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LPG Recovery Unit Optimization
Thesis · June 2015

DOI: 10.13140/RG.2.2.14475.90402
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New Mexico Institute of Mining and Technology
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Dedication
I especially dedicate this humble work to,

My Twin brother, Mehdi MEZNI, for his unconditional love, unyielding support and generous
help,
My father, Abderazzak MEZNI, for his permeant assistance, his kind care and his precious
backing,
My Mother Faouzia ZEHIRI, for her warm care, hearty approbation and lavish praise
To my eldest Brother and his wife Hichem and Basma MEZNI, and their future child,
To my friends who have been there for me in times of need,
and
To the long nights, to the dark fights and to those who are keeping on spreading light over my
way.
Acknowledgement
I want to express my profound gratitude to my Project tutors, Mr. Mondher KHOUDI at ENI
Tunisia B.V. and Mr. Elyes KHEDHER at INSAT for their valuable guidance, scientific support
and their enlightening discussions.
I want to thank Mr. Sandor GRUTTADAURIA and Mr. Gaetano DI RAUSO for accepting me
to realize my project of end of studies within Eni Tunisia B.V.
A special thanks go to the Jury crew, Mrs NARJES BATIS, and Mr Taieb SAID for honoring me
by assessing my work, I hope they will be satisfied.
I would also like to extend my whole-hearted thanks and gratitude to my colleagues at Eni
Maamoura & Baraka field for their untiring help and constructive criticism, especially, Miss Hager
ABDELLI and Mr. Haykel ABDI.
I would also like to sincerely thank everyone who contributed in the accomplishment of this
thesis, may they find in here my endless gratitude.
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Summary
GENERAL INTRODUCTION ............................................................................................................. 12
CHAPTER 1 – NATURAL GAS & LPG FUNDAMENTALS .......................................... 13
1. NATURAL GAS FUNDAMENTAL............................................................................................ 14
1.1. INTRODUCTION ................................................................................................................... 14
1.2. NATURAL GAS ORIGIN AND COMPOSITION ......................................................... 14
1.3. NATURAL GAS PHASE BEHAVIOR ............................................................................... 16
2. NATURAL GAS PROPERTIES ................................................................................................... 17
2.1. MOLECULAR WEIGHT ....................................................................................................... 17
2.2. DENSITY................................................................................................................................... 17
2.3. SPECIFIC VOLUME .............................................................................................................. 17
2.4. SPECIFIC GRAVITY .............................................................................................................. 17
2.5. COMPRESSIBILITY FACTOR ............................................................................................ 17
2.6. GAS VISCOSITY ..................................................................................................................... 18
2.7. HYDROCARBON DEW POINT ........................................................................................ 19
2.8. HEATING VALUE ................................................................................................................. 19
3. NATURAL GAS PROCESSING .................................................................................................. 21
3.1. GAS-OIL SEPARATORS ....................................................................................................... 22
3.2. CONDENSATE SEPARATOR ............................................................................................ 22
3.3. ACID GAS REMOVAL .......................................................................................................... 22
3.4. DEHYDRATION .................................................................................................................... 23
3.5. MERCURY REMOVAL ......................................................................................................... 24
Summary Page 4/ 84
3.6. NITROGEN REJECTION .................................................................................................... 25
3.7. FRACTIONATION ................................................................................................................. 25
4. LPG PROPRIETIES ........................................................................................................................ 26
4.1. INTRODUCTION ................................................................................................................... 26
4.2. DEFINITION AND PROPERTIES OF LPG................................................................... 26
4.3. LPG APPLICATIONS AND MARKETS ........................................................................... 27
4.4. CHEMICAL PROPERTIES OF LPG .................................................................................. 28
4.5. PHYSICAL PROPERTIES OF LPG.................................................................................... 28
5. CONVENTIONAL LPG PROCESSING TECHNOLOGY .................................................. 30
5.1. LPG FRACTIONATION PLANT ....................................................................................... 30
5.2. DEETHANIZER ..................................................................................................................... 31
5.3. DEPROPANIZER ................................................................................................................... 31
5.4. DEBUTANIZER ...................................................................................................................... 31
CHAPTER 2 – LPG RECOVERY TECHNOLOGIES .................................................... 32
1. INTRODUCTION ........................................................................................................................... 33
2. LEAN OIL ABSORPTION ............................................................................................................ 34
3. SOLID BED ADSORPTION ........................................................................................................ 35
4. MEMBRANE SEPARATION PROCESS ................................................................................... 37
5. REFRIGERATION PROCESSES ................................................................................................ 38
5.1. MECHANICAL REFRIGERATION .................................................................................. 39
5.2. SELF-REFRIGERATION...................................................................................................... 40
5.3. CRYOGENIC REFRIGERATION...................................................................................... 41
CHAPTER 3 – MAÂMOURA & BARAKA FIELD PRESENTATION .......................... 46
1. INTRODUCTION ........................................................................................................................... 47
