Kurdistan Regional ‫هەرێمى كوردستانى عيراق‬

Government
‫سەرۆكايەتى ئەنجومەنى وەزيران‬
Presidency of Ministers
Council ‫وەزارەتى خوێندنى‬
Ministry of Higher Education ‫باالوتوێژينەوەى زانستى‬
and Scientific Research ‫سەرۆكايەتى زانكۆى كۆيە‬
Koya University ‫فاكەلتى ئەندازيارى‬
Faculty of Engineering
‫بەشى کيمياوی‬
Department of Chemical

METHYLDIETHANOLAMINE AS
A SOLVENT FOR GAS
DESULFURIZATION:
PROCESS SIMULATION AND
OPTIMIZATION
A Project Submitted to the
Chemical Engineering Department
Faculty of Engineering/Koya University
In partial Fulfillment of the Requirement for the Degree of Bachelor in
Chemical Engineering.
Prepared by
SAFEEN YASEEN JA’FAR
RIVAN DLER ALI
IBRAHIM ALI
RAMAZAN SHKUR KAKL
Supervised by
MR. REBWAR K. ABDULRAHMAN
-- DEC. 2022
ACKNOWLEDGMENT
All praise to Allah, Lord of all the worlds, with blessing, peace and mercy upon his Prophet
Mohammed. Allah gave us strength and health to perform and accomplish our project.

We would like to express our sincere and deepest gratitude and appreciation to our beloved
supervisor (Mr. Ribwar K. Abdulrahman) for making this research possible by his
guidance, support, encouragement, and valuable scientific suggestions throughout the
course of my research.

Finally, we wholeheartedly thank and pay tribute to the continuous support of our families
and to all those we forgot here to mention their name that helped and guided us even by
one useful scientific word directly or indirectly and everyone who wish us success.

I
ABSTRACT
Natural gas is the most important and popular fossil fuel for the past decades and it will continue to be in
the future. Probably the main reason is that natural gas ‘emissions are the cleanest among all other sources
of energy. However, before it is ready for domestic and industrial use, unwanted non-hydrocarbon
components such as Hydrogen Sulfide and Carbon Dioxide must be removed. These impurities are
undesirable due to their toxicity and lack of heating value. Some of the problems that these acid gases can
cause are corrosion and environment pollution. The process of their removal is called sweetening and this
project focuses on H2S removal by aqueous amine solution. This removal method is proven to be one of
the most efficient and widely used in the industry. one amine solvent are considered for this study –
methyldiethanolamine (MDEA). Furthermore, simulation is made with the help of specialized software –
ProMax V5.

II
TABLE OF CONTENTS
CHAPTER 1: INTRODUCTION ............................................................................................................... 1
1.1 INTRODUCTION TO NATURAL GAS............................................................................................ 1
1.2 NATURAL GAS HISTORY ............................................................................................................ 3
1.3 NATURAL GAS SOURCE .............................................................................................................. 3
1.3.1 NON-ASSOCIATED GAS ........................................................................................................... 4
1.3.2 ASSOCIATED GAS ................................................................................................................... 4
1.3.3 UNCONVENTIONAL GAS ......................................................................................................... 5
1.4 NATURAL GAS ORIGIN AND COMPOSITION .............................................................................. 5
1.5 NATURAL GAS BEHAVIORS........................................................................................................ 8
1.5.1 GENERAL GAS PROPERTIES ................................................................................................... 8
1.5.2 NATURAL GAS PROPERTIES ................................................................................................... 8
1.6.1 NATURAL GAS PRODUCTION ANS TRANSPORTATION ............................................................ 9
1.6.2 NATURAL GAS PROCESSING OVERVIEW .............................................................................. 10
1.6.3 NATURAL GAS TREATING & PROCESSES .............................................................................. 10
CHAPTER 2: LITERATURE REVIEW ................................................................................................... 19
2.1 NATURAL GAS PROCESSING .................................................................................................... 19
2.2 SOUR & SWEET NATURAL GAS ................................................................................................ 20
2.2.1 SOUR GAS ............................................................................................................................. 20
2.2.2 SWEET GAS ........................................................................................................................... 20
2.2.3 WHAT IS THE DIFFERENCE BETWEEN SWEET AND SOUR NATURAL GAS? .......................... 20
2.3 GAS SWEETENING PROCESS CLASSIFICATIONS ..................................................................... 22
2.4 PHYSICAL SOLVENT PROCESSES ............................................................................................. 25
2.5 DIRECT CONVERSION PROCESSES ........................................................................................... 26
2.6 DRY BED PROCESSES (SOLID BED PROCESSES) ...................................................................... 28
2.7 MISCELLANEOUS PROCESSES .................................................................................................. 29
2.8 CHEMICAL SOLVENT PROCESSES. ........................................................................................... 30
2.8.1 AMINE PROCESSES OVERVIEW ............................................................................................ 30
2.8.2 BASIC PROCESS DESCRIPTION ............................................................................................. 30
2.9 MONOETHANOLAMINE (MEA) SYSTEM................................................................................... 31
2.9.1 REGENERATION ................................................................................................................... 31
2.9.2 ADVANTAGES ....................................................................................................................... 32

III
 2.9.3 DISADVANTAGES .................................................................................................................. 32
2.9.4 CORROSION CONSIDERATIONS ............................................................................................ 32
2.9.5 FOAM CONSIDERATIONS...................................................................................................... 32
2.9.6 MEA LOSSES ......................................................................................................................... 32
2.10 DIETHANOLAMINE (DEA) SYSTEMS ...................................................................................... 33
2.10.1 ADVANTAGES...................................................................................................................... 33
2.10.2 DISADVANTAGES ................................................................................................................ 33
2.10.3 AMINE LOSSES .................................................................................................................... 33
2.11 METHYLDIETHANOLAMINE (MDEA SYSTEM)....................................................................... 34
2.11.1 MDEA SYSTEM OVERVIEW .................................................................................................. 34
2.11.2 PRODUCTION AND USES OF MDEA .................................................................................... 34
2.11.3 STRUCTURE OF MDEA ........................................................................................................ 35
2.11.4 PROPERTIES OF MDEA ....................................................................................................... 36
2.11.5 ADVANTAGES...................................................................................................................... 37
2.11.6 WHY MDEA?........................................................................................................................ 37
2.11.7 AMINE CONCENTRATION ................................................................................................... 38
2.11.8 MDEA CONCENTRATION: ................................................................................................... 38
2.12 GAS DESULFURIZATION/SWEETENING BY ADSORPTION .................................................... 39
2.13 GAS DESULFURIZATION/SWEETENING BY ABSORPTION (MDEA) ....................................... 40
2.13.1 EQUIPMENT DESCRIPTION ................................................................................................ 41
2.13.2 PROCESS DESCRIPTION: .................................................................................................... 46
CHAPTER 3: METHODOLOGY ............................................................................................................ 51
3.1 SIMULATION OVEVIEW ............................................................................................................ 51
3.2 WHY SIMULATE? ....................................................................................................................... 51
3.3 SIMULATION USES IN PROCESS/CHEMICAL ENGINEERING ................................................... 51
3.4 PROCESS SIMULATION SOFTWARE ......................................................................................... 52
3.5 PROMAX .................................................................................................................................... 52
3.6 WHY DO YOU NEED PROMAX .................................................................................................. 52
CHAPTER 4: MASS & ENERGY BALANCE .......................................................................................... 54
4.1 MASS BALANCE ........................................................................................................................ 54

IV
LIST OF FIGURES
FIGURE 1: PRIMARY GLOBAL ENERGY CONSUMPTION 2021 (Rapier, 2022) ............................. 2
FIGURE 2: CRUDE OIL, ASSOCIATED GAS, ANDNON-ASSOCIATED GAS RESERVOIRS
(Jemo, 2017) ............................................................................................................................................... 4
FIGURE 3: THE DIAGRAM ABOVE DISPLAYS THE SEGMENTS OF THE OIL AND NATURAL
GAS INDUSTRY (Us Epa, 2016). ............................................................................................................. 9
FIGURE 4: HORIZONTAL SEPARATOR SCHEMATIC (Steward and Arnold, 2008). ...................... 13
FIGURE 5: VERTICAL SEPARATOR SCHEMATIC (Steward and Arnold, 2008). ............................ 14
FIGURE 6: SPHERICAL SEPARATOR SCHEMATIC (Steward and Arnold, 2008). .......................... 14
FIGURE 7: SCHEMATIC OF A HORIZONTAL THREE-PHASE SEPARATOR WITH INTERFACE
(Steward and Arnold, 2008). ..................................................................................................................... 15
FIGURE 8: SCHEMATIC OF A VERTICAL THREE-PHASE SEPARATOR WITH INTERFACE
(Steward and Arnold, 2008). ..................................................................................................................... 16
FIGURE 9: NATURAL GAS PROCESS FLOW DIAGRAM (Uwitonze, Hwang and Lee, 2020)........ 18
FIGURE 10: TYPICAL FLOW SCHEMATIC FOR A PHYSICAL SOLVENT PROCESS (Stewart and
Arnold, 2011). ........................................................................................................................................... 26
FIGURE 11: SIMPLIFIED FLOW SCHEMATIC OF THE STRETFORD PROCESS (Stewart, 2014).
................................................................................................................................................................... 27
FIGURE 12: TYPICAL IRON OXIDE PROCESS FLOWSHEET (Abdel-Aal and Aggour, 2003). ..... 29
FIGURE 13: GENERAL FLOW DIAGRAM FOR AMINE PLANT (Abdulrahman and Ibtisam, 2015).
................................................................................................................................................................... 31
FIGURE 14: STRUCTURE OF METHYL-DIETHANOLAMINE (IN 2D)........................................... 35
FIGURE 15: STRUCTURE OF METHYL-DIETHANOLAMINE (IN 3D)........................................... 35
FIGURE 16: NATURAL GAS SWEETENING UNIT (GSU) BY AMINE (MDEA) (Steward and
Arnold, 2011). ........................................................................................................................................... 40
FIGURE 17: INLET SEPARATOR/SCRUBBER ................................................................................... 41
FIGURE 18: AMINE ABSORBER/CONTRACTOR.............................................................................. 42
FIGURE 19: FLASH SEPARATOR ........................................................................................................ 43
FIGURE 20: LEAN/RICH CROSS HEAT EXCHANGE ....................................................................... 44
FIGURE 21: REBOILER .......................................................................................................................... 45
FIGURE 22: STRIPPER COLUMN ........................................................................................................ 45
FIGURE 23: BUBBLE CAP TRAYS IN AN ABSORBER .................................................................... 47
FIGURE 24: MIST EXTRACTOR .......................................................................................................... 47

