Professional Documents
Culture Documents
By
Farman Saeed Abd. Zangana
(B.Sc. in Chemical Engineering 2004)
Supervised by
Assist.Prof. Dr.Anaam A.Sabri
2012
CERTIFICATE
We certify that we have read this research entitled " A study of the
dehydration process of natural gas in Iraqi North Gas Company and
the treatment methods of molecular sieve problems " by Farman
Saeed Abd. Zangana and as an Examining Committee examined the
student in its contents and that in our opinion it meets the standard of a
research for the degree of Higher Diploma in Chemical Engineering
/Petroleum Refining and Gas Technology.
Signature:
Assistant Prof. Dr. Anaam A.Sabri
(Supervisor)
Date: / / 2012
Signature: Signature:
Assist. Prof. Dr.Mohammed F.Abid Prof. Dr. Mumtaz A. Zablouk
(Member) (Chairman)
Date: / / 2012 Date: / / 2012
Signature:
Prof. Dr. Mumtaz A. Zablouk
Head of Chemical Engineering Department
Date: / / 2012
CERTIFICATION
This is to certify that I have read the research titled " A study
of the dehydration process of natural gas in Iraqi North Gas
Company and the treatment methods of molecular sieve
problems " and corrected any grammatical mistakes I found. The
research is therefore qualified for debate.
Signature:
Prof. Dr. Mumtaz A. Zablouk
University of Technology
Date: / / 2012
Acknowledgments
First of all, praise is to Allah for every thing. Without his great
assistance the work wouldn't have been finished.
I would like to express my sincere appreciation and thanks to my
supervisor Assist.Prof. Dr.Anaam A.Sabri, for his constant guidance and
valuable comments, without which, this research would not have been
successfully completed.
My grateful thanks to Prof. Dr. Mumtaz A. Zablouk, the Chairman
of the Department of Chemical Engineering at the University of
Technology for the provision of research facilities.
My deep thanks go to Assist. Prof. Dr. Mohammed I. Mohammed,
the head of post graduate committee for all the help and encouragement,
also I wish to express my sincere gratitude to my family for them
encouragement and helpful.
Also I would like to convey my sincere appreciation to any one that
helped me in Iraqi North Cas Company.
Also I would like to convey my sincere appreciation to all staff of
Chemical Engineering Department in the University of Technology and the
workshops unit.
Finally, to all that helped me in one way or another, I wish to express
my thanks.
Farman
Abstract
The purpose of this research is to study the dehydration process of
natural gas by adsorption using molecular sieve as it is in the North Gas
Company. Dehydration of natural gas is needed to remove the water that is
associated with natural gas in vapor form. The natural gas industry has
recognized that dehydration is necessary to insure smooth operation of gas
transmission lines, dehydration prevents the formation of gas hydrates and
reduces corrosion. Unless gases are dehydrated, liquid water may condense
in pipeline and accumulate at low point along the line and reducing its
flow capacity. Several methods have been developed to dehydrate gases in
an industrial scale . The four major methods of dehydration are direct
cooling , indirect cooling , absorption and adsorption. This study focuses
on the adsorption method which is used to dehydrate the natural gas in
North Gas Company and also focuses on the problem of breaking up and
aging of the molecular sieve before ending its real life time .Some testing
were made on the aging and the new molecular sieve to show the difference
between them. Some suggestions are made to overcome the problem of
aging of the molecular sieve, like improve the efficiency of gas
separator,using antifoaming to prevent liquid carryover, choose the
regeneration conditions carefully, using multi bed technology and using
glycol dehydration unit with molecular sieve dehydration unit to reduce the
water content of natural gas.
Contents
Subject Page
1 Chapter One
Introduction 1-3
1-1 Problem Statement 3
1-2 Scope of the Study 3
2 Chapter Two 4
Literature Review 4
2-1 Types of Dehydration of Natural Gas 4
2-1-1 Direct Cooling 4
2-1-2 Indirect Cooling 4-5
2-1-3 Dehydration by Absorption 5-9
2-1-4 Dehydration by Adsorption (Solid Desiccant) 10
2-2 Types of Adsorbents 11
2-2-1 Alumina 11
2-2-2 Silica Gel and Silica-Alumina Gel 11
2-2-3 Molecular Sieves 11-13
2-3 Some Types of Molecular Sieves 14
2-3-1 3A Molecular Sieve 14
2-3-2 4A Molecular Sieve 14-15
2-3-3 5A Molecular Sieve 15-16
2-3-4 13X Molecular Sieve 16
2-4 Solid Desiccant Adsorption Kinetics 16-17
2-5 Fundamentals of Adsorption 17-18
2-6 Development of Adsorption Isotherms 18-19
2-6-1 Freundlich Isotherms 19- 20
2-6-2 Langmuir Isotherm 20-21
2-7 Some previous Work on Dehydration of Natural Gas
3 Chapter Three 23
Design and Theoretical Considerations 23
3-1 Design Consideration 23
3-1-1 Solid Desiccant Dehydration 23
3-1-1-1 Allowable Gas Velocity 23-24
3-1-1-2 Bed Length to Diameter Ratio 24-25
3-1-2-8 Filters 29
3-2-2-3 Reboiler 34
3-2-2-3-1 Salt Contamination 34
3-2-2-3-2 Glycol Degradation 34-35
3-2-2-3-3 Acid Gas 35
3-2-2-3-4 Surge Tank 35
3-2-2-3-5 Heat Exchanger 35-36
3-2-2-3-6 Phase Separator (Flash Tank) 36
3-2-2-3-7 Glycol Circulation Pump 36
4 Chapter Four 37
Case Study 37
4-1 Dehydration Process 37-38
4-2 Regeneration Process 38-39
4-3 The Molecular Sieve Dehydrate 39-42
5 Chapter Five 43
5-1 Result and Discussion 43-49
5-2 Overcome the Breaking Up and Aging Problems of the 49-50
Molecular Sieve
6 Chapter Six 51
Conclusions and Recommendations 51-53
6-1 Conclusions 51-52
6-2 Recommendations 53
Chapter One Introduction
Introduction
Today, natural gas is one of the most important fuel in our life and one
of the principle sources of energy for many of our day-to-day needs and
activities. It is an important factor for the development of countries that
have strong economies because it is a source of energy for household,
industrial and commercial use, as well as to generate electricity.