2. GEOGRAPHIC LOCATION ........................................................................................................ 47
Summary Page 5/ 84
3. PLANT DESCRIPTION................................................................................................................. 47
4. PRODUCT SPECIFICATIONS .................................................................................................... 48
4.1. SALES GAS SPECIFICATIONS .......................................................................................... 49
4.2. BUTAPRO SPECIFICATION .............................................................................................. 49
5. CONTROL UNITS FOR SALES GAS ........................................................................................ 49
5.1. HYDROCARBON DEW POINT CONTROL ................................................................. 49
5.2. WOBBE INDEX CONTROL ............................................................................................... 51
5.3. HYDRATE FORMATION CONTROL ............................................................................. 51
CHAPTER 4 – DETAILED CASE STUDY & SIMULATION........................................ 53
1. INTRODUCTION ........................................................................................................................... 54
2. PROCESS DESCRIPTION ............................................................................................................ 54
3. PROCESS EQUIPMENTS ............................................................................................................. 55
4. UNIT PERFORMANCE................................................................................................................. 57
5. HYSYS SIMULATION.................................................................................................................... 58
5.1. FEED CHARACTERISTICS ................................................................................................. 58
5.2. REFRIGERATION UNIT SIMULATION RESULTS .................................................... 59
5.3. PROPANE REFRIGERATION CYCLE............................................................................ 61
5.4. THEORETICAL FORMULATION .................................................................................... 61
5.5. COOLING CAPACITY .......................................................................................................... 62
5.6. OVERALL PROCESS SIMULATION RESULTS ............................................................ 65
6. CONCLUSION ................................................................................................................................. 69
CHAPTER 5 – LPG RECOVERY PROCESS OPTIMIZATION .................................... 70
1. INTRODUCTION ........................................................................................................................... 71
2. CHILLER HYDRATES INHIBITION ....................................................................................... 71
2.1. CHOICE OF THE INHIBITOR .............................................................................................. 71
Summary Page 6/ 84
2.2. SPRAY NOZZLE DESIGN ...................................................................................................... 73
3. STUDY OF EG INJECTION PERFORMANCE ..................................................................... 77
3.1. HYSYS SIMULATION ........................................................................................................... 77
3.2. HYSYS RESULTS AND DISCUSSION.............................................................................. 77
3.3. GLYCOL REGENERATION PRINCIPLE ...................................................................... 79
4. CONCLUSION ................................................................................................................................. 81
GENERAL CONCLUSION & PROSPECTS .................................................................................... 82
LIST OF REFRENCES ........................................................................................................................... 83
Summary Page 7/ 84
List of Figures
Figure 1 - Typical Composition of Natural Gas .................................................................................... 15
Figure 2 - PT Diagram for a typical Natural Gas mixture ................................................................... 16
Figure 3- Compressibility Factor of Natural Gas .................................................................................. 18
Figure 4 - Hydrocarbon gas viscosity ...................................................................................................... 18
Figure 5 - Typical Gas plant...................................................................................................................... 21
Figure 6 - PFD of Amine Treating using MEA ..................................................................................... 23
Figure 7 - Glycol dehydration unit........................................................................................................... 24
Figure 8 - Properties of LPG .................................................................................................................... 26
Figure 9 - LPG Prices Variation............................................................................................................... 27
Figure 10 - 2010 Market Prices of LPG in Europ ................................................................................. 28
Figure 11 - LPG Fractionnation Process ................................................................................................ 30
Figure 12 - PFD of an Oill Absorption Plant ........................................................................................ 35
Figure 13 – PFD of a Solid Bed Adsorption Plant ............................................................................... 36
Figure 14 - PFD of a Membrane Separation Process ........................................................................... 37
Figure 15 - Thermodynamic pathways of different NGL Recovery Technologies .......................... 38
Figure 16 - PFD of mechanical separation process .............................................................................. 39
Figure 17 - PFD of Self-refrigeration Process ....................................................................................... 40
Figure 18 - PFD of a cryogenic refrigeration process ........................................................................... 42
Figure 19 - Field location .......................................................................................................................... 47
Figure 20 - Sales Gas Specifications ........................................................................................................ 49
Figure 21 - HDCP Unit ............................................................................................................................. 50
Figure 22 - Retrograde phase envelope for Natural Gas ...................................................................... 50
Figure 23 - Combustion properties as a function of HHV and Wobbe Index ................................. 51
List of figures Page 8/ 84