V
LIST OF TABLES
TABLE 1: TYPICAL NATURAL GAS COMPOSITION (Wójcik, 2014). .............................................. 6
TABLE 2: SHALE GAS COMPOSITION IN THE USA (Wójcik, 2014). ............................................... 7
TABLE 3: COMMERCIAL GAS SWEETENING PROCESSES (A.H Younger, 2004). ...................... 23
TABLE 4: MDEA PROPERTIES (ChemicalBook, 2022)....................................................................... 36

VI
LIST OF ABBREVIATIONS
LNG Liquified Natural Gas
LPG Liquified Petroleum Gas
MDEA Methyl Diethanolamine
MEA Monoethanolamine
MEG Monoethylene Glycol
DEG Diethylene Glycol
DEG Diethylene Glycol
H 2S Hydrogen Sulphide
NG Natural Gas
NGL Natural Gas Liquids
PPM parts per million
TEG Triethylene Glycol
TREG Tetraethylene Glycol

VII
CHAPTER 1: INTRODUCTION
1.1 INTRODUCTION TO NATURAL GAS

Nowadays, natural gas provided about 23% of the total world energy supply, and that share
would certainly increase. While coal is a solid and oil is a liquid, natural gas is a gaseous-
phase fossil fuel. It is colorless, odorless, shapeless, and lighter than air. When burned, it
gives off about 1,000 Btu (British thermal unit) per standard cubic foot and is used for
domestic applications such as space heating, cooking and, increasingly, to generate
electricity. It only ignites when the air-and-gas mixture is between 5 and 15 percent natural
gas. When compared with coal and oil, it burns cleaner, more efficiently, and with lower
levels of potentially harmful byproducts that are released into the atmosphere. More
important, there are very large deposits of natural gas in the world—far more than oil—
Because this resource is difficult to transport, a lot of it has been labeled as “stranded.” For
these reasons, there has been a considerable increase in new gas exploration, field
development, and production activities. To develop a natural gas field, one of the first
important steps is to understand the fundamentals of natural gas. What follows is a
summary of basic petroleum geology, natural gas origins, resources, and properties (Wang
& Economides, 2010).

Although natural gas has been utilized as a fuel for more than 150 years, the large demand
for it has developed fairly recently. The principal reason for this is the greater difficulty of
storing and transporting gas as compared to liquid fuels. Initially, natural gas was used only
in the areas in which it was produced, with excess production being vented to the air or
flared. This was especially true of gas produced along with the oil in oil fields. The
development of large diameter, high pressure pipelines and compressors, along with the
technology of gas storage in reservoirs, has spurred both the demand for natural gas and
the development of the technology required to produce and transport it. This is illustrated
in the United States by the fact that natural gas supplied more than 30% of the total energy
demand in 1980 as compared to 18% in 1950 and less than 4% in 1920. Natural gas
supplied about 20% of the energy worldwide in 1980. The increased demand has also
greatly increased the price obtained for the gas. In 1950 the average price for natural gas
in the United States was about $0.07 per thousand standard cubic foot (Mscf), and as late
as 1970 the price averaged only about $O.17/Mscf. In 1980 the average price had increased

1
to more than $0.90/Mscf with gas in some areas selling for as much as $9.00/Mscf. The
large difference in the average and maximum selling price is due to the huge quantities
being sold at very low prices under long term contracts made many years ago. Natural gas
is used primarily as a fuel for space heating and for generating steam for electric power
plants, although its use as a feedstock for petrochemical plants is increasing rapidly.
Because of the necessity of using very high pressure to store significant quantities of
natural gas in small spaces, its use as a fuel for motor vehicles is very limited. However,
as the supply of liquid fuels such as gasoline diminishes, it is likely that technology will be
developed to overcome this problem (Beggs, 1984).

FIGURE 1: PRIMARY GLOBAL ENERGY CONSUMPTION 2021 (Rapier, 2022)

2
1.2 NATURAL GAS HISTORY

The discovery of natural gas dates from ancient times in the Middle East. Thousands of
years ago, it was noticed that natural gas seeps ignited by lightning created burning springs.
In Persia, Greece, or India, people-built temples around these eternal flames for their
religious practices. However, the energy value of natural gas was not recognized until
approximately 900 BC in China, and the Chinese drilled the first known natural gas well
in 211 BC. In Europe, natural gas was unknown until it was discovered in Great Britain in
1659, although it was not commercialized until about 1790. In 1821 in Fredonia, United
States, residents observed gas bubbles rising to the surface from a creek. William Hart,
considered as America’s father of natural gas, dug the first natural gas well in North
America. Historically, natural gas was discovered as a consequence of prospecting for
crude oil. Natural gas was often an unwelcome by-product, as natural gas reservoirs were
tapped in the drilling process and workers were forced to stop drilling to let the gas vent
freely into the air. Now, and particularly after the crude oil shortages of the seventies,
natural gas has become an important source of energy in the world (Speight, 1993)

The first commercialized natural gas occurred in Britain. Around 1785, the British used
natural gas produced from coal to light houses and streets. In 1816, Baltimore, Maryland
used this type of manufactured natural gas to become the first city in the United States to
light its streets with gas. In the United States, the properties of natural gas were discovered
by Native Americans, who would ignite the gases that seeped into and around Lake Erie.
French explorers witnessed this practice around 1626. In 1821, William Hart dug the first
successful natural gas well in the U.S. in Fredonia, New York. Eventually, the Fredonia
Gas Light Company was formed, becoming the first American natural gas distribution
company (American Public Gas Association, 2022).

1.3 NATURAL GAS SOURCE

It is commonly accepted that natural gas, like oil, has been generated from organic debris
that have been deposited in geologic time and have been embedded along with inorganic
matter at a considerable depth below today’s surface. Over time (tens to hundreds of
millions of years), because of compaction, high pressure, and temperature, the organic
material gradually became coal, oil, or natural gas. Because natural gas and oil are found
with water, and because they are less dense, they would rise vertically, including all the
way to the atmosphere. Much has escaped over time and continues to this day. However,

3
if a vertical barrier is encountered (cap rock), it stops the migration and confines gas-in-
place. Therefore, for natural gas to accumulate, three things have to be present: the source
rock (compacted organic materials) for the creation of natural gas; the porous media
(reservoir) to accommodate the created gas; and the impermeable rock on top to trap the
gas inside the porous rock-reservoir (Wang, Economides, 2010).

FIGURE 2: CRUDE OIL, ASSOCIATED GAS, ANDNON-ASSOCIATED GAS RESERVOIRS

(Jemo, 2017)

1.3.1 NON-ASSOCIATED GAS

These are reservoirs that contain almost entirely natural gas at reservoir conditions. They
are generally found at greater depth. If the fluid at the surface still remains gas, then it is
called “dry gas.” If the surface pressures cause some liquid hydrocarbons to evolve, it is
called a “wet gas” reservoir. It must be emphasized that while non-associated gas reservoirs
are likely to be found at greater depths, upward migration from the source rock, in geologic
time, can result in shallow gas reservoirs, and in some cases, such as the Arctic, the cap
rock may be the permafrost (Wang and Economides, 2010).

1.3.2 ASSOCIATED GAS

Associated gas is produced during crude oil production and is the gas that is associated
with crude oil. Crude oil cannot be produced without producing some of its associated gas,
which comes out of solution as the pressure is reduced on the way to and on the surface.
4
Properly designed crude oil well completions and good reservoir management are used to
minimize the production of associated gas so as to retain the maximum energy in the
reservoir and thus increase ultimate crude oil recovery. Crude oil in the reservoir with
minimal or no dissolved associated gas is rare and as dead crude oil is often difficult to
produce as there is little energy to drive it (Mokhatab et al, 2006).

1.3.3 UNCONVENTIONAL GAS

The term unconventional gas is widely used, but it refers more to the geological setting and
rock type rather than to the gas itself, which is nearly all methane. When the term was
coined, it implied that these reservoirs presented operational or economic challenges, or
both, which would not be ordinarily found in conventional reservoirs (Wang and
Economides, 2010).

1.4 NATURAL GAS ORIGIN AND COMPOSITION

Millions of years ago, the remains of plants and animals decayed and built up in thick
layers. This decayed matter from plants and animals is called organic material –a
compound that capable of decay or sometime refers as a compound consists mainly carbon.
Over time, the mud and soil changed to rock, covered the organic material and trapped it
beneath the rock. Pressure and heat changed some of this organic material into coal, some
into oil (petroleum), and some into natural gas – tiny bubbles of odorless gas. The main
ingredient in natural gas is methane, a gas (or compound) composed of one carbon atom
and four hydrogen atoms, CH4. It is colorless, shapeless, and odorless in its pure form
(Abubakar, 2010).

Natural gas exists in nature under pressure in rock reservoirs in the Earth’s crust, either in
conjunction with and dissolved in heavier hydrocarbons and water or by itself. It is
produced from the reservoir similarly to or in conjunction with crude oil. Natural gas has
been formed by the degradation of organic matter accumulated in the past millions of years.
Two main mechanisms (biogenic and thermogenic) are responsible for this degradation
(Rojey et al., 1997). Biogenic gas is formed at shallow depths and low temperatures by the
anaerobic bacterial decomposition of sedimentary organic matter. In contrast, thermogenic
gas is formed at deeper depths by (1) thermal cracking of sedimentary organic matter into
hydrocarbon liquids and gas (this gas is cogenetic with oil and is called “primary”
thermogenic gas) and (2) thermal cracking of oil at high temperatures into gas (“secondary”
thermogenic gas) and pyrobitumen. Biogenic gas consists almost entirely of methane. In
5
contrast, thermogenic gas can also contain significant concentrations of ethane, propane,
butanes, and heavier hydrocarbons. Knowing whether a natural gas show is biogenic gas
or thermogenic gas can have critical implications for the presence of liquid hydrocarbons
in a basin. Gas geochemistry readily reveals whether a gas is biogenic or thermogenic
(Mokhatab et al, 2006).

Natural gas consists mainly of methane and a small addition of higher hydrocarbons. In
addition to the organic components of natural gas deposits accompany the inorganic gases.
The most important non-hydrocarbon components are nitrogen, carbon dioxide, hydrogen
sulfide, and helium. The presence of helium or other noble gases are extremely desirable
because of the versatility of this gas and its high market value 9 (Wójcik, 2014).

TABLE 1: TYPICAL NATURAL GAS COMPOSITION (Wójcik, 2014).