Natural gas, in itself, might be considered a very uninteresting gas - it
is colorless, shapeless, and odorless in its pure form, but it is one of the
cleanest, safest ,and most useful of all energy sources. Natural gas is a
gaseous fossil fuel. Fossil fuels are essentially, the remains of plants and
animals and microorganisms that lived millions and millions of years
ago. It consists primarily of methane but including significant quantities of
ethane, propane, butane, and pentane. Methane is a molecule made up of
one carbon atom and four hydrogen atoms, and is referred to as CH4.
Natural gas is considered 'dry' when it is almost pure methane, having
had most of the other commonly associated hydrocarbons removed. When
other hydrocarbons are present, the natural gas is 'wet'.The natural gas used
by consumers is composed almost entirely of methane .However, natural
gas found at the wellhead, although still composed primarily of methane, is
by no means as pure. Raw natural gas comes from three types of wells: oil
wells, gas wells, and condensate wells.
Natural gas that comes from oil wells is typically termed 'associated
gas'. This gas can exist separately from oil in the formation of (free gas),or
dissolved in the crude oil (dissolved gas). Natural gas from gas and
condensate wells ,in which there is little or no crude oil, is termed non
associated gas. Gas wells typically produce raw natural gas by itself, while
condensate wells produce free natural gas along with a semi-liquid
hydrocarbon condensate. Whatever the source of the natural gas, once
Page 1
Chapter One Introduction
separated from crude oil it commonly exists in raw natural gas or sour
gas.The raw natural gas contains water vapor, hydrogen sulfide
(H2S),carbon dioxide, helium, nitrogen, and other compounds .In order to
meet the requirements for a clean, dry, wholly gaseous fuel suitable for
transmission through pipelines and distribution for burning by end users,
the gas must go through several stages of processing, including the removal
of entrained liquids from the gas, followed by drying to reduce water
content. In order to remove water content, dehydration process is used to
treat the natural gas. Dehydration is the removal of water from an object. In
Physiologic terms, it entails a relative deficiency of water molecules in
relation to other dissolved solutes. Gas dehydration is one of the most
prominent unit operations in the natural gas industry(1).
There are five major reasons for natural gas treating from water contents:
• Liquid water and natural gas can form hydrates which causes plug the
pipelines and other equipments such as valves, collectors etc. (Gas
Hydrate: are solids formed by the physical combination of water and other
small molecules of hydrocarbons. They are icy hydrocarbon compounds of
about 10% hydrocarbon and 90% water).
• Natural gas containing H2S and/or CO2 is corrosive when liquid water is
present (corrosion often occurs when liquid water is present along with
acidic gases, which tend to dissolved and disassociate in the water phase,
forming acidic solutions).
• Water content of natural gas decreases of it is heat value.
• Liquid water in natural gas pipelines potentially causes slugging flow
conditions resulting in lower flow efficiency of the pipelines.
• In most commercial hydrocarbon processes, the presence of water may
cause side reactions, foaming or catalyst deactivation(2).
Page 2
Chapter One Introduction
Page 3
Chapter Two Literature Review
Literature Review
Page 4
Chapter Two Literature Review
● Low affinity for hydrocarbons to minimize their loss during the process.
There are numbers of liquids that can be used to absorb water from
natural gases such as calcium chloride, lithium chloride and glycols. Glycol
dehydration is a liquid desiccant system for the removal of water from
natural gas. It is the most common and economic means of water removal
from these streams .Glycol, the principal agent in this process, has a
chemical affinity for water. The liquid glycol will absorbs the water content
in the natural gas. This means that, when in contact with a stream of natural
gas that contains water, glycol will serve to 'steal' the water out of the gas
Page 5
Chapter Two Literature Review
stream. This operation is called absorption (1) . There are a few types of
glycol usually used in industry with their advantages and disadvantages
like ethylene glycol (EG), diethylene glycol (DEG), triethyleneglycol
(TEG), and tetraethylene glycol (TREG). Glycols typically seen in industry
include monoethylene glycol (MEG) Table( 2-1) shows the properties of
the glycols (1) .The commonly available glycol and their uses are described
as follows.
1. Monoethylene glycol (MEG);high vapor equilibrium with gas so tend to
lose Monoethylene glycol to gas phase in contactor. Use as hydrate
inhibitor where it can be recovered from gas by separation at temperature
below 50ºF.
2. Diethylene glycol (DEG); high vapor pressure leads to high losses in
contactor. Low decomposition temperature requires low reconcentrator
temperature (315 to 340ºF) and thus cannot get pure enough for most
applications.