Figure 24 - Simplified PFD of CP Maamoura & Baraka field refrigeration unit .............................. 55
Figure 25- H-P Diagram of propane ....................................................................................................... 61
Figure 26 - Cold Separator Process Data ................................................................................................ 65
Figure 27 - Temperature in Cold separator stream ............................................................................... 66
Figure 28 - Composition in Cold Separator ........................................................................................... 66
Figure 29 - Hydrates Formation Area ..................................................................................................... 67
Figure 30 - Hydrates Formation Area (Simulation Results) ................................................................. 68
Figure 31 - Glycol Injection PFD ............................................................................................................ 71
Figure 32 - Spray Nozzle Used in glycol injection ................................................................................ 74
Figure 33 - Glycol Stream injected into chiller ...................................................................................... 77
Figure 34 - Simulation Results using Hysys ............................................................................................ 78
Figure 35 - Hydrates Formation Curve ................................................................................................... 79
Figure 36 - Typical Glycol Injection / Recovery Unit .......................................................................... 79
List of figures Page 9/ 84

List of Tables
Table 1- R290 characteristics .................................................................................................................... 57

Table 2 - Simulation Feed Compostion .................................................................................................. 58
Table 3 - Simulation Feed Charecteristics .............................................................................................. 58
Table 4 - Diffrent state cycle points proprieties .................................................................................... 61
Table 5 - Main characteristics of some thermodynamic hydrate inhibitors ....................................... 73
Table 6 -Physical constants of inhibitors. ............................................................................................... 75
List of tables Page 10/ 84

Glossary
COP: Coefficient of performance
EG: Ethylene glycol
HC dew point: Temperature at which a hydrocarbon gas begins to condense
J-T: Joule–Thompson (constant enthalpy) expansion
LCV: Lower calorific value
LNG: Liquefied natural gas
LP: Low pressure
LPG: Liquefied petroleum gas
Mcf: One million cubic feet
Mcfd: Thousand cubic feet per calendar day
MMscfd: Million standard cubic feet per calendar day
MTA: Mass transfer agent, e.g., absorber oil
MTZ: Mass transfer zone
MW: Molecular weight
NCV: Net calorific value
NGL: Natural Gas Liquids
Qc: Heat removed from the cold reservoir.
Qh: Heat supplied to the hot reservoir
RVP: Reid vapor pressure
Scfm: Standard cubic feet per minute
SG: Specific gravity
TEG: Trictylene glycol
General Introduction Page 11/ 84