Compound Molar fraction

Hydrocarbons
Methane 0.75 – 0.99

Ethane 0.01 – 0.15

Propane 0.01 – 0.10

n-Butane 0.00 – 0.02

Isobutene 0.00 – 0.01

n-Pentane 0.00 – 0.01

Isopentane 0.00 – 0.01

Hexane 0.00 – 0.01

Heptane + higher hydrocarbons 0.00 – 0.001

Nonhydrocarbons
Nitrogen 0.00 – 0.15

Carbon dioxide 0.00 – 0.30

Hydrogen sulfide 0.00 – 0.30

Helium 0.00 – 0.05

6
In addition to the proven conventional natural gas reserves in the world, there are huge
deposits of methane trapped in clathrates (methane hydrates) located at the bottom of the
oceans. In contrast, of particular importance for the Polish economy are layers of shale gas
and the possible recovery of methane from coal mines (currently 80% of coal production
comes from deposits reach in methane). Shale gas is formed in shale rocks that contain a
lot of organic matter. Its composition is similar to the composition of the natural gas derived
from conventional deposits. Typical shale gas contains methane (75– 95%) and nitrogen,
and sometimes traces amounts of ethane, propane, noble gases, oxygen, and carbon
monoxide. Shale gas does not contain harmful hydrogen sulfide. Averaged composition of
shale gas extracted in the US is shown in Table 1.2 (Wójcik, 2014).

TABLE 2: SHALE GAS COMPOSITION IN THE USA (Wójcik, 2014).

Compound vol %

Hydrocarbons

Methane 94.3

Ethane 2.7

Propane 0.6

Butane 0.2

Pentane 0.2

Nonhydrocarbons

Nitrogen 1.5

Carbon dioxide 0.5

7
1.5 NATURAL GAS BEHAVIORS

A gas is a form of matter that lacks a defined shape or volume. Gases share important
properties, plus there are equations you can use to calculate what will happen to the
pressure, temperature, or volume of a gas if conditions are changed.

1.5.1 GENERAL GAS PROPERTIES

There are three gas properties that characterize this state of matter:

▪ Compressibility - Gases are easy to compress.

▪ Expandability - Gases expand to completely fill their containers.

▪ Because particles are less ordered than in liquids or solids, the gas form of the same
substance occupies much more space.

All pure substances display similar behavior in the gas phase. At 0° C and 1 atmosphere of
pressure, one mole of every gas occupies about 22.4 liters of volume. Molar volumes of
solids and liquids, on the other hand, vary greatly from one substance to another. In a gas
at 1 atmosphere, the molecules are approximately 10 diameters apart. Unlike liquids or
solids, gases occupy their containers uniformly and completely. Because molecules in a
gas are far apart, it is easier to compress a gas than it is to compress a liquid. In general,
doubling the pressure of a gas reduces its volume to about half of its previous value.
Doubling the mass of gas in a closed container doubles its pressure. Increasing the
temperature of a gas enclosed in a container increases its pressure (Helmenstine, 2008).

1.5.2 NATURAL GAS PROPERTIES

The behavior of natural gas, whether pure methane or a mixture of volatile hydrocarbons
and the nonhydrocarbons nitrogen, carbon dioxide, and hydrogen sulfide, must be
understood by the engineer who is designing the operating equipment for its production,
processing, and transportation. The constituents of natural gas are most likely to be found
in the gaseous state but can occur as liquids and solids. Gases and liquids are composed of
molecules and may be treated on a molecular basis. The nature of the molecules and the
forces existing between them control the properties of the fluid. The kinetic theory of gases
treats a gas as a group of molecules, each moving on its own independent path, entirely
uncontrolled by forces from the other molecules, although its path may be abruptly altered
in both speed and direction whenever it collides with another molecule or strikes the

8
boundary of the containing vessel. In its simplest state, a gas may be considered as being
composed of particles that have no volume and between which there are no forces
(Bahadori, 2014).

1.6 NATURAL GAS PROCESSING PLANT

1.6.1 NATURAL GAS PRODUCTION ANS TRANSPORTATION

Oil and natural gas systems encompass wells, gas gathering and processing facilities,
storage, and transmission and distribution pipelines. These components are all important
aspects of the natural gas cycle—the process of getting natural gas out of the ground and
to the end user. Natural gas systems encompass the following industry segments:
• Production: Taking raw natural gas from underground formations.
• Gathering and Processing: Stripping out impurities and other hydrocarbons and fluids
to produce pipeline grade natural gas that meets specified tariffs (pipeline quality
natural gas is 95-98 percent methane).
• Transmission: Delivery of natural gas from the wellhead and processing plant to city
gate stations or industrial end users. Transmission occurs through a vast network of
high-pressure pipelines. Natural gas storage falls within this sector. Natural gas is
typically stored in depleted underground reservoirs, aquifers, and salt caverns.
• Distribution: Delivery of natural gas from the major pipelines to the end users (e.g.,
residential, commercial and industrial). (Us Epa, 2016)

FIGURE 3: THE DIAGRAM ABOVE DISPLAYS THE SEGMENTS OF THE OIL AND NATURAL
GAS INDUSTRY (Us Epa, 2016).

9
1.6.2 NATURAL GAS PROCESSING OVERVIEW

Natural gas processing consists of separating all of the various hydrocarbons and fluids
from the pure natural gas, to produce what is known as ‘pipeline quality’ dry natural gas.
Major transportation pipelines usually impose restrictions on the make-up of the natural
gas that is allowed into the pipeline. That means that before the natural gas can be
transported it must be purified. While the ethane, propane, butane, and pentanes must be
removed from natural gas, this does not mean that they are all waste products. In fact,
associated hydrocarbons, known as ‘natural gas liquids’ (NGLs) can be very valuable by-
products of natural gas processing. NGLs include ethane, propane, butane, iso-butane, and
natural gasoline. These NGLs are sold separately and have a variety of different uses;
including enhancing oil recovery in oil wells, providing raw materials for oil refineries or
petrochemical plants, and as sources of energy (NatGas, 2013).

1.6.3 NATURAL GAS TREATING & PROCESSES

The actual practice of processing natural gas to pipeline dry gas quality levels can be quite
complex, but usually involves four main processes to remove the various impurities:
1- Oil and Condensate Removal (Separation Process)
2- Water Vapor Removal (Natural Gas Dehydration)
3- Separation of Natural Gas Liquids (NGL Extraction)
4- Sulfur and Carbon Dioxide Removal (Natural Gas Sweetening Plant)

1.6.3.1 OIL AND CONDENSATE REMOVAL BY SEPARATORS

In order to process and transport associated dissolved natural gas, it must be separated from
the oil in which it is dissolved. This separation of natural gas from oil is most often done
using equipment installed at or near the wellhead. The actual process used to separate oil
from natural gas, as well as the equipment that is used, can vary widely. Although dry
pipeline quality natural gas is virtually identical across different geographic areas, raw
natural gas from different regions may have different compositions and separation
requirements. In many instances, natural gas is dissolved in oil underground primarily due
to the pressure that the formation is under. When this natural gas and oil is produced, it is
possible that it will separate on its own, simply due to decreased pressure; much like
opening a can of soda pop allows the release of dissolved carbon dioxide. In these cases,
separation of oil and gas is relatively easy, and the two hydrocarbons are sent separate ways
for further processing. The most basic type of separator is known as a conventional
10
separator. It consists of a simple closed tank, where the force of gravity serves to separate
the heavier liquids like oil, and the lighter gases, like natural gas (NatGas, 2013).

The separator sections described below utilize gravity settling, velocity separation by
centrifugal force or impingement, and filtration. Additional methods of separation are
sometimes required after primary separation, such as thermal (crude oil heater-treaters),
electrostatic precipitation (crude oil electrostatic coalescing treaters), adhesive separation
(gas-filter separators and water clean-up precipitators), and adsorption (gas molecular
sieves, silica gels, and alumina gels). Regardless of the size or shape of a separator, each
gas–liquid separator contains four major sections. Figures 3.4 and 3.5 illustrate the four
major sections of a horizontal and vertical two-phase gas–liquid separator (Steward, 2008).

1.6.3.1.a Two-Phase Separator (Gas-Liquid Separator)

Functional sections of a gas–liquid separator:

- Inlet Diverter: This abruptly changes the direction of flow by absorbing the momentum
of the liquid and gas to separate. This results in the initial “gross” separation of liquid
and gas (Steward, 2008).
- Gravity Settling Section: This section is sized so that liquid droplets greater than 100–
140 mm fall to the gas–liquid interface, while smaller liquid droplets remain with the
gas. Liquid droplets, greater than 100 mm, are undesirable as they can overload the mist
extractor at the separator outlet (Steward, 2008).
- Mist Extractor Section: Before the gas leaves the vessel, it passes through a coalescing
section or mist extractor. This section uses coalescing elements that provide a large
amount of surface area used to coalesce and remove the small droplets of liquid. As the
gas flows through the coalescing elements, it must make numerous directional changes.
Due to their greater mass, the liquid droplets cannot follow the rapid changes in
direction of flow. These droplets impinge and collect on the coalescing elements, where
they fall to the liquid collection section (Steward, 2008).

11
HORIZONTAL SEPARATORS

Figure 1.4 is a cutaway of a horizontal two-phase separator. Fluid enters the separator and
hits an inlet diverter, causing a sudden change in momentum. The initial gross separation
of liquid and vapor occurs at the inlet diameter. The force of gravity causes the liquid
droplets to fall out of the gas stream to the bottom of the vessel, where it is collected.
The liquid collection section provides:
• the retention time required to let entrained gas evolve out of the oil and rise to the
vapor space and reach a state of equilibrium, and
• a surge volume, if necessary, to handle intermittent slugs of liquid.
The liquid leaves the vessel through the liquid dump valve. The liquid dump valve is
regulated by a level controller. The level controller senses changes in liquid level and
controls the dump valve accordingly. Gas and oil mist flow over the inlet diverter and then
horizontally through the gravity settling section above the liquid. As the gas flows through
this section, small droplets of liquid that were entrained in the gas and not separated by the
inlet diverter are separated out by gravity and fall to the gas–liquid interface. Some of the
drops are of such a small diameter that they are not easily separated in the gravity settling
section. Before the gas leaves the vessel, it passes through a coalescing section or mist
extractor that removes very small droplets of liquid in one final separation before the gas
leaves the vessel (Steward and Arnold, 2008).
The pressure in the separator is maintained by a pressure controller mounted on the gas
outlet. Horizontal separators are:
• smaller and thus less expensive than a vertical separator for a given gas and liquid
flow rate, and
• commonly used in flow streams with high gas–liquid ratios and foaming crude.

12
 FIGURE 4: HORIZONTAL SEPARATOR SCHEMATIC (Steward and Arnold, 2008).

VERTICAL SEPARATORS

Figure 1.5 is a cutaway of a vertical two-phase separator. Inlet flow enters the vessel
through the side. The inlet diverter does the initial gross separation. The liquid flows down
to the liquid collection section of the vessel. There are seldom any internals in the liquid
collection section except possibly a still well for the level control float or displacer. Liquid
continues to flow downward through this section to the liquid outlet. As the liquid reaches
equilibrium, gas bubbles flow counter to the direction of the liquid flow and eventually
migrate to the vapor space. The level controller and the dump valve operate the same as in
a horizontal separator. The gas flows over the inlet diverter and then vertically upward
toward the gas outlet. Secondary separation occurs in the upper gravity settling section.
Liquid droplets fall vertically downward counter-current to the upward gas flow. The
settling velocity of a liquid droplet is directly proportional to its diameter. If the size of the
liquid droplet is too small, it will be carried up and out with the vapor. A mist extractor
section is added to capture small liquid droplets. Gas goes through the mist extractor
section before it leaves the vessel. Pressure and level are maintained as in a horizontal
separator (Steward and Arnold, 2008).