3.Triethylene glycol (TEG); most common. Reconcentrate at 340-400ºF,for
high purity. At contactor temperatures in excess of 120ºF, there is a
tendency to high vapor losses. Dew point depressions up to 150ºF are
possible with stripping gas.
4. Tetraethylene glycol (TREG); more expensive than TEG but less loss at
high gas contact temperatures. Reconcentrate at 400 to 430ºF.
TEG is by far the most common liquid desiccant used in natural gas
dehydration. It exhibits most of the desirable criteria of commercial
suitability listed here.
1.TEG is regenerated more easily to a concentration of 98-99% in an
atmospheric stripper because of its high boiling point and decomposition
temperature.
2. TEG has an initial theoretical decomposition temperature of 404ºF,
whereas that of diethylene glycol is only 328ºF.
Page 6
Chapter Two Literature Review
Page 7
Chapter Two Literature Review
Page 8
Chapter Two Literature Review
The wet or "rich" glycol exiting the absorber flows through a coil in
the accumulator where it is preheated by hot lean glycol. After the glycol-
glycol heat exchanger, the rich glycol enters the stripping column and
flows down the packed bed section in to the reboiler . Steam generated in
the reboiler strips absorbed water and VOCs out of the glycol as it rises up
the packed bed. The water vapor and desorbed natural gas are vented from
the top of the stripper. The hot regenerated lean glycol flows out of the
reboiler into the accumulator (surge tank) where it is cooled via cross
exchanger with returning rich glycol; it is pumped to a glycol/gas heat
exchanger and back to the top of the absorber. Glycol unit decreases the
water content to 60 ppm (3) .
Sweet
gas
inlet
Page 9
Chapter Two Literature Review
Page
10
Chapter Two Literature Review
Page
11
Chapter Two Literature Review
Page
12
Chapter Two Literature Review
the sieve type. In addition, the pore size plays a significant role, allowing or
prohibiting the entrance of molecules to the pore system (3) .Some types of
molecular sieves and it application in table (2-2).
Page
13
Chapter Two Literature Review
Applications
Page
14
Chapter Two Literature Review
Formula
Na2O . Al2O3 . 2SiO2 . 4.5 H2O
Applications
Deep drying of air, Natural gas, alkane and refrigerant. Generation and
purification of argon. Static dehydration of electronic element,
pharmaceutical and unstable materials. Desiccant for paint, dope and foul
etc. Type 4A molecular sieve is typically used in regenerable drying systems
to remove water vapor or contaminants which have a smaller critical
diameter than four angstroms.
2-3-3 5A Molecular Sieve
Formula
0.75 CaO . 0.25 Na2O . Al2O3 . 2 SiO2 . 4.5H2O
Applications Oxygen/hydrogen PSA (Pressure Swing Adsorption) process
for removal of water and carbon dioxide from air. Type 5A separates normal
Page
15
Chapter Two Literature Review
Molecular Sieve 13X is the sodium form of the type X crystal and has a
much larger pore opening than the type A crystals.The pore size 13X
molecular sieve is about 10 Å . It can adsorb any molecular smaller than 10
Å , mainly used as catalyst carrier, co-adsorption of CO2 and H2O, H2O and
H2S, as desiccant for medical and air compressor system, and can also be
adjusted to fit other various applications. Regeneration : molecular sieve
Type 13X can be regenerated by evacuating or purging, usually at elevated
temperatures. The purge gas temperature must be sufficiently high to bring
the molecular sieve to a level of 250°C - 350°C (8) .
Formula
Na2O . Al2O3 . (2.8±0.2) SiO2 . (6~7)H2O.
Applications
Page
16
Chapter Two Literature Review
0 t1
BED LENGTH
(a)
SAT
ADSORBATE BED
H2O C6+ C5 C4
SATURATION
0 1
BED LENGTH
(b)
Page
18
Chapter Two Literature Review
(𝐶𝐶𝑜𝑜−𝐶𝐶𝐶𝐶)𝑉𝑉
qe = (2-1)
𝑚𝑚
m= mass of adsorbent, g
1
𝑥𝑥
= Kƒ𝐶𝐶𝑒𝑒
𝑛𝑛
(2-2)
𝑚𝑚
Page
19
Chapter Two Literature Review
𝑥𝑥
Where = mass of adsorbate adsorbed per unit mass of adsorbent, mg
𝑚𝑚
1
Log ﴾ 𝑚𝑚𝑥𝑥 ﴿ = log Kƒ + log Ce (2-3)
𝑛𝑛
𝑥𝑥 𝑎𝑎𝑎𝑎𝑎𝑎𝑎𝑎
= (2-4)
𝑚𝑚 1+𝑏𝑏𝑏𝑏𝑏𝑏
a, b = empirical constants
2. Adsorption is reversible.
Page
20
Chapter Two Literature Review
Page
21
Chapter Two Literature Review
adsorbent. Siti (4) studied, the dehydration of natural gas by adsorption using
silica gel as a solid desiccant and he focuses on designing, fabrication,
hydrostatic test and experimental part . Lukás (5) focused on dehydration of
natural gas by absorption drying using triethylene glycol (TEG) its benefits
and disadvantages. Then the dehydration is simulated with Aspen Hysys
software. The minimum glycol mass flow and specific glycol circulation rate
is calculated. Mohamadbeigy (20) presented a comprehensive study on gas
drying unit and investigated the effectiveness parameters such as glycol flow
rate, stages number of absorption tower and stripping gas rate on water
content in glycol dehydration units. Mohamadbeigy,et al (7) investigated
effectiveness parameter of water adsorption on molecular sieve to find
optimum operating condition. The obtained experimental breakthrough
curves were fitted to theoretical models in order to establish the main
mechanisms of mass transfer. Mohamadbeigy , Kasir and Hormozdi (21)
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22
Chapter Three Design and Theoretical Consideration
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23
Chapter Three Design and Theoretical Consideration
for Equation (3-1) given in Table (3-1) for molecular sieve materials.