General Introduction
When we look up to the Olympic flame, we picture Ancient Greece’s glory and celebrate the
humanity for its values. No one focuses on the actual flame, constantly lighting since 1928.
Indeed, LPG has been used to fuel the Olympic flame due to its safety, environmental and
practical characteristics.
Liquefied Petroleum Gas (LPG) is a hydrocarbon mixture (basically made of propane and
butane), extracted from crude oil (40%) or from natural gas (60%). It’s commonly used as a fuel,
autogas and refrigerant, and widely approved for its efficiency and cleanness [1].
This project mainly focuses on a detailed study and simulation of an LPG plant operated by ENI
in Tunisia.
The plant processes include natural gas processing, LPG production, and natural gasoline (C5+)
production. Aspen Hysys Software has been used to carry out accurate simulation leading to new
process flow sheets and a proper sizing of the propane chiller heat exchanger.
Split into five chapters, the work was done using the following plan:
The first chapter is a literature overview of natural gas, LPG, their proprieties and their
processing.
The second chapter is a general study of the LPG recovery technologies from natural gas, with a
detailed study of the refrigeration process.
The third chapter is an overview of Maamoura and Baraka field Gas plant. It includes the process
description, facilities, and product specifications.
The forth chapter is a case study which describes the propane refrigeration loop of the plant and
its equipment. Aspen HYSYS has been used for simulation and performance evaluation
purposes.
The last part chapter focuses on results discussion, and conclusions leading to LPG Recovery
Process Optimization.
General Introduction Page 12/ 84

Chapter 1 – Natural Gas &
LPG Fundamentals
1. NATURAL GAS FUNDAMENTAL
1.1. INTRODUCTION
Natural gas is used primarily as a fuel and as a raw material in manufacturing. It is used in home
furnaces, water heaters, and cooking stoves.
As an industrial fuel, it is used in brick, cement, and ceramic-tile kilns; in glass making; for
generating steam in water boilers; and as a clean heat source for sterilizing instruments and
processing foods. As a raw material in petrochemical manufacturing, natural gas is used to
produce hydrogen, sulfur, carbon black, and ammonia. The ammonia is used in a range of
fertilizers and as a secondary feedstock for manufacturing other chemicals, including nitric acid
and urea. Ethylene, an important petrochemical, is also produced from natural gas.[1]
Natural gas is considered as an environmentally friendly clean fuel, offering important

environmental benefits when compared to other fossil fuels. The superior environmental qualities
over coal or crude oil are that emissions of sulfur dioxide are negligible or that the levels of
nitrous oxide and carbon dioxide emissions are lower. This helps to reduce problems of acid rain,
ozone layer, or greenhouse gases. [1],[2] Natural gas is also a very safe source of energy when
transported, stored, and used.
1.2. NATURAL GAS ORIGIN AND COMPOSITION
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. [4] Natural gas has been formed
by the degradation of organic matter accumulated in the past millions of years.
The principal constituent of natural gas is methane. Other constituents are paraffinic
hydrocarbons such as ethane, propane, and the butanes.
Many natural gases contain nitrogen as well as carbon dioxide and hydrogen sulfide. Trace
quantities of argon, hydrogen, and helium may also be present. The composition of natural gas
can vary widely. Figure 1 [3] outlines the typical makeup of natural gas before it is refined.
Natural gas can also contain a small proportion of C+5 hydrocarbons. When separated, this
fraction is a light gasoline. Some aromatics such as benzene, toluene, and xylenes can also be
present, raising safety issues due to their toxicity. [4]
Chapter I - Natural Gas & LPG Fundamentals Page 14/ 84

Figure 1 - Typical Composition of Natural Gas
Natural gas can contain other contaminants too. Acid contaminants such as mercaptans—R-SH,
carbonyl sulfide (COS), and carbon disulfide (CS2)—may be present in small quantities. Mercury
can also be present either as a metal in vapor phase or as an organometallic compound in liquid
fractions.
The composition of natural gas varies depending on the field, formation, or reservoir from which
it is extracted. Since the composition of natural gas is never constant, there are standard test
methods by which the composition of natural gas can be determined and thus prepared for use.
Natural gas is characterized in several ways dependent on the content of these components: [5]
 Wet gas is raw gas with a methane content of less than 85%.
 Dry gas is raw or treated natural gas that contains less than 15 liters of condensate per
1,000 SM3. (0.1 gallon per 1000 SCF).
 Sour gas is raw gas with a content of more than 5.7 mg hydrogen sulfide (H2S) per SCM
(0.25 grains per 100 SCF); this is about 4 ppm.
 Acid gas has a high content of acidic gases such as carbon dioxide (CO 2) or H2S. Pipeline
natural gas specification is typically less than 2% CO2. Acid gas fields with up to 90%
CO2 exist, but the normal range for sour raw gas is 20-40%.
 Condensates are a mixture of hydrocarbons and other components in the above table.
These are normally gaseous from the well but condense out as liquid during the
production process.

