubble formation points in the condition of
hydrate formation were determined in the
intended station. Using the result we can help the
operator to adjust the station heater temperature
with use of the simulator results to prevent the
hydrate formation conditions.
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