Table (3-1) Parameters used in Equation (3-1)
Particle type
coefficients
B C
1/8-in. beads 0.0560 0.0000889
1/8-in. extrudate 0.0722 0.000124
1/16-in. beads 0.152 0.000136
1/16-in. extrudate 0.238 0.000210
The design pressure drop across the entire bed should be about 5 psi;
values higher than approximately 8 psi are not recommended. Most designs
are based on∆P/L of about 0.31 -0.44 psi/ft , and typical superficial gas
velocities of 30-60 ft/min(3).
3-1-1-2 Bed Length to Diameter Ratio
After superficial gas velocity is determined, then the diameter and
length of the bed can be calculated from geometry of the adsorber. The
adsorber is normally a cylindrical tower filled with a solid desiccant. The
depth of the desiccant may vary from a few feet to 30 ft or more. The
minimum bed internal diameter for a specified superficial gas velocity is
given by the following equation (Ergun,) (12).
D²= 25(QG)(T)(Z)/(P)(VsG) (3-2)
Where D is bed diameter,ft, QG is gas flow rate, MMscfd;T is inlet gas
temperature, ºR; P is inlet gas pressure, psia; Z is compressibility factor and
VsG is superficial gas velocity, ft/min.
Also, the bed length, can be determined by the following equation (Collins,)
(13) .
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24
Chapter Three Design and Theoretical Consideration
in the absorber to reduce the water content of the gas to the required
specifications (3) .
The water removal rate, assuming the inlet gas is water saturated, can be
determined as:
Wr = QG (Wi –wo)/24 (3-8)
Where Wr is water removed, Ib/hr; Wi is water content of inlet gas,
Ib/MMscf; Wo is water content of outlet gas, Ib/MMscf; and QG gas flow
rate,MMscfd.
The glycol circulation rate is determined on the basis of the amount of
water to be. Higher circulation rates provide little additional dehydration
while increasing reboiler fuel and pumping requirements. Problems can arise
if the TEG circulation rate is too low (3) .
The minimum glycol circulation rate can then be calculated as
QTEG,min = G * Wr (3-9)
Where QTEG,min is the minimum TEG circulation rate (gal TEG/hr) and G is
the glycol-to-water ratio (gal TEG/Ib water removed).
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26
Chapter Three Design and Theoretical Consideration
disengagement area above the top tray and an inlet gas area at the bottom of
the column (3).
D = 9(QTEG)º·⁵ (3-11)
Where QTEG is TEG circulation rate, gal/min ;and D is inside diameter of
stripping column,inch. Smaller diameter towers (less than 2 ft in diameter)
are often packed with ceramic intalox saddles or stainless steel pall rings
instead of trays. Larger-diameter towers may be designed with 10 to 20
bubble cap trays or structured packing.
3-1-2-3 Reboiler
The reboiler and still are typically a single piece of equipment. The
reboiler supplies heat to regenerate the rich glycol in the still by simple
distillation. Reboiler duty can be estimated by the following equation
(Sivalls,) (18).
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27
Chapter Three Design and Theoretical Consideration
Lean glycol from the reboiler is routed through an overflow pipe or weir
to a surge tank or accumulator. Because this vessel is not insulated in many
cases, the lean glycol is cooled to some extent via heat loss from the shell.
This type of exchanger uses the exiting dry natural gas to control the
lean glycol temperature to the absorber. High glycol temperature relative to
the gas temperature reduce the moisture absorption capacity of TEG (3) .
Page
28
Chapter Three Design and Theoretical Consideration
the still vent. Because the hydrocarbons are collected under a vacuum,they
are stable and no vapor losses or weathering occurs. The design of the three-
phase separator is similar to that of two-phase separator except that it has a
second control valve and liquid level controller to drain the accumulated
hydrocarbon phase.
A circulation pump is used to move the glycol through the unit. A wide
variety of pump and driver types are used in glycol systems, including
gas/glycol-powered positive displacement or glycol balance pumps (e.g.,
kimray pumps) and electric motor-driven reciprocating or centrifugal pumps.
3-1-2-8 Filters
Two types of filters are commonly used in glycol system.
The suspended solids content of glycol should be kept below 0.01 wt%
to minimize pump wear,plugging of exchangers,fouling of absorber trays and
stripper packing,solids deposition on the firetube in the reboiler, and glycol
foaming. Solid filters are selected to remove particles with a diameter of 5
µm and larger. A common design is a 3-inch diameter by 36-inch-long
cylindrical element in housing,sized for a flow rate of 1 to 2 gallon per
minutes per element. The filters are sized for a 12 – to 15-psi pressure drop
when plugged. This filter will remove any foreign solid particles picked up
in the absorber before entering the glycol pump.