1.3. NATURAL GAS PHASE BEHAVIOR
The natural gas phase behavior is a plot of pressure vs temperature that determines whether the
natural gas stream at a given pressure and temperature consists of a single gas phase or two
phases: gas and liquid.
The phase behavior for natural gas with a given composition is typically displayed on a phase
diagram, an example of which is shown in Figure 2. [6] The left-hand side of the curve is the
bubble point line and divides the single phase liquid region from the two-phase gas–liquid region.
The right-hand side of the curve is the dew point line and divides the two-phase gas– liquid
region and the single-phase gas region.
The bubble point and dew point lines intersect at the critical point, where the distinction between
gas and liquid properties disappears. Note that dew point temperatures are possible at a given
pressure, and two dew point pressures are possible at a given temperature. This phenomenon is
known as retrograde condensation.
The maximum pressure at which liquids can form (Pmax) is called the cricondenbar, and the
maximum temperature at which liquids can form (Tmax) is called the cricondentherm. [5] [6]
The natural gas phase behavior is a function of the composition of the gas mixture and is
strongly influenced by the concentration of the heavier hydrocarbons, especially C+6 .
The presence of heavier hydrocarbons will increase the phase envelope and failure to include
them in a phase calculation will underpredict the phase envelope.
Figure 2 - PT Diagram for a typical Natural Gas mixture

2. NATURAL GAS PROPERTIES
2.1. MOLECULAR WEIGHT
The molecular weight (MW) is calculated as a function of the molecular weight of the individual
components (MWi), provided that both the composition of the gas (yi) [7]
MWg = ∑i MWi
2.2. DENSITY
The density of a gas represents the mass per unit volume of gas and is expressed in kg/m3. It is a
function of the temperature and pressure. Apart from specified conditions, referenced is made to
so-called normal and standard conditions. [6]
2.3. SPECIFIC VOLUME

It represents the volume occupied per unit mass of gas. It is reciprocal of the density, and is
expressed in m3 /kg. [6]
2.4. SPECIFIC GRAVITY

Of a gas is defined as the ratio of the density of the gas at reference conditions to the density of
air at the same conditions, by referring either to normal conditions or to standard conditions.
Assuming that the reference condition considered, one mole of gas analyzed occupies the same
volume as one mole of air, the specific gravity of the gas becomes equal to the ratio of the
molecular weight of the gas Mg to the molecular weight of air Ma:[7]
d = Mg/Ma
2.5. COMPRESSIBILITY FACTOR

The factor of compressibility Z, is a measure of a real gas’s deviation from ideal gas behavior.
PV=ZnRT
It is 1 for ideal gas but for natural gas it varies with the pressure, it tends toward 1 as the pressure
tends toward zero, and the behavior of the gas approaches that of an ideal gas. As the pressure
rises, it goes through a minimum and then increases for high pressures [6] as shown in the
Figure 4 below:

Figure 3- Compressibility Factor of Natural Gas
2.6. GAS VISCOSITY

The knowledge of the viscosity of the gases and condensates is necessary to perform flow
calculations in the different stages of production.
The dynamic and kinematic viscosities are related by the following equation:[6]
γ=µ/ρ
Figure 4 - Hydrocarbon gas viscosity

Figure 4 can be used to estimate the viscosity of a hydrocarbon gas. [7]
2.7. HYDROCARBON DEW POINT

The hydrocarbon dew point is the temperature at which hydrocarbons start to condense from a
gas stream. This is important in in gas production and transmission because condensation in a
natural gas line will lower the capacity of the line to carry gas. Consequently, this could damage
compressors and other processing equipment. More importantly, liquid in a gas line make it
impossible to accurately measure the gas. [7]
2.8. HEATING VALUE