13
 FIGURE 5: VERTICAL SEPARATOR SCHEMATIC (Steward and Arnold, 2008).

SPHERICAL SEPARATORS

Figure 1.6 shows a typical spherical separator. The same four sections are found in this
vessel. They are a special case of the vertical separator where there is not cylindrical shell
between the two heads. Fluid enters the vessel through the inlet diverter where the flow
stream is split into two streams. Liquid falls to the liquid collection (Steward, 2008).

FIGURE 6: SPHERICAL SEPARATOR

SCHEMATIC (Steward and Arnold,
2008).

14
1.6.3.1.b Three-Phase Separator (Gas-Oil-Water Separator)

HORIZONTAL 3-PHASE SEPARATORS

Three-phase separators are designed as either horizontal or vertical pressure vessels. Figure
1.7 is a schematic of a typical horizontal three-phase separator. The fluid enters the
separator and hits an inlet diverter. This sudden change in momentum does the initial gross
separation of liquid and vapor. In most designs the inlet diverter contains a down-comer
that directs the liquid flow below the oil–water interface. This forces the inlet mixture of
oil and water to mix with the water continuous phase in the bottom of the vessel and rise
through the oil–water interface. This process is called water washing, and it promotes the
coalescence of water droplets, which are entrained in the oil continuous phase (Steward
and Arnold, 2008).

FIGURE 7: SCHEMATIC OF A HORIZONTAL THREE-PHASE SEPARATOR WITH INTERFACE

(Steward and Arnold, 2008).

15
VERTICAL 3-PHASE SEPARATORS

Figure 1.8 shows a typical configuration for a vertical three-phase separator. Flow enters
the vessel through the side as in the horizontal separator. The inlet diverter separates the
bulk of the gas. A downcomer is required to route the liquid through the oil–gas interface
so as not to disturb the oil skimming action taking place. A chimney is needed to equalize
gas pressure between the l
ower section and the gas section. The spreader, or down-comer, outlet is located just below
the oil–water interface, thus water washing the incoming stream. From this point, as the oil
rises, any free water trapped within the oil phase separates out. The water droplets flow
countercurrent to the oil. Similarly, the water flows downward, and oil droplets trapped in
the water phase tend to rise countercurrent to the water flow (Steward and Arnold, 2008).

FIGURE 8: SCHEMATIC OF A VERTICAL THREE-PHASE SEPARATOR WITH INTERFACE

(Steward and Arnold, 2008).

16
1.6.3.2 WATER REMOVAL (DEHYDRATION)

In addition to separating oil and some condensate from the wet gas stream, it is necessary
to remove most of the associated water. Most of the liquid, free water associated with
extracted natural gas is removed by simple separation methods at or near the wellhead.
However, the removal of the water vapor that exists in solution in natural gas requires a
more complex treatment. This treatment consists of ‘dehydrating’ the natural gas, which
usually involves one of two processes: either absorption, or adsorption (NatGas, 2013).

1.6.3.3 SEPARATION OF NATURAL GAS LIQUIDS

Natural gas coming directly from a well contains many natural gas liquids that are
commonly removed. In most instances, natural gas liquids (NGLs) have a higher value as
separate products, and it is thus economical to remove them from the gas stream. The
removal of natural gas liquids usually takes place in a relatively centralized processing
plant, and uses techniques similar to those used to dehydrate natural gas. There are two
basic steps to the treatment of natural gas liquids in the natural gas stream. First, the liquids
must be extracted from the natural gas. Second, these natural gas liquids must be separated
themselves, down to their base components (NatGas, 2013).

1.6.3.4 SULFUR AND CARBON DIOXIDE REMOVAL (SWEETENING)

In addition to water, oil, and NGL removal, one of the most important parts of gas
processing involves the removal of sulfur and carbon dioxide. Natural gas from some wells
contains significant amounts of sulfur and carbon dioxide. This natural gas, because of the
rotten smell provided by its sulfur content, is commonly called ‘sour gas’. Sour gas is
undesirable because the sulfur compounds it contains can be extremely harmful, even
lethal, to breathe. Sour gas can also be extremely corrosive. Sulfur exists in natural gas as
hydrogen sulfide (H2S), and the gas is usually considered sour if the hydrogen sulfide
content exceeds 5.7 milligrams of H2S per cubic meter of natural gas. The process for
removing hydrogen sulfide from sour gas is commonly referred to as ‘sweetening’ the gas.
The primary process for sweetening sour natural gas is quite similar to the processes of
glycol dehydration and NGL absorption. In this case, however, amine solutions are used to
remove the hydrogen sulfide. This process is known simply as the ‘amine process’, or
alternatively as the Girdler process, and is used in 95 percent of U.S. gas sweetening
operations. The sour gas is run through a tower, which contains the amine solution. This
solution has an affinity for sulfur, and absorbs it much like glycol absorbing water. There
17
are two principal amine solutions used, Monoethanolamine (MEA) and diethanolamine
(DEA). Either of these compounds, in liquid form, will absorb sulfur compounds from
natural gas as it passes through. The effluent gas is virtually free of sulfur compounds, and
thus loses its sour gas status. Like the process for NGL extraction and glycol dehydration,
the amine solution used can be regenerated (that is, the absorbed sulfur is removed),
allowing it to be reused to treat more sour gas (NatGas, 2013).

FIGURE 9: NATURAL GAS PROCESS FLOW DIAGRAM (Uwitonze, Hwang and Lee, 2020).

18
CHAPTER 2: LITERATURE REVIEW
2.1 NATURAL GAS PROCESSING

As discussed, natural gas produced from either an oil or gas reservoir is a complex mixture
with different compounds of hydrocarbons (primarily methane and varying amounts of
ethane, propane, butane, and even higher molecular weight hydrocarbons), an amount of
water vapor, small amounts of nonhydrocarbon gases (hydrogen sulfide, carbon dioxide,
and mercaptans such as methane thiol and ethanethiol), and even neutral gases such as
nitrogen and helium, etc. The gas composition depends on the geological area, as well as
the underground deposit type, depth, and location. The gas that is finally transported in
pipelines, on the other hand, must meet the quality standards specified by pipeline
companies. Those quality standards vary from pipeline to pipeline and are usually a
function of a pipeline system’s design, its downstream interconnecting pipelines, and its
customer base. Sulfur exists in natural gas as hydrogen sulfide (H2S), and the gas is usually
considered sour if the hydrogen sulfide content exceeds 5.7 mg of H2S per cubic meter of
natural gas. The process for removing hydrogen sulfide and carbon dioxide from a natural
gas stream is referred to as “sweetening” the gas. The primary process for sweetening
natural gas is similar to processes of glycol dehydration and NGL absorption. Amine
solutions are used to remove the hydrogen sulfide and carbon dioxide. Process is known
simply as the “amine process” and is used in the majority of onshore gas sweetening
operations. Gas with hydrogen sulfide and/or carbon dioxide is run through a tower, which
contains the amine solution. This solution has an affinity for carbon dioxide and hydrogen
sulfide, and absorbs these contaminants much like glycol absorbing water. The three
principal amine solutions used are Monoethanolamine (MEA), Diethanolamine (DEA),
Mathyldiethanolamine (MDEA). Either of the above compounds, in liquid form, absorbs
carbon dioxide and hydrogen sulfide from natural gas as it passes through. The effluent gas
is virtually free of carbon dioxide and hydrogen sulfide compounds. Like the process for
NGL extraction and glycol dehydration, the amine solution used can be regenerated (i.e.,
the absorbed sulfur is removed), allowing it to be reused to treat more gas. Although many
gas sweetening plants use the amine absorption process, it is also possible to use solid
desiccants like iron sponges and gas permeation (Wang, Economides, 2010).

19
2.2 SOUR & SWEET NATURAL GAS

2.2.1 SOUR GAS

As far as a pipeline company supplying industrial or domestic consumers is concerned, any

gas which contains greater than 1 grain of H2S per 100 CF or 16 ppm is sour. When the gas
is used as a fuel for boilers, fired heater or for compressor engines, then gas containing up
to 10 grains of H2S/100 CF of gas is generally considered acceptable. Also, sometimes in
remote locations compressors are driven by gas containing up to 2 % H2S. Another case is
the use of sour gas at wellhead as a fuel. This depends on the proximity of habitation and
vegetation but 3-4 % H2S content gas can be successfully used (A.H Younger, 2004).

2.2.2 SWEET GAS

Sweet natural gas is a type of natural gas containing trace amounts of hydrogen sulfide and
carbon dioxide. This natural gas is non-corrosive in its pure form, and it requires little
refining. We can also transport and market this gas safely (Madhu, 2021).

2.2.3 WHAT IS THE DIFFERENCE BETWEEN SWEET AND SOUR NATURAL GAS?

The key difference between sweet and sour natural gas is that the sweet natural gas contains
trace amounts of hydrogen sulfide, whereas the sour natural gas contains large amounts of
hydrogen sulfide. Moreover, sweet natural gas is non-corrosive, less acidic, and requires
little refining. Also, it is easy to transport and handle the sweet natural gas. Meanwhile,
sour natural gas is corrosive, can damage piping due to sulfide stress cracking process,
requires more refining, difficult to handle (Madhu, 2021).

20
 SWEET VS SOUR NATURAL GAS

Sweet Natural Gas Sour Natural Gas

Sweet natural gas is a type of natural Sour natural gas is a type of natural gas
Definition

gas containing trace amounts of containing large amounts of hydrogen

hydrogen sulfide and carbon dioxide. sulfide.
Composition

Trace amounts of hydrogen sulfide and

Large amounts of hydrogen sulfide
carbon dioxide.

Non corrosive, less acidic, requires little Corrosive can damage piping due to
Properties

refining and easy to transport and sulfide stress cracking process, requires
handle. more refining, difficult to handle.

21
2.3 GAS SWEETENING PROCESS CLASSIFICATIONS

There are many processes for removing acid gases. The choice of a particular process is
affected greatly by the specification required for the residue gas, the quantity of gas
processed and the composition of the raw gas being treated. The various processes will be
outlined and then described in more detail. It should be noted that in most processes, CO2
is also removed but not in all. In fact, a great deal of the technology for the removal of H2S
was developed first for CO2 removal in the preparation of synthesis gas for ammonia
production (A.H Younger, 2004).