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29
Chapter Three Design and Theoretical Consideration
High dew point is one of the two common problems that can cause
operating trouble. Possible causes include the following.
1."wet" inlet gas bypasses the dehydrator through cracks in the internal
insulation. Cracks in a liner or in sprayed-on insulation can be detected by
"hot spots" and peeling paint on the outer shell. Other symptoms are fast
water breakthrough and an unusually rapid rise in the effluent gas
temperature during regeneration.
2.Leaking valves also permit wet gas to bypass the dehydrators. Even a
slight leak of hot gas usually produces a detectable temperature rise in what
should be the cold side of the valve. Ultrasonic translators are also useful.
Page
30
Chapter Three Design and Theoretical consideration
regenerate the adsorbents the inlet and outlet temperatures of the adsorber in
regeneration should be analyzed. At the end of the heating step the outlet
temperature should be almost contact during a certain time (30 minutes to 2
hours) depending on the design of the adsorber,and the temperature
difference between inlet and outlet should not be more than 59-68ºF
depending on the quality of the heat insulation.
4.Excessive water content in the wet feed gas due to increased flow
rate,higher temperatures,and lower pressure. It is very important to respect
the inlet temperature (feed temperature) of the adsorbers in case of saturated
gas. Small variations in temperature will lead to significant increases in the
water content (3) .
Satisfactory dew points are observed at the beginning but not for the
entire duration of the drying cycle. Desiccant capacity should decrease with
use but should stabilize at 55-70% of the initial capacity Ballard,
(24).However, premature symptoms of "old gas" are caused by an
unrecognized increase in inlet water loading, an increase in heavy
hydrocarbons (C4+) in feed gas, methanol vapor in feed, desiccant
contamination, or incomplete regeneration.
Page
31
Chapter Three Design and Theoretical Consideration
Sometimes operators have problems with the support grid and leakage
of molecular sieves through the support grid. As a result, they have to
replace the whole bed. Important point here is the good mechanical design of
the support bed, putting three wire mesh on the support grid (4, 10,20 mesh)
and installing the correct quantity and size of ceramic balls.
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32
Chapter Three Design and Theoretical Consideration
3-2-2-1 Absorber
3-2-2-1-2 Foaming
Foaming causes glycol to be carried out of the absorber top with the
gas stream, resulting in large glycol losses and decreased glycol unit
efficiency. Foaming can normally be traced to mechanical or chemical
causes. High gas velocity is usually the source of mechanical entrainment.
Chemical foaming is caused by contaminants in the glycol, liquid
hydrocarbons, well-treating chemicals, salts, and solid. Adequate inlet
separation and filtration system (cartridge filter and activated carbon bed) are
therefore needed to prevent foaming due to chemical contamination.
3-2-2-3 Reboiler
Carry over of brine solution from the field can lead to salt
contamination in the glycol system. Sodium salt(typically sodium chloride,
NaCl) are a source of problems in the reboiler, as NaCl is less soluble in hot
TEG than in cool TEG; NaCl will precipitate from the solution at typical
reboiler temperature of 350-400ºF. The salt can deposit on the fire tube,
restricting heat transfer. If this occurs,the surface temperature of the fire tube
will increase,causing hot spots and increased thermal degradation of the
glycol. The deposition of salt may also result in corrosion of the fire tube.
Dissolved salt cannot be removed by filtration. As a general rule, when the
salt content reaches 1%, the glycol should be drained and reclaimed. If the
level of salts is allowed to increase beyond 1% both severe corrosion and
thermal degradation threaten the system.
Some natural gas contains H2S and/or CO2, and these acid gases may
be absorbed in the glycol. Acid gases can be stripped in the reboiler and still.
Mono-,di-, or triethanolamine may be added to the glycol to provide
corrosion protection from the acid gases(3) .
When surge tanks also serve as glycol/glycol heat exchanger, the level
must be monitored to ensure that the lean glycol covers the rich glycol coil.
Otherwise, inadequate heat exchange will occur, and the lean glycol will
enter the absorber at an excessively high temperature.
Page
35
Chapter Three Design and Theoretical Consideration
poor dehydration and insufficient dew point depression can result. Also,
glycol vaporization losses to the product gas may be higher with increased
lean glycol temperature. Poor heat transfer and the resulting high lean glycol
temperature are usually caused by fouled heat exchangers. Exchangers may
be fouled by deposits such as salt, solids,coke,or gum. Corrosion of the coil
in surge tank heat exchangers can also present operating problems, as it can
lead to cross-contamination of rich and lean glycol.
Major problems associated with the circulation pump and rates are
related to reliability,pump wear, and overcirculation or undercirculation(3) .