The Btu, or British thermal unit, is a measure of the energy produced by burning natural gas. The
Btu factors of the individual components in natural gas increase with the number of carbon
atoms. [8]
The gross or higher heating value is obtained when:
 All products of the combustion are cooled down to the temperature before the combustion.
 The water vapor formed during combustion is condensed.
The lower or net heating value is obtained when:
 Subtracting the latent heat of vaporization of the water vapor formed by the combustion
from the HHV.
 Most performance heat rates are based on the lower heating value.
Raw gas is processed into various products or fractions:
 Natural gas in its marketable form has been processed for a specific composition of
hydrocarbons, sour and acid components, etc., and energy content. Content is typically 90%
methane, with 10% other light alkenes.
 Natural gas liquids (NGL) is a processed purified product consisting of ethane, propane,
butane or some higher alkenes separately, or in a blend. It is primarily a raw material for
petrochemical industry and is often processed from the condensate.
 Liquefied petroleum gas (LPG) refers to propane or butane or a mixture of these that has
been compressed to liquid at room temperature (200 to 900 kPa depending on composition).
LPG is filled in bottles for consumer domestic use as fuel, and is also used as aerosol
propellant (in spray cans) and refrigerant (e.g., in air conditioners). Energy to volume ratio is
74% of gasoline.

 Liquefied natural gas (LNG) is natural gas that is refrigerated and liquefied at below -162
°C, for storage and transport. It is stored at close to atmospheric pressure, typically less than
125 kPa. As a liquid, LNG takes up 1/600 of the volume of the gas at room temperature.
Energy to volume ratio is 66% of gasoline. After transport and storage, it is
reheated/vaporized and compressed for pipeline transport.
 Compressed natural gas (CNG) is natural gas that is compressed at 2-2,2 MPa to less than
1% of volume at atmospheric pressure. Unlike higher alkenes, methane cannot be kept liquid
by high pressure at normal ambient temperatures because of a low critical temperature. CNG
is used as a less costly alternative to LNG for lower capacity and medium distance transport.
Methane for vehicle fuel is also stored as CNG. Energy to volume ratio is typically 25% of
gasoline. [9]

3. NATURAL GAS PROCESSING
Raw natural gas must be processed to meet the trading specifications of pipeline and gas
distribution companies. As part of the purification, other components such as NGL are
produced, and pollutants extracted.
The diagram in Figure 5 [10] shows an overview of a typical gas plant. Marketable products are
listed in blue and the production process is shown in grey as it is not considered part of the gas
plant.
Figure 5 - Typical Gas plant
There are several stages of gas processing:

3.1. GAS-OIL SEPARATORS
In many instances, pressure relief at the wellhead will cause a natural separation of gas from oil
(using a conventional closed tank, where gravity separates the gas hydrocarbons from the heavier
oil). In some cases, however, a multi-stage gas-oil separation process is needed to separate the gas
stream from the crude oil. These gas-oil separators are commonly closed cylindrical shells,
horizontally mounted with inlets at one end, an outlet at the top for gas removal, and an outlet at
the bottom for oil removal.
3.2. CONDENSATE SEPARATOR
Condensates are most often removed from the gas stream at the wellhead through the use of
mechanical separators. In most instances, the gas flow into the separator comes directly from the
wellhead, since the gas-oil separation process is not needed.
3.3. ACID GAS REMOVAL
Acid gases such as carbon dioxide and hydrogen sulfide form acids when reacting with water, and
must be removed to prevent corrosive damage to equipment and pipelines. Hydrogen sulfide is
also toxic and total sulfur content is normally regulated.
The main removal process can be based on several principles, Amine absorption is the most
common process for acid gas removal.
A typical amine gas treating process (as shown in the figure 6 [11] below) consists of an absorber
unit, a regenerator unit and accessory equipment.
In the absorber, a "lean" amine solution absorbs H2S and CO2 from the up flowing sour gas to
produce a sweetened gas stream as a product. The "rich" amine solution contains the absorbed
acid gases and is routed into the regenerator (a stripper with a reboiler). The stripped overhead
gas from the regenerator is concentrated H2S and CO2. [11]

