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