Gas sweetening processes can be divided into five categories:

22
 TABLE 3: COMMERCIAL GAS SWEETENING PROCESSES (A.H Younger, 2004).

1 Physical solvent processes Solvent

Selexo 1 Dimethyl ether of polyethylene glycol (DMPEG)

Fluor solvent Propylene carbonate

Purisol N-methyl-pyrrolidone (NMP)

Rectisol Methanol

Sepasolv MPE Oligoethylene glycol methyl isopropyl ethers

Sulfinol Mixture of sulfolane, DIPA and H2O

Aminsol Mixture of MEA, DEA with methanol

2 Direct conversion processes Solvent

Sodium carbonate, sodium vanadate anthraquinone
Stretford
disulfonic acid and traces chelated iron
Sodium carbonate and 1.4 naphthoquinone, 2-
Takahax
sulfonate sodium
Sodium or ammonium thioarsenate solution Ferrox
Thylox
Sodium carbonate and ferric hydroxide solution

Manchester Sodium carbonate and ferric hydroxide solution

Perox Aqueous ammonia solution with hydroquinone

Townsend Triethylene glycol with dissolved

Fugapol Polyethylene glycol with metal salt catalyst

G.V. -sulphur Alkali arsenates and arsenites solution

Lo Cat Chelated iron in solution

Sulferox Chelated iron in solution

23
3 Dry-bed processes Packing

Iron sponge Iron oxide

Zinc oxide Zinc oxide

Mol sieves Molecular sieve

Haines Molecular sieve

4 Miscellaneous process

H2S Scavenging process

These are chemical processes that are used to remove H2S on a non-regenerable basis. The
chemicals used include formaldehyde, iron oxide, zinc oxide, sodium hydroxide, sodium nitrite.
For each use it is necessary to go to the literature.

Membrane processes

5 Chemical solvent processes Solvent

A. Alkanolamines (typical)

MEA 2.5 N-Monoethanolamine (=15% in water)

UCAR 5 N-Monoethanolamine (=30%) with inhibitor

DEA 2 N-Diethanolamine (=21%)

SNEA-DEA 3 N-Diethanolamine (=32%)

DIPA 2 N-Diisopropanolamine (=27%)

MDEA 2 N-Methyldiethanolamine (=24%) or higher %

DGA (Econamine) 6 N-Diglycolamine (=63%)

Inhibited Amines (both MEA and DEA (30-50%)

Hindered Amines varying amines

B. Hot Potassium Carbonate

24
 Catacarb pot.carb.solution with catalyst

Benfield pot.carb. solution with catalyst

Giammarco-Vetrocoke pot.carb. solution + arsenic trioxide

Alkacid-M pot.salt of methyl amino propionic acid

Alkacid-DIK pot.salt of dimethyl amino acitic acid

2.4 PHYSICAL SOLVENT PROCESSES

Physical solvent systems are similar to chemical solvent systems but are based on the gas
solubility within a solvent instead of a chemical reaction. Acid gas solubility depends on
acid gas partial pressure and system temperature. Higher acid gas partial pressures increase
the acid gas solubility. Low temperatures increase acid gas solubility, but, in general,
temperature is not as critical as pressure. Various organic solvents are used to absorb the
acid gases based on partial pressures. Regeneration of the solvent is accomplished by
flashing to lower pressures and/or stripping with solvent vapor or inert gas. Some solvents
can be regenerated by flashing only and require no heat. Other solvents require stripping
and some heat, but typically the heat requirements are small compared to chemical
solvents. Physical solvent processes have a high affinity for heavy hydrocarbons. If the
natural gas stream is rich in C3+ hydrocarbons, then the use of a physical solvent process
may result in a significant loss of the heavier mole weight hydrocarbons. These
hydrocarbons are lost because they are released from the solvent with the acid gases and
cannot be economically recovered (Stewart and Arnold, 2011).

Physical solvent processes should be considered for gas sweetening under the following
circumstances:

▪ Partial pressure of the acid gases in the feed is 50 psi (345 kPa) or higher.
▪ Concentration of heavy hydrocarbons in the feed is low.
▪ Only bulk removal of acid gases is required.
▪ Selective H2S removal is required.

25
 FIGURE 10: TYPICAL FLOW SCHEMATIC FOR A PHYSICAL SOLVENT PROCESS (Stewart
and Arnold, 2011).

Four typical physical processes are showed below:

a) Fluor Solvent Process

b) Sulfinol Process
c) Selexol Process
d) Rectisol Process

2.5 DIRECT CONVERSION PROCESSES

Direct conversion processes use chemical reactions to oxidize H2S and produce elemental
sulfur. These processes are generally based either on the reaction of H2S and O2 or H2S and
SO2. Both reactions yield water and elemental sulfur. These processes are licensed and
involve specialized catalysts and/or solvents. Figure 2.2 shows a simplified diagram of the
Stretford process (Stewart and Arnold, 2011).

26
FIGURE 11: SIMPLIFIED FLOW SCHEMATIC OF THE STRETFORD PROCESS (Stewart, 2014).

Chemical reactions involved are:

H2S + Na2CO3 → NaHS + NaHCO3

Sodium carbonate provides the alkaline solution for initial adsorption of H2S and the
formation of hydrosulfide (HS). The hydrosulfide is reduced in a reaction with sodium
meta vanadate to precipitate sulfur

HS + V+5 → S + V+4

Anthraquinone disulfonic acid (ADA) reacts with 4-valent vanadium and converts it back
to 5-valent

V+4 + ADA → V+5 + ADA (reduced)

Oxygen from the air converts the reduced ADA back to the oxidized state as shown
below:

Reduced ADA + O2 → ADA + H2O

The overall reaction is

2H2S + O2 → 2H2O + 2S

27
2.6 DRY BED PROCESSES (SOLID BED PROCESSES)

A fixed bed of solid particles can be used to remove acid gases either through chemical
reactions or through ionic bonding. This process flows the gas stream through a fixed bed
of solid particles, which removes the acid gases and holds them in the bed. When the bed
is spent, the vessel must be removed from service and the bed regenerated or replaced.
Since the bed must be removed from service to be regenerated, some spare capacity is
normally provided (Stewart, 2014).

Four commonly used processes under this category are:

▪ Iron sponge
▪ Sulfa-Treat
▪ Molecular sieve process
▪ Zinc oxide process

THE IRON SPONGE PROCESS

The iron sponge process is economically applied to gases containing small amounts of
H2S (<300 ppm) operating at low to moderate pressures in the range of 50-500 psig
(344.7-3447 kPa). This process does not remove CO2 (Stewart, 2014).

The reaction of iron oxide and H2S produces iron sulfide and water as follows:

Fe2O3 + 3H2S → Fe2S3 + 3H2O

FeO + H2S → FeS + H2O

The reaction requires the presence of slightly alkaline water (pH 8-10) and a temperature
below 110 F (47 oC). When temperatures exceed 110 oF (47 oC), careful control of pH must
be maintained. If the gas does not contain sufficient water vapor, water may need to be
injected into the inlet gas stream. The pH level can be maintained through the injection of
caustic soda, soda ash, lime, or ammonia with the water. pH control should be avoided
whenever possible (Stewart, 2014).

28
 FIGURE 12: TYPICAL IRON OXIDE PROCESS FLOWSHEET (Abdel-Aal and Aggour, 2003).

2.7 MISCELLANEOUS PROCESSES

These include some special methods such as:

▪ Membrane Technology: In the past, membranes could only be used for co-removal of
H2S and CO2 when the acid gas sulfur level is low. But some wellhead sources of natural
gas may contain acid gas sulfur level as high as 80%. Upon combination with water,
these gas streams are highly corrosive and can rapidly destroy pipelines and equipments
unless they are partially removed. Hence, exotic and expensive materials are required
for the construction of pipeline and downstream facilities (Ron Smith, 2020).
▪ Water Wash: In this method, high pressure water is used for physically absorbing the
acid gases.
▪ Low Temperature Condensation: Liquid H2S is condensed out by means of low
temperatures.
▪ Townsend Process: In this process the gas is dried with glycol and then the H 2S is
reacted with SO2 to form elemental sulphur.
▪ Ammonia Solution: This can be used for small concentrations.

29
▪ Molecular Sieves: These desiccants have been proposed and used for treating low
concentration of sour gases.
▪ The Rectisol Process: The process uses cold methanol as an absorbent. The process is
primarily used in synthesis gas application or the cleanup in LNG plants (A.H Younger,
2004).

2.8 CHEMICAL SOLVENT PROCESSES.

Utilize an aqueous solution of a weak base to chemically react with and absorb the acid
gases in the natural gas stream. Absorption occurs as result of the partial pressure
differential between the gas and the liquid phases. Most Common Chemical Solvents:
Amines, Carbonates (Steward and Arnold, 2008).

2.8.1 AMINE PROCESSES OVERVIEW

What are Amines? In natural gas processing, an “amine” is an aqueous solution containing
several alkylamines. A variety of amines are used in the sweetening of acid gasses. Which
amine solution is used depends on several factors (carverpump, 2021).

Several processes have been developed using the basic action of various amines.
Categorized by the number of organic groups bonded to the central nitrogen atom, as
primary, secondary, or tertiary. Primary amines form stronger bases than secondary
amines, which form stronger bases than tertiary amines. Amines with stronger base
properties Are more reactive toward CO2 and H2S gases and form stronger chemical bonds.
Implies that the acid gas vapor pressure will be lower for a given loading as amine reactivity
increases and a higher equilibrium loading may be achieved (Steward and Arnold, 2008).

2.8.2 BASIC PROCESS DESCRIPTION

Amine gas sweetening process is shown in Figure 2.3. Firstly, sour gas stream is usually
entering to scrubber to remove sour gas constants. Secondly, sour gas enters to the bottom
side of amine absorber tower and flow countercurrent to amine solvent and sweet gas will
leave the top of the contactor tower and need to be processed to dehydration process to
remove saturated water. Moreover, Dirty or rich amine will leave bottom of contactor tower
and need to be regenerate. Finally, Amine stripping tower (regenerator) is used to
regenerate the dirty amine hot lean amine need to be cooled therefore it flows to amine heat
exchanger and then back to contactor tower (Abdulrahman and Ibtisam, 2015).

30
The brief of amine process could be described by simple diagram as follow:

FIGURE 13: GENERAL FLOW DIAGRAM FOR AMINE PLANT (Abdulrahman and Ibtisam, 2015).

Most common amine processes are:

1- Monoethanolamine (MEA)
2- Diethanolamine (DEA)
3- Methyldiethanolamine (MDEA)

All processes above can remove CO2 and H2S to pipeline specifications.