Figure 6 - PFD of Amine Treating using MEA
3.4. DEHYDRATION
Water levels in natural gas can be reduced to the 10 pmm range in a physical absorption process
in which the gas is contacted with a liquid that preferentially absorbs the water vapor.
In practice, the glycols, ethylene glycol (EG), diethylene glycol (DEG), triethylene glycol (TEG),
tetraethylene glycol (TREG) and propylene glycol are the most commonly used absorbents; [12]
triethylene glycol is the glycol of choice in most instances. For operations in which frequent brine
carryover into the contactor occurs, operators use EG because it can hold more salt than the
other glycols.
Figure 7 [5] below shows a typical, simplified flow sheet for a glycol absorption unit.
The wet gas passes through an inlet scrubber to remove solids and free liquids, and then enters
the bottom of the glycol contactor. Gas flows upward in the contactor, while lean glycol solution
(glycol with little or no water) flows down over the trays [12]. Rich glycol absorbs water and
leaves at the bottom of the column while dry gas exits at the top.
The rich glycol flows through a heat exchanger at the top of the still where it is heated and
provides the coolant for the still condenser. Then the warm solution goes to a flash tank, where
dissolved gas is removed. The rich glycol from the flash tank is further heated by heat exchange
with the still bottoms, and then becomes the feed to the still. The still produces water at the top
and a lean glycol at the bottom, which goes to a surge tank before being returned to the
contactor.
Principally the degree of dehydration required, the physical properties of the glycol solutions, and
the inlet pressure of the gas to the processing unit govern operating conditions for glycol units.
[12]
Figure 7 - Glycol dehydration unit
3.5. MERCURY REMOVAL
Mercury removal is generally based on molecular sieves. A molecular sieve is a substance

containing a material with tiny pores to achieve a large surface area, such as activated carbon.
The surface of the material allows certain molecules to bind by surface tension. The molecules
can later be extracted and the sieve material regenerated by heating, pressure and/or purging with
a carrier gas. A molecular sieve is commonly cyclic with one active unit and one (or more) units
in regeneration.

3.6. NITROGEN REJECTION
Although a less common process in the gas industry, nitrogen rejection will become more
important as we shift to lower-quality gas feedstock. This process is typically cryogenic, although
membrane and absorbent technology are becoming attractive. [13]
3.7. FRACTIONATION
Remaining NGLs are recovered from the gas stream in most modern plants by a cryogenic turbo
expander-based process followed by a fractionating process. This process leads the cooled NGLs
though distillation columns, to extract ethane, propane and butane and leave a residual stream of
pentane and higher hydrocarbons. [14]
Liquid petroleum gas (LPG) mainly contains n-butane, iso-butane, and propane. LPG is generally
manufactured from natural gas or from cracking units of petroleum refineries. The mixture of
low hydrocarbons is condensed under high pressure in refrigeration unit and fractionated
commonly in a deethanizer and debutanizer respectively. [13]
In general LPG contains hydrocarbons of such volatility that they can exist as gas under
atmospheric pressure, but can be readily liquefied under pressure.

4. LPG PROPRIETIES
4.1. INTRODUCTION
In natural gas processing plants, several stages of separation and fractionation are used to purify
the natural gas from the liquid heavier hydrocarbons. This separated liquid is named as natural
gas liquids (NGL). The raw NGL is sent to LPG recovery plant to separate LPG (C3 and C4)
from stabilized NGL (C5+). Both products are very valuable and expensive in the market. [15]
LPG is commonly used as a fuel in heating appliances and vehicles and increasingly replacing
chlorofluorocarbons as an aerosol propellant and a refrigerant to reduce damage to the ozone
layer. [15]
In this project, Eni Maamoura & Baraka LPG recovery plant performance is studied using
commercial software (Aspen Hysys) and investigated for economics of the process. Furthermore,
the existent process is assessed and modified in order to find the most performant process for
LPG production.
4.2. DEFINITION AND PROPERTIES OF LPG

Liquefied Petroleum Gas (LPG) is a mixture of hydrocarbon gases, primary propane and butane.
The exact composition of LPG varies according to its source, processing principles and depends
on the season. For example, in winter it contains more propane (propane vapor pressure at 25⁰C
is 9.36 bar), in summer more butane (butane vapor pressure at 25⁰C is 2.44 bar). [16]
LPG is odorless, colorless and non-toxic. To reduce the danger of an explosion from undetected
leaks, commercial LPG usually contains an odorizing agent, such as ethanethiol, which gives it a
distinctive pungent odor. LPG has a higher calorific value (94 MJ/m³ equivalents to 26.1 kWh)
than natural gas (38 MJ/m³ equivalents to 10.6 kWh) [17]. The properties of LPG are tabulated
in the Figure 8 below:
Figure 8 - Properties of LPG