Page
36
Chapter Four Case Study
Case Study
In the north gas company the treated gas stream from the sweetening
unit is cooled to approximately 38ºC through EA-1305 to condense out
excess water.This cooling reduces significantly the required amount of
molecular sieve .The water condensate ,after separation from the gas stream
in the K.O.(knock-out) drum which is a vapor-liquid separator. It is a vertical
vessel used in several industrial applications to separate a vapor-liquid
mixture. There is a barrier inside K.O drum to separator the gas by bang to
it .Gravity causes the liquid to settle to the bottom of the vessel ,where it is
withdrawn and there is a clip upper the drum to prevent crossing of the liquid
with gas . (FA-1304), is returned to the sweetening unit for re-use. The gas
is normally not cooled enough to condense hydrocarbons. Any condensed
hydrocarbons ,if present in the K.O. drum, are sent to the Burning pit (BT-
0603). The gas from K.O. drum flows to the charge-Gas Dryer (FF-1301
A/B) before proceeding to the downstream , low-temperature separation
section. The gas is dried to prevent plugging due to freeze-ups and hydrate
formation at low temperatures . Two vessels containing molecular sieve
(type 4A) desiccant are provided ; these alternate between on-stream drying
service and regeneration , on an 8-hour cycle (cycle length will be longer
with new desiccant and progressively decline with time). An inter-bed
moisture probe monitors operation and detects water break-through from the
bed .The dried gas is sent to the activated carbon Bed (FA-1305), where any
trace amounts of mercury in the gas stream are removed .The gas then flows
through the filter (FD-1301 A/B), to remove desiccant dust and other solids
which may cause plugging in the down-stream equipment. Then the gas is
sent to section drum (surge drum)(FA-1302) where its given enough time to
process. The gas is then compressed to approximately 46 kg/cm²G with
Page
37
Chapter Four Case Study
Page
38
Chapter Four Case Study
the K.O. drum (FA-1308) where water is removed . The water separated
from the K.O. (knock-out) drum is degassed in the degassing Drum (FA-
1306) before being discharged to the waste water treatment . The
regeneration gas from the K.O. (knock-out) drum (FA-1308) is recycled
back to the Absorber in the sweetening unit , for acid gas removal (DA-
1201) (10) . Anti surge out from the top of the vessel FA-1303 and enter the
path to enter the gas to the compressor GB-1301. Figure (4-1) illustrates this
process, and table (4-1) shows the composition of natural gas in dehydration
unit.
In the North Gas Company, the molecular sieve bed for dehydration of
natural gas as shown in figure (4-2) consists of the following:-
1. The upper ceramic balls layer used as a support to the molecular sieve
and facilitates the passage of gas to the molecular sieve. The diameter of
single ball is (19mm) and the height of ceramic balls layer is (250mm) .
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39
Chapter Four Case Study
2.The wire mesh layer is used to isolated molecular sieves from ceramic
balls and keeps the molecular sieves from coming up with gas.
4700 mm I.D
1. Ceramic balls
250mm
4800mm
2. Wire mesh
6800mm
3. Molecular sieves
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40
Chapter Four Case Study
3.The molecular sieves layer of type 4A represents the main part for
adsorbing the water from the inlet gas. The height of the molecular sieve
layer is (4800mm).
4.The lower ceramic balls layer is used to support the molecular sieve and
facilitates the passage of gas to the molecular sieve passage of gas to the
molecular sieve. The diameter of single ball is (6.2mm) and the height of
ceramic balls layer is (100mm) .
5.Bottom support grid, used to support the heavy weight of molecular sieve
(53.325ton).
Two beds are used in cyclic operation to dry the natural gas on a
continuous basis , one bed operates in adsorption , while the second operates
in desorption , and both beds are switched periodically. For dehydration , of
natural gas 4A type of molecular sieve is used in the North Gas
Company.This is a good choice because of its high selectivity and affinity
for water but the problem is after a certain number of cycles , molecular
sieve beds show broken particles and dust ,leading to aging of the molecular
sieve after (1.5-2) years instead of three years (the real life time of the
molecular sieve).
Many tests are made for the aging molecular sieve and the new
molecular sieve to show the difference between them.
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41
Chapter Four Case Study
4. The surface area and the pore volume of the aging and the new molecular
sieve were measured at the Petroleum Research and Development Center.
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42
Chapter Five Results and Discussion
The results of testing the aging and the new molecular sieve are shown
in figure (5-1) and figure (5-2) . The results of X-ray Diffraction test showed
no large and influential different between the new and the aging molecular
sieve as shown in figures (5-1) and (5-2). The results of (FT-IR) (Fourier
Transform Infra Red) as in figure (5-3) showed no difference between the
new and the aging of molecular sieve. The crystal structure of the aging and
the new molecular sieve were tested by microscope with magnification
power (100X ) (BEL. Italy ) and a picture was taker for the result of the
tested samples, the microstructure of each sample is different as shown in
figures (5-4) and (5-5).From these figures, it can be seen that the dark
regions in the aging molecular sieve are less than in the new molecular
sieves. This means that most of the pores (dark regions) in the aging
molecular sieve are blocked by contaminants which causes the decreasing in
the adsorption capacity of the molecular sieves. Also the surface area and the
pore volume of the aging and the new molecular sieve were measured as
shown in table (5-1). It can be seen that the surface area and the pore volume
for the aging molecular sieve are lower than for the new molecular sieve.
This confirms the above result about the blocking of the molecular sieve.
Table (5-1) Values of Surface Area and Pore volume as means the new
and aging molecular sieve
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43
Chapter Five Result and Discussion
Page
44
Chapter Five Result and Discussion
Page
45
Chapter Five Result and Discussion
Page
46
Chapter Five Result and Discussion
Page
47
Chapter Five Result and Discussion
1.The incomplete removal of free liquid water in the inlet gas separator , so
the natural gas enters the dehydrator with a large amount of water
(2800ppm). This is a very important part of the system because free water
can cause the adsorbent materials to break down.This leads to higher
pressure drop and channeling , reducing the overall performance of the unit.
2. Liquid (particularly amines from sweetening unit) may carry over in the
molecular sieve bed which has a negative impact on the drying process (i.e.
poor gas flow distribution due to fines formation as a consequence of
chemical attack causing an increase of the pressure drop and a decrease of
adsorption time).