2.9 MONOETHANOLAMINE (MEA) SYSTEM

Primary amine, which has had widespread use as a gas sweetening agent Process is well
proven and can meet pipeline specifications. MEA is a stable compound and in the absence
of other chemicals suffers no degradation or decomposition at temperatures up to its normal
boiling point (Steward and Arnold, 2011).

2.9.1 REGENERATION

Reactions are reversible by changing the system temperature. Reactions with CO2 and H2S
are reversed in the stripping column by heating the rich MEA to approximately 245 F at
10 psig (118 oC at 69 kPa). Acid gases evolve into the vapor and are removed from the still
overhead. Thus, the MEA is regenerated (Steward and Arnold, 2011).

31
2.9.2 ADVANTAGES

▪ Good pickup of acid gas.

▪ Well known and tried process (problems already known).
▪ Makes specification gas easily.

2.9.3 DISADVANTAGES

▪ High capital cost compared to some newer processes because high circulation rate.
▪ High chemical losses with some impurities.
▪ Some corrosion problems (A.H Younger, 2004)..

2.9.4 CORROSION CONSIDERATIONS

Acid gases in the rich amine are corrosive, but the above concentration limits may hold
corrosion to acceptable levels. Corrosion commonly shows up:

- Areas of carbon steel that have been stressed, such as heat affected zones near welds
- Areas of high acid gas concentration, or at a hot gas and liquid interface.

Thus, stress relieving all equipment after manufacturing is necessary to reduce corrosion,
and special metallurgy is usually used in specific areas such as the still overhead or the
reboiler tubes (Steward and Arnold, 2011).

2.9.5 FOAM CONSIDERATIONS

MEA systems foam rather easily resulting in excessive amine carryover from the absorber.
Foaming can be caused by a number of foreign materials such as Condensed hydrocarbons
Degradation products Solids such as carbon or iron sulfide Excess corrosion inhibitor
Valve grease, etc. (Steward and Arnold, 2011).

2.9.6 MEA LOSSES

MEA has the lowest boiling point and the highest vapor pressure of the amines. Results
in MEA losses of 1–3 lbs/MMSCF (16–48 kg/MM m3) of inlet gas (Steward and Arnold,
2011).

32
2.10 DIETHANOLAMINE (DEA) SYSTEMS

Secondary amine is also used to treat natural gas to pipeline specifications. As a secondary
amine, DEA is less alkaline than MEA. DEA systems do suffer the same corrosion
problems, but not as severely as those using MEA. Solution strengths are typically from
25% to 35% DEA by weight in water. DEA has significant advantages over MEA when
COS or CS2 are present DEA reacts with COS and CS2 to form compounds which can be
regenerated in the stripping column. Thus, COS and CS2 are removed without a loss of
DEA (Steward and Arnold, 20011).

2.10.1 ADVANTAGES

▪ Resistance to degradation by COS and CS2.

▪ Lower vaporization losses and regeneration energy required.
▪ Less corrosive.

2.10.2 DISADVANTAGES

▪ Lower reactivity.
▪ Higher recirculation rates.
▪ Higher solvent costs.
▪ In CO2 only, services it will degrade and be very corrosive.
▪ Lack of selectivity for H2S and CO2.
▪ If gas is not saturated reverse osmosis water or equivalent is needed to maintain amine
concentration, it will re-hydrate dry gas.
▪ Freeze point 80ºF – Transportation of 15% water solution may be required (Freeze
point 28ºF).
▪ Difficult to reclaim – Vacuum distillation, ion exchange.

2.10.3 AMINE LOSSES

Vapor pressure of DEA is approximately 1/30 of the vapor pressure of MEA. Thus, DEA
amine losses are much lower than in an MEA system (Steward and Arnold, 2011).

33
2.11 METHYLDIETHANOLAMINE (MDEA SYSTEM)

2.11.1 MDEA SYSTEM OVERVIEW

MDEA's popularity as a solvent for gas treating stems from several advantages it has when
compared to other alkanolamines. One of these advantages is a low vapor pressure, which
allows for high amine compositions without appreciable losses through the absorber and
regenerator. MDEA is also resistant to thermal and chemical degradation and is largely
immiscible with hydrocarbons. MDEA is a common base note in perfumes to allow the
fragrance to last. Lastly, MDEA has a relatively low heat of reaction with hydrogen sulfide
and carbon dioxide, which allows for lower reboiler duties, thus lower operating costs
(Raphael, 2005).

This is a direct proton transfer instantaneous reaction in an ionized medium. Its rate is very
fast or infinite for all amines. To achieve selective desulphurization of acid gas streams
using MDEA, the gas–liquid contact time in the absorber should be such long that it
removes H2S. However, CO2 reacts with water to produce carbonic acid which finally
reacts with MDEA. Since the reaction of MDEA with CO2 is slow, it hinders the absorption
process. Thus, allowing H2S to be readily absorbed by MDEA solution and making it
selective for H2S removal (Younas and Banat, 2014). In the real gas sweetening MDEA
plant, natural gas containing hydrogen sulfide/carbon dioxide is dispersed in aqueous
alkanolamine solution (45–50 weight % MDEA in GASCO Company, Habshan, Abu
Dhabi) in tray tower to absorb the acid gases (Priyabrata Pal., 2015).

2.11.2 PRODUCTION AND USES OF MDEA

Methyldiethanolamine is an amino alcohol, organic compound. It is obtained in industry

through the interaction of ethylene oxide and methylamine. Methyldiethanolamine, as well
as special sorbents based on it (various grades of special modified MDEA), are widely used
in amine treatment for the removal of acidic impurities from natural and process gases.
Other important areas where this product is used are the chemical industry and the
production of synthetic detergents. Global methyldiethanolamine demand exceeds 200,000
tons per year (HimTech Engineering, 2022).

34
Production/Preparing of MDEA

MDEA is produced by ethoxylation of methylamine using ethylene oxide:

CH3NH2 + 2C2H4O → CH3N(C2H4OH)2

Uses of MDEA

N-methyldiethanolamine is used as an intermediate in the synthesis of numerous products.

Its unique chemistry has resulted in its use in diverse areas, including coatings, textile
lubricants, polishes, detergents, pesticides, personal-care products, pharmaceuticals,
urethane catalysts, and water-treatment chemicals. It is also used in absorption of acidic
gases, catalyst for polyurethane foams, pH control agent. N-Methyldiethanolamine is a
reagent used for protection of boronic acids as N-methyl-O,O- diethanolamine esters
(ChemicalBook, 2022).

2.11.3 STRUCTURE OF MDEA

FIGURE 14: STRUCTURE OF METHYL-DIETHANOLAMINE (IN 2D)

FIGURE 15: STRUCTURE OF METHYL-DIETHANOLAMINE (IN 3D)

35
2.11.4 PROPERTIES OF MDEA

TABLE 4: MDEA PROPERTIES (ChemicalBook, 2022).

Melting point -21 °C

Boiling point 246-248 °C (lit.)
Density 1.038 g/mL at 25 °C(lit.)
vapor density 4 (vs air)
vapor pressure 0.01 mm Hg (20 °C)
refractive index n20/D 1.469 (lit.)
Flash point 260 °F
storage temp. Store below +30°C.
Form Liquid
Pka 14.41 ± 0.10(Predicted)
Color Clear colorless to light yellow
PH 11.5 (100g/l, H2O, 20℃)
Odor Ammonical
PH Range 11.5 at 100 g/l at 20 °C
explosive limit 0.9-8.4 % (V)
Water Solubility MISCIBLE

36
2.11.5 ADVANTAGES

Higher allowable MDEA concentration and acid gas loading results in reduced circulation
flow rates. Significant capital savings are realized due to reduced pump and regeneration
requirements. MDEA has a lower heat requirement due to its low heat of regeneration. In
some applications, energy requirements for gas treating can be reduced as much as 75% by
changing from DEA to MDEA (Steward and Arnold, 2011).

Advantages Summary:

▪ Selectivity to hydrogen Sulphide.

▪ Reduction of 30% in energy consumption.
▪ Increased productivity.
▪ Low corrosiveness.
▪ No resin formation.
▪ Reduction in circulating absorbent consumption.

2.11.6 WHY MDEA?

In recent years, the specialty formulated MDEA solvents offered by several solvent
vendors have gained a significant share of the market. The introduction of the formulated
MDEA solvents has been the major innovation within the gas treating industry over the
past decade. This commercial success is due principally to the ability of MDEA to
selectively remove H2S when treating a gas stream containing both H2S and CO2 while
slipping a significant portion of the CO2. This slippage of CO2 can be useful in applications
requiring the upgrading of H2S content for sulfur plant feed gas or adjusting the CO2
content of the treated gas while at the same time removing H2S to less than 1/4 grain per
100 scf (4 ppmv). Originally, the most significant application of MDEA and the various
formulated MDEA solvents were in tail gas treating units but increasingly the formulated
solvents have displaced primary and secondary amines in refinery primary treating systems
and in high pressure natural gas applications. The advantages of MDEA and the formulated
MDEA solvents are Selectivity of H2S over CO2 in mixed acid gas applications, essentially
complete H2S removal while only a portion of CO2 is removed enriching the acid gas feed
to the sulfur recovery unit (SRU), Low vapor pressure which results in potentially lower
solvent losses, less corrosive, High resistance to degradation, and, Efficient energy
utilization means capital and operating cost savings (Mitra, 2015).
37
2.11.7 AMINE CONCENTRATION

The choice of amine concentration may be quite arbitrary and is usually made on the basis
of operating experience. Typical concentrations of monoethanolamine range from 12 wt%
to a maximum of 32 wt%. On the basis of operating experience in five plants, Feagan et al.
(1954) recommended the use of a design concentration of 15 wt% monoethanolamine in
water. The same solution strength was recommended by Connors (1958). Dupart et al.
(1993A, 1993B) recommends a maximum MEA concentration of 20 wt%. However, it
should be noted that higher amine concentrations, up to 32% wt MEA, may be used when
corrosion inhibitors are added to the solution and when C02 is the only acid gas component.
Diethanolamine solutions that are used for treatment of refinery gases typically range in
concentration from 20 to 25 wt% while concentrations of 25 to 30 wt% are commonly used
for natural gas purification. Diglycolamine solutions typically contain 40 to 60 wt% amine
in water, and MDEA solution concentrations may range from 35 to 55 wt% (Kohl and
Nielsen, 1997).

2.11.8 MDEA CONCENTRATION:

The reason behind the MDEA concentration being 35 to 55wt%, It should be noted that
increasing the amine concentration will generally reduce the required solution circulation
rate. and therefore, the plant cost. However, the effect is not as great as might be expected,
the principal reason being that the acid-gas vapor pressure is higher over more concentrated
solutions at equivalent acid-gaslamine mole ratios. In addition, when an attempt is made to
absorb the same quantity of acid gas in a smaller volume of solution, the heat of reaction
results in a greater increase in temperature and a consequently increased acid-gas vapor
pressure over the solution (Kohl and Nielsen, 1997).