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48
Chapter Five Result and Discussion
2. Liquid (particularly amines) carry over in the molecular sieve bed must be
prevented by using antifoaming material, in the previous unit , and the gas
flow rate must be controlled carefully because at excessive velocities, amines
can be lifted up of the sweetening unit with the gas to the molecular sieve
bed.
Page
49
Chapter Five Result and Discussion
6-1 Conclusions
From this research it can be concluded that the reason for breaking
up,blocking and aging the molecular sieve, is one or more of the following:
2. Water condensed.
3. Liquid (particularly amines) carry over in the molecular sieve bed must be
prevent by using antifoaming material.
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51
Chapter Six Conclusions and Recommendations
Page
52
Chapter Six Conclusions and Recommendations
6-2 Recommendations
After finishing this study there are some recommendations that may
be useful for research in the future work.
2. Study the feasibility when glycol dehydration unit is used at the first to
reduce the water content of natural gas to around 60 ppm v and then use
molecular sieve for final drying in steal of using only molecular sieve for
dehydration of natural gas . In this case , molecular sieve problems which
may occur because of high water content of natural gas.
Page
53
Page
54
References
Petroleum & Coal 49 (1), 41-45, 2007. Received December 21, 2006;
accepted June 25, 2007.
8.From the internet (the chemical structure of molecular sieve types).
9.Metcalf and Eddy., "wastewater engineering treatment and reuse" 4th
edition. 2003.
10.Iraqi North Gas project process plant operating manual vol 1.
11.Activated alumina &Molecular Sieves. Quality and advanced
technology.Company Axens , Procatalyse Catalysts & Adsorbents.
12. Ergun, S ., Fluid flow through packed column. Chem. Eng. prog. 48, 2
1952. Cited in reference (3).
13. Collins,J.J., AIChE Symp. Ser., No. 74, 63: 31, 1967. Cited in
reference (3).
14.Simpson,E.A., and Cummings, W.P., A practical way to predict silica
gel performance."chem. Eng. Prog. 60(4), 57-60 ,1964. Cited in reference
(3).
15. Ledoux, E., Chem. Eng. (March 1948). Cited in reference (3).
16. McCabe, W.L., Smith, C.J., and Harriott, P., "Unit Operations of
Chemical Engineering," 4th Ed. McGraw-Hill, New York (1985). Cited in
reference (3).
17. Souders, M., and Brown, G.G., Fundamental design of absorbing and
stripping columns for complex vapours Ind. Eng. Chem. 24, 519. Cited in
reference (3).
18. Caldwell, R.E., "Glycol Dehydration Manual,"NATCO Group,
Tulsa,OK (Jan 30, 1976) (Sivalls, C.R., "Glycol Dehydration Design
Manual." Sivalls, Inc., Odessa, TX (June 1976). Cited in reference (3).
19 . Abu Phabi "Middle east adsorbents and gas processing Technology
conference" uAE , 2008.
20. Kh. Mohamadbeigy"Studying Of The Effectiveness Parameters On Gas
Dehydration Plant" Received December 15, 2007, accepted May 15, 2008.
21. N.Kasiri , Sh .Hormozdi "Improving performance of absorption tower
in natural gas dehydration process .
22. Vincente n. Hernandez-Valencia and et al"design glycol units for
maximum efficiency".
23. M. Gholaml and et al. Ind . engineering. Chemical .Res. 2010 , 49(2) ,
pp838-846 ).
24. Ballard, D., "How to Improve Cryogenic Dehydration."petroenergy,
83,Houston, TX (sept. 12-16, 1983). Cited in reference (3).
ﺍﳋﻼﺻﺔ U
اﳍﺪف ﻣﻦ ﻫﺬا اﻟﺒﺤﺚ ﻫﻮ دراﺳﺔ ﻋﻤﻠﻴﺔ اﻟﺘﺠﻔﻴﻒ ﻟﻠﻐﺎز اﻟﻄﺒﻴﻌﻲ ﻋﻦ ﻃﺮﻳﻖ اﻻﻣﺘﺰاز ﺑﺎﺳﺘﺨﺪام اﳌﻨﺎﺧﻞ
اﳉﺰﻳﺌﻴﺔ ﻛﻤﺎ ﻫﻮ اﳊﺎل ﰲ ﺷﺮﻛﺔ ﻏﺎز اﻟﺸﻤﺎل .ﲡﻔﻴﻒ اﻟﻐﺎز اﻟﻄﺒﻴﻌﻲ ﺿﺮوري ﻹزاﻟﺔ اﳌﺎء اﳌﺼﺎﺣﺐ ﻟﻠﻐﺎز
اﻟﻄﺒﻴﻌﻲ ﻋﻠﻰ ﺷﻜﻞ ﲞﺎر.ﺻﻨﺎﻋﺔ اﻟﻐﺎز اﻟﻄﺒﻴﻌﻲ أدرﻛﺖ ان اﻟﺘﺠﻔﻴﻒ ﻫﻮ ﺿﺮوري ﻟﻀﻤﺎن اﻟﺘﺸﻐﻴﻞ اﻟﺴﻬﻞ
ﰲ ﺣﺎﻟﺔ ﻋﺪم اﺟﺮاء ﳋﻄﻮط ﻧﻘﻞ اﻟﻐﺎز ,اﻟﺘﺠﻔﻴﻒ ﳝﻨﻊ ﺗﻜﻮﻳﻦ ﻫﻴﺪرات اﻟﻐﺎز ,وﻳﻘﻠﻞ ﻋﻤﻠﻴﺔ اﻟﺘﺄﻛﻞ .
ﻋﻤﻠﻴﺔ اﻟﺘﺠﻔﻴﻒ ﻗﺪ ﻳﺘﻜﺜﻒ اﳌﺎء اﻟﺴﺎﺋﻞ ﰲ اﻷﻧﺒﻮب وﻳﺘﺠﻤﻊ ﰲ ﻧﻘﻄﺔ ﻣﻨﺨﻔﻀﺔ ﻋﻠﻰ ﻃﻮل اﳋﻂ وﻳﻘﻠﻞ ﻣﻦ
ﺪرﻬﺗﺎ ﻋﻠﻰ اﻟﺘﺪﻓﻖ .وﻗﺪ وﺿﻌﺖ اﻟﻌﺪﻳﺪ ﻣﻦ اﻟﻄﺮق ﻟﺘﺠﻔﻴﻒ اﻟﻐﺎزات ﻋﻠﻰ ﻣﺴﺘﻮى ﺻﻨﺎﻋﻲ .وﻫﻨﺎك ارﺑﻌﺔ
ﻃﺮق رﺋﻴﺴﻴﺔ ﻟﻠﺘﺠﻔﻴﻒ ﻫﻲ اﻟﺘﱪﻳﺪ اﳌﺒﺎﺷﺮ ,واﻟﺘﱪﻳﺪ ﻏﲑ اﳌﺒﺎﺷﺮ ,اﻣﺘﺼﺎص ,اﻣﺘﺰاز .وﺗﺮﻛﺰ ﻫﺬﻩ اﻟﺪراﺳﺔ ﻋﻠﻰ
ﻃﺮﻳﻘﺔ اﻻﻣﺘﺰاز واﻟﺬي ﻳﺴﺘﺨﺪم ﻟﺘﺠﻔﻴﻒ اﻟﻐﺎز اﻟﻄﺒﻴﻌﻲ ﰲ ﺷﺮﻛﺔ ﻏﺎز اﻟﺸﻤﺎل ،وﻳﺮﻛﺰ أﻳﻀﺎ ﻋﻠﻰ ﻣﺸﻜﻠﺔ
ﺑﻌﺾ اﻟﺘﺠﺎرب اﺟﺮﻳﺖ ﻟﻠﻤﻨﺎﺧﻞ ﺗﻔﺘﻴﺖ واﻧﺘﻬﺎء ﻛﻔﺎءة اﳌﻨﺎﺧﻞ اﳉﺰﻳﺌﻴﺔ ﻗﺒﻞ أن ﻳﻨﺘﻬﻲ ﻋﻤﺮﻩ اﻟﺘﺸﻐﻴﻠﻲ .
اﳉﺰﻳﺌﻴﺔ ﻟﻠﺠﺪﻳﺪ واﻟﺘﺎﻟﻒ ﻷﻇﻬﺎر اﻟﻔﺮق ﺑﻴﻨﻬﻤﺎ .ﺑﻌﺾ اﳌﻘﱰﺣﺎت وﺿﻌﺖ ﻟﻠﺘﻐﻠﺐ ﻋﻠﻰ ﻣﺸﻜﻠﺔ اﻧﺘﻬﺎء ﻛﻔﺎءة
اﳌﻨﺎﺧﻞ اﳉﺰﻳﺌﻴﺔ ,ﻣﺜﻞ ﺗﺤﺴﻴﻦ ﻛﻔﺎءة وﻋﺎء ﻓﺼﻞ اﻟﻐﺎز ,اﺳﺘﺨﺪام ﻣﺎﻧﻊ اﻟﺮﻏﻮة ﻟﺘﺠﻨﺐ ﻋﺒﻮر اﻷﻣﲔ ﻣﻊ
اﻟﻐﺎز,اﺧﺘﻴﺎر ﻇﺮوف اﻋﺎدة اﻟﺘﻨﺸﻴﻂ ﺑﺪﻗﻪ ,اﺳﺘﺨﺪام ﺗﻜﻨﻮﻟﻮﺟﻴﺎ ﺛﻨﺎﺋﻲ اﳌﺎدة واﺳﺘﺨﺪام وﺣﺪة اﻟﺘﺠﻔﻴﻒ
ﺑﺎﻟﻜﻼﻳﻜﻮل ﺑﺎﻷﺿﺎﻓﺔ اﱃ وﺣﺪة اﻟﺘﺠﻔﻴﻒ ﺑﺎﳌﻨﺎﺧﻞ اﳉﺰﻳﺌﻴﺔ ﳋﻔﺾ ﳏﺘﻮى اﳌﺎء ﻣﻦ اﻟﻐﺎز اﻟﻄﺒﻴﻌﻲ.
ﻭﺯﺍﺭﺓ ﺍﻟﺗﻌﻠﻳﻡ ﺍﻟﻌﺎﻟﻲ ﻭﺍﻟﺑﺣﺙ ﺍﻟﻌﻠﻣﻲ
ﺍﻟﺟﺎﻣﻌﺔ ﺍﻟﺗﻛﻧﻭﻟﻭﺟﻳﺔ
إﻋداد
ﺒﺈﺸراف