38
2.12 GAS DESULFURIZATION/SWEETENING BY ADSORPTION

Sour natural gas sweetening by adsorption is considered the oldest method to treat the sour
natural gas. Fixed bed of solid particles could be adopted to remove acid gases either
through chemical reactions or through ionic bonding. Gas stream flows through a fixed bed
of solid particles which removes the acid gases and holds them in the bed. When the bed
is spent, the vessel must be removed from service and the bed regenerated or replaced.
Since the bed must be removed from service to be regenerated, some spare capacity is
normally provided. Furthermore, this method consists of several processes that it has the
same concept for instance, iron sponge process and zinc oxide proses. Infect, it achieves
by using solid sweetening agents. Furthermore, solid bed sweetening method bases on
adsorption principles (Abdulrahman and Immanuel, 2013).

Moreover; it is used fixed bed of solid particulars which it can remove the acid gases from
the natural gas. As Stewart, M. and Arnold, K. (2011) notated that “Fixed bed of solid
particles be used to remove acid gas either through chemical reactions or through ionic
bonding”. Indeed, the modus operandi of this method is achieved by passing the sour gas
through a fixed bed of solid particles that adsorbs the acid gases and removes it from the
Natural gas. Therefore, the bed should be regenerated time to time to remove the impurities
and make sure it at high purity to achieve maximum sweetening efficiency (Abdulrahman
and Immanuel, 2013).

https://www.researchgate.net/publication/237081404_Desulphurisation_of_Natural_Gas_
by_Using_Adsorption_Method_A_Case_Study_of_Lennox_Gas_Field/related

39
2.13 GAS DESULFURIZATION/SWEETENING BY ABSORPTION (MDEA)

Figure 16 shows a typical amine system for removing H2S from the feed stream. In this
chapter all units will be briefly explained –purpose of the unit, characteristics and etc.
Depending on the amine solvent that is selected for the gas sweetening process slight
modifications can appear, as well as optimizations for specific purposes.

FIGURE 16: NATURAL GAS SWEETENING UNIT (GSU) BY AMINE (MDEA) (Steward and
Arnold, 2011).

40
2.13.1 EQUIPMENT DESCRIPTION

Inlet Separator/Scrubber

The design and type of inlet separation should be carefully considered. Inlet separation
equipment can vary from slug catchers, which are generally designed to catch large slugs
of liquids from gas gathering systems where condensing hydrocarbons are prevalent, to
cutting edge technology reverse flow filter coalescers. Experience indicates that inlet feed
gas filtration is very important and critical in the trouble-free operation of the amine
treating system. The cleaner an amine system is, the better the system operates. Many of
the contaminants that cause poor performance can enter the amine system via the inlet feed
gas. In most cases, the inlet separator of the amine system is sized based on the feed gas
being a relatively dry stream, removing only condensed water and hydrocarbons. The
separator is typically a vertical vessel with a side inlet and top outlet for the feed gas to the
absorber with a wire-mesh mist pad in the top of the separator. Standard mist elimination
pads common in inlet separation vessels have 99% efficiency down to about 10 microns.
But, the efficiency drops rapidly for droplets below 10 microns. Wire-mesh pads have been
reported to have 97 per cent removal efficiency at 8 microns; falling off to 50 per cent
efficiency at the 2½ micron level. In applications where it is anticipated that the inlet gas
may contain particulate such as FeS, a filter-separator may be required. This equipment
typically consists of a horizontal vessel with filters in the inlet end of the vessel to remove
the FeS followed by mist pads or impingement baffles with a separator chamber to collect
any separated liquids. Aerosols, which may be as small as ½ micron, are not removed
effectively by standard mist elimination pads. If
aerosols are determined to be present, high
technology coalescing filtration systems are
available which can remove aerosols in the sub-
micron range. A water wash system on the inlet
feed gas consisting of a small trayed (4-5 trays) or
packed column is also effective in removing
aerosols formed by upstream equipment.
Consideration of a reverse flow coalescer may
also be dictated by the necessity to remove iron
sulfide from the inlet feed gas that can be as small FIGURE 17: INLET
as sub-micron in size (Mitra, 2015). SEPARATOR/SCRUBBER

41
Amine Absorber/Contactor

The amine solution temperature entering the absorber should be 10 to 15 °F higher than
the inlet feed gas temperature to prevent condensation of hydrocarbon in the contactor,
which can cause foaming. The inlet feed gas typically enters the absorber at 100to 120 °F.
Therefore, the typical range of lean amine solvent temperature is 115 to 135 °F. As a
practical maximum, though dependent upon the particular amine and absorber application,
the lean amine solvent temperature should generally not exceed 135 °F. High lean solvent
temperatures can lead to poor solvent performance due to H2S equilibrium problems on
the top tray of the absorber or increased solution losses due to excessive vaporization
losses. (Mitra, 2015).

FIGURE 18: AMINE ABSORBER/CONTRACTOR

42
Flash Vessel Separation

The rich amine flash vessel is designed to remove soluble and entrained hydrocarbons from
the amine solution and should be operated at as low a pressure as possible in order to
maximize hydrocarbon recovery. The removal of hydrocarbons reduces the amine solution
foaming potential. Normal operating pressure of the flash vessel ranges from 5 psig to 75
psig, depending upon the disposition of the flash vessel vent stream. A rich amine pump is
usually required to pump the rich amine through the lean/rich cross exchanger to the
regenerator if the flash vessel operating pressure is lower than 50 psig (Mitra, 2015).

FIGURE 19: FLASH SEPARATOR

43
Lean/Rich Cross Heat Exchanger

The temperature of rich amine leaving the absorber will be 130 to 160 °F and the lean
amine from the reboiler will be 240 to 260 °F. The rich amine outlet from the lean/rich
cross exchanger is typically designed for a temperature of 200-210 °F. Based upon the
above amine temperatures, the lean amine from the lean/rich cross exchanger will be
cooled to about 180 °F. The most common problem encountered in the lean/rich cross
exchanger is corrosion due to flashing acid gases at the outlet of the exchanger or in the
rich amine feed line to the regenerator. High rich amine loading due to reduced circulation
rate or low solvent concentration increases the potential for acid gas flashing. Adequate
pressure should be maintained on the rich solution side of the lean/rich exchanger to reduce
acid gas flashing and two-phase flow through the exchanger. Two-phase flow through the
exchanger can be a major cause of erosion/corrosion in the cross exchanger. In order to
reduce flashing and two-phase flow, the final letdown valve on the rich amine, i.e. the flash
tank level control valve, should be located downstream of the exchanger and as close as
practical to the feed nozzle of the regenerator (Mitra, 2015).

FIGURE 20: LEAN/RICH CROSS HEAT EXCHANGE

Stripper/Reboiler

The purpose of the stripper is to regenerate the amine solution by stripping the rich amine
of the H2S and CO2 with steam generated by the reboiler. The vast majority of the stripping
should occur in the stripper rather than in the reboiler. If substantial stripping occurs in the
reboiler, excessive corrosion and premature reboiler tube failure is likely, especially in
applications with substantial CO2. The regeneration requirement to reach a typical lean
loading is a reflux ratio of 1.0 to 3.0. A reflux ratio of 1.0 should be considered as a practical

44
minimum. In some low pressure or tail gas treating applications, higher reflux ratios may
be required to meet the product specifications. In order to ensure adequate stripping while
at the same time optimizing energy utilization, control of the heat input to the reboiler
should be accomplished by monitoring the stripper overhead temperature. The overhead
temperature correlates directly with the reboiler energy input. The reboiler temperature is
not affected by the amount of stripping steam generated in the reboiler since the boiling
point of the amine solution is dependent upon the amine concentration and reboiler
pressure. Therefore, the reboiler temperature is not a controlled variable. The heat input to
the reboiler should be set to achieve a specified stripper overhead temperature, typically
210 to 230 °F depending upon the gas treating application and amount of reflux desired.
To prevent thermal degradation of the amine solvent, steam or hot oil temperatures
providing heat to the reboiler should not exceed 350 °F. Superheated steam should be
avoided. 50 psig saturated steam is recommended. The maximum bulk solution
temperature in the reboiler should be limited to 260 °F to avoid excessive degradation
(Mitra, 2015).

FIGURE 21: REBOILER

FIGURE 22: STRIPPER COLUMN

45
2.13.2 PROCESS DESCRIPTION:

Inlet separator
The feed gas stream, also called sour gas stream, containing the acid gases H2S and/or CO2
must always pass through an Inlet Separator. The purpose of inlet separator is to catch the
entrained hydrocarbon liquids, occasional slugs and entrained solids. The separator must
be designed in such a way that it will have a demister pad, in order to prevent liquid droplets
carry-over to the amine system. Generally, vertical drums are used as inlet separators.

Absorber Column
After the gas passed through the inlet separator and cleaned form excessive contamination
the gas will fed to another unit operation named Absorber or (contactor). The primary
function of the contactor is to provide an extensive area of liquid surface which will be in
contact with the gas phase in such conditions that will favor mass transfer. After the gas
passes through the inlet separator, it enters the Absorber (Contactor) from the bottom, while
the aqueous amine solution or also called lean solution, enters from the top. This way the
gas flows in upward direction through the column where it makes an intimate counter-
current contact with the lean solution. Chemical reaction between the amine and the sour
gas occurs and the amine solution absorbs the Hydrogen Sulfide and the Carbon Dioxide.
The temperature of the treated gas will rise, due to the heat reaction between the acid gas
and the lean solution. Therefore, the chemical reaction is exothermic. The treated gas
leaves the column from the top, while the rich solution (small amount of hydrocarbons with
amine and acid gas) leaves from the bottom of the column. The gas absorber is usually a
tray column. The tray column is consisting of certain number of trays, the most efficient
number of trays used in the industry is between 15 and 20. The trays are equipped with
weirs (in most cases with a high of around 5 –7.6 cm), which help for maintaining a certain
level of solvent on each tray, Figure 23. As mentioned above, the gas goes in upward
direction and passes through the trays, which have openings such as bubble caps,
perforations or valves. When the gas passes through the openings in the trays it disperses
into bubbles, forming froth. Continuing to travel upwards in the vapor space the entrained
amine solution in the gas has time to fall back on the liquid tray, while the gas will continue
through the next tray.

46
 FIGURE 23: BUBBLE CAP TRAYS IN AN ABSORBER

FIGURE 24: MIST EXTRACTOR

To reduce the amine losses, 2 to 5 trays can be installed at the top of the absorber. These
additional trays will function as a water wash section and it will minimize the vaporization
losses of amine. Furthermore, demister pad can be installed near the gas outlet of the
contactor, which will trap the entrained solvent in the sweetened gas.

47
Absorber operation conditions:
The accepted operating conditions of the contactor are as follows:
▪ The operating pressure normally matches the feed gas pressure. Hence, minimum
operating pressure of 4-5 bar is required to maintain feasible and operable process. As
far as the process is concerned there aren’t any limitations on high pressure, except that
with higher pressure the thickness of the steel plates that form the absorber must be
increased.
▪ In order to avoid foaming in the contactor due to hydrocarbon condensation (if the gas
is saturated) the amine solution temperature must be maintained with 10 to 15°F (5.55
to 8.33°C). However, there are limitations on high temperature of the lean amine stream
and the feed stream. High temperatures will affect the sweetening process –it will lower
the acid gas pick up by the lean amine solution and it will increase the water losses.
Throughout the extensive experience of the oil and gas industry a normal temperature
range for the feed gas stream should be between 80 -120°F (26.7 -48.9°C), while the
temperature of the lean amine solution –90 to 130°F (32.2 –54.4°C).

Flash Tank:
On one hand the treated Gas flash tank is a unit with the main purpose to reduce the losses
of amine solution. The treated gas that is coming out from the top of the absorber gets into
the drum, where the sweetened gas is dried by removing the entrained amine. Usually, a
vertical drum is used and is equipped with demister pad. When the treated gas comes from
the drum it can be routed to the downstream facilities. On the other hand, Amine Flash
Drum is a unit which is installed to carry over the rich amine solution coming out from the
bottom of the absorber. Depending on the composition of the rich stream, 3 phase
horizontal or 2 phase vertical separator is used. The drum’s purpose is to recover the
hydrocarbons that may have dissolved or condensed in the amine solution. To achieve that,
the pressure is significantly reduced to a range between 3 and 5 bar. In this way the lightest
of the hydrocarbons flash, while the heavier hydrocarbons remain as liquid as well as the
aqueous amine solution, forming two separate liquid layers. The two layers are formed,
because of the different densities of the solutions. The hydrocarbons have lower density;
therefore, they occupy the upper liquid layer and can be skimmed off the top. On the other
side the aqueous amine solutions is freed from the hydrocarbons and can be drained from
the bottom of the drum.

48
Rich Amine/Lean Amine Heat Exchanger
After the rich amine solution is freed from the dissolved hydrocarbons the next step is the
amine to be regenerated, but before entering the regenerator column the stream must be
preheated. The lean amine, coming out from the reboiler (it is explained further on) is of
higher temperature than the rich amine entering. The lean amine must be cooled therefore
there is a very good opportunity to exchange heat between the lean amine and the rich
amine stream. This way the lean stream will be cooled, while the rich stream will be
preheated. By using cross-flow heat exchanger the total artificial heat requirements for the
process are lowered, which leads to lower costs. The types of heat exchangers that are used
for this purpose are usually shell and tube exchanger and plate and frame. Where, for the
shell and tube the rich solution flows through the tubes and the lean solution through the
shell. In order to reduce the corrosion in the tubes a velocity of 1 m/s is recommended. In
the industry, the flow coming from the bottom of the separator enters the heat exchanger
with its current pressure and the temperature range for each stream is as follows –outlet
rich amine (90 –110°C), inlet lean amine (110 -130°C).

Regeneration or Stripping
The Regenerator (also called stripper) as well as the absorber is a tray tower and is generally
designed with between 15 to 20 trays. This fractionation column is also equipped with
condenser (using water or air as cooling medium) and a reboiler (using hot oil or steam as
heating medium). After the rich amine is preheated in the cross-flow heat exchanger, it
enters the stripper near the top and flows down countercurrent to a gas stream of steam,
Hydrogen Sulfide and Carbon Dioxide. The partial pressure of H2S and CO2 in the gas
stream is lowered, due to the steam generated in the reboiler, which leads to enhancing the
driving force of the acid gases from the amine solution. The liberated H2S and CO2 as well
as the remaining steam keep its way in upward direction until they exit the stripping section.
On the other side, the rich amine keeps making its way down the regenerator column and
steadily gives up the absorbed Hydrogen Sulfide and Carbon Dioxide and becomes leaner
until it leaves the regenerator from the bottom. At the top of the stripper the vapor leaves
and enters the reflux section where it is cooled in a condenser. The steam is condensed and
separated from the H2S and CO2 gas in the reflux drum and then recycled back as reflux.
The acid gas stream is sent for further treatment and compression in order to meet the end
use specifications. Similarly, to the absorber column, in the regenerator also can be
installed a demister pad to reduce the amine loss caused by physical entrainments.

49
Depending on the given case the best operating pressure for the process can be between
1.2 and 2 bar or between 2.1 and 3 bar.

Reboiler
The objectives of the reboiler are “to heat up the rich solution, to produce the energy to
reverse the chemical reaction, to free acid gas from the amine solution and to generate
steam to strip acid gas from solution. The stripping efficiency is controlled by the overhead
reflux ratio. The reboiler is usually a shell and tube exchanger, which uses hot oil or steam
as heating medium. The temperature inside the tube should not exceed 145°C, because
above this temperature will cause amine degradation.

Condenser and Reflux Drum

The top product of the stripper is a water vapor and acid gas mixture. This mixture is
condensed in the Condenser to generate reflux to the regenerator. It uses ambient available
cooling medium, such as water or air. The type of exchanger used for this purpose is shell
and tube. After the mixture of water and acid gas is condensed the next step is to be
collected and separated. The Reflux Drum, or also called regenerator overhead drum,
separates the mixture into water and acid gas. The water leaves the drum from the bottom
and is handled by reflux pumps to the top of the regenerator. The acid gas leaves the drum
from the top and is routed to the acid gas disposal system. The reflux drum is vertical or
horizontal and it is equipped with demister pad. The temperature must be maintained as
low as possible in order to minimize the concentrations of amine and water entrainments
in the stream routed to the downstream facilities. Such facilities could be for example –
Sulfur recovery unit.

Amine Surge Tank

The final stage, before the lean amine is cooled and recycled to the absorber, is to pass
through an Amine Surge Tank. One of the tank’s purposes is that in event of process
shutdown it contains the entire contents of the circulating system. Moreover, it also
maintains the strength of the lean amine solution by periodic make-ups. In this way any
minor or major amine losses due to thermal degradation will be covered, as well as water
losses during the absorption and the regeneration stages. The characteristics of the tank are
as follows – atmospheric classical storage tank with fixed or cone roof; the operating
temperature should be above the freezing point of the solution; the tank must be blanketed
with nitrogen or treated gas in order to avoid amine degradation due to contact with air.

50
CHAPTER 3: METHODOLOGY
3.1 SIMULATION OVEVIEW

Simulation is the use of a physical or logical representation of a given system to generate

data and help determine decisions or make predictions about the system. Simulation is
widely used in the social and physical sciences, engineering, manufacturing and product
development, among many other areas (TechTarget Contributor, 2022).

3.2 WHY SIMULATE?

An alternative approach to computer simulation is direct experimentation. In the bagel shop

setting, we could wait for the shop to open and observe its workings by having a different
number of employees on different days. Considered against real experimentation,
simulation has the following advantages:

▪ It is cheaper to implement and does not require a disruption of the real-world system.
▪ It is faster to implement and time can be compressed or expanded to allow for a speed-
up or a slow-down of the system of interest.
▪ It can be replicated multiple times and the workings of the systems can be observed a
large number of times.
▪ It is safe since it does not require an actual disruption of the system.
▪ It is ethical and legal since it can implement changes in policies that would be unethical
or illegal to do in real-world.

Another alternative is to use a mathematical model representing the system. However, it is

often infeasible, if not impossible, to come up with an exact mathematical model which
can faithfully represent the system under study (Manuele Leonelli, 2021).

3.3 SIMULATION USES IN PROCESS/CHEMICAL ENGINEERING

Chemical process simulation aims to represent a process of chemical or physical

transformation through a mathematic model that involves the calculation of mass and
energy balances coupled with phase equilibrium and with transport and chemical kinetics
equations. All this is made looking for the prediction of the behavior of a process of known
structure, in which some preliminary data of the equipment that compose the process are
known (Chaves, G., Ricardo, J., García, L., Alexander Leguizamón Robayo and Gerardo
Rodríguez Niño 2016).

51
3.4 PROCESS SIMULATION SOFTWARE

A process simulator is software that calculates pressures, temperatures, and flows in order
to replicate the behavior of a chemical process in steady state. Nowadays, computer
programs used in process simulation are used to investigate the dynamic behavior of
processes, as well as control systems and their responses to operational perturbations.
Software for equipment sizing, cost estimation, property assessment and analysis,
operability study, and process optimization are also available (BRE, 2022).

Process simulation software allow:

− Predict the behavior of a process.
− Analyze in a simultaneous way different cases, changing the values of main operation.
− Optimize the operating conditions of new or existing plants.
− Track a chemical plant during its whole useful life, in order to expect
extensions o process improvements.

Common Simulator Software for Chemical Process Simulation

Aspen HYSYS, Pro II, ChemCAD, UniSIM, etc. In this project we will use ProMax
which explained in the next page.

3.5 PROMAX

ProMax is a comprehensive suite of process simulation software developed by engineers for engineers. It
is intended to maximize chemical, refinery, and gas processing facilities. With the most recent version,
we have placed an emphasis on environmentally friendly technologies like carbon capture, renewable
natural gas, green hydrogen, and renewable diesel. With the new Data Exchange feature, you can read
from and write to your historian to keep tabs on your plant's operations and compile useful performance
data. Our objective is to assist our clients in reducing emissions in order to contribute to the construction
of a more sustainable future that will enable succeeding generations (BR&E, 2022).

3.6 WHY DO WE USE PROMAX

ProMax is a powerful and versatile stream-based process simulation package. It is used by engineers
around the world to design and optimize gas processing, refining, and chemical facilities. ProMax contains
over 50 packages, over 2300 components for instance, solvers, crude oil characterization and Microsoft
Excel® spreadsheet. ProMax offers all of this with amazing flexibility and ease of use. ProMax is built
on technology proven over the past 30 years. With ProMax, BR&E has continued to build on its reputation
as a leading provider of simulation technology by focusing on several key processes. These processes
include amine sweetening, glycol dehydration, equipment rating/sizing, crude oil refining, LPG/NGL

52
recovery & fractionation. These processes are not the limit. ProMax was created by engineers for
engineers. Because of this, ProMax is the "must have" simulation resource for engineers throughout the
oil, gas and chemical industries. Its intuitive interface makes setting up even the most complex of
flowsheets a relatively simple task. Tools are available to interact with Excel and other powerful programs
to make ProMax a powerful and versatile tool (BR&E, 2022).

53
CHAPTER 4: MASS & ENERGY BALANCE
4.1 MASS BALANCE

54
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