4.3. LPG APPLICATIONS AND MARKETS
Application of LPG varies from food to transport industry. Its consumption depends on the
local market conditions. LPG is widely used in the Food Industry like hotels, restaurants,
bakeries, canteens, resorts etc. Low sulphur content and controllable temperature makes LPG the
most preferred fuel in the food industry. [16]
 Glass & Ceramic
 Building Industry
 Metal Industry
 Farming Industry
 Aerosol Industry
 Automotive Industry
 Cogeneration using LPG
Besides, LPG is an ideal fuel for electricity & heat / electricity and comfort cooling. This finds
varied applications in industries requiring power and steam, power and hot air. LPG is ideally
suited for shopping malls, offices requiring power and air conditioning.
LPG has lower calorific value then petrol, so it provides less miles per gallon, however in
European countries LPG tax levels are much lower than both diesel and unleaded so it is still a
far more cost effective way to run your car. The tax break is due to evidence that suggests that
LPG is better for the environment than the mainstream fuels.
The cost of LPG is a lot lower than unleaded or diesel fuel, but its price has been gradually rising
since it was first introduced (Figure 9) [18]. The chart below tracks the historical prices for LPG.
Figure 9 - LPG Prices Variation

The current LPG Prices in Europe are presented in Figure 10 [18] (2010 Prices).
Figure 10 - 2010 Market Prices of LPG in Europ
4.4. CHEMICAL PROPERTIES OF LPG

Whatever the source of the LPG, one common factor is found. It comprises hydrocarbons
containing three or four carbon atoms per molecule. It is only these hydrocarbon gases, often
referred to as C3 or C4 gases that are easily liquefied by moderate compression at ambient
temperature. By comparison, natural gas (methane- CH4) can be liquefied only by refrigeration.
Saturated hydrocarbons generally constitute the bulk of commercially available LPG, these being
in the form of propane (C3H8) and butane (C4H10), the latter being found as isobutene and
normal butane. Whilst saturated hydrocarbons are found in LPGs produced from refinery pipe
stills and distillation units, other processes, particularly cracking plants, will result in unsaturated
C3 and C4 which are usually propylene (C 3H6), normal and iso-butylene and transbutylene (C4H8)
[17]
4.5. PHYSICAL PROPERTIES OF LPG

- Vapour pressure: Having subjected the vapor to moderate pressure so as to achieve
liquefaction, the resultant liquid must be contained within a pressurized system (a
pressure vessel), until the gaseous state LPG is required by the consumer.
Vapour pressure is a measure of the volatility of the gas. Where vapour exists, in an
enclosed system, in conjunction with the liquid phase the pressure exerted is referred to
as the ‘saturated vapour pressure’. At the boiling point this pressure is equal to
atmospheric pressure and it increases as the temperature rises to the critical.
Propane, with its lower boiling point (-45°C) thus exerts, under identical conditions, a
greater vapour pressure than butane. [19]
- Boiling points of LPGs: The constituent of gases found in the commercial LPG
mixture all have very low boiling points and therefore normally exist in the vapour phase,
under atmospheric conditions.
Above ambient temperature, the gases exert an increasing vapour pressure thus increasing
the pressure required to achieve liquefaction. This pressure continues to increase until the
‘critical temperature’ is reached ( 96.67 °C for propane, 152.03 °C for n-butane) [20],
above which temperature the gases cease to exist in the liquid state even if further
pressure is applied.
- Coefficient of cubical expansion of liquid: Liquid phase LPG expands considerably as
its temperature increases. The coefficients of cubical expansion at 15°C are approximately
0.0029/°C for propane and 0.0020/°C for butane. [20] This high rate of expansion has to
be fully considered when specifying the maximum quantity of LPG permitted to be filled
into any pressure vessel.
- Limits of Flammability: A mixture of LPG and air is highly combustible within certain
concentrations, known as the flammable range. This range is bounded by the lower and
upper limits of flammability which are proximately 1.8-8.4% for butane and 2.4-9.5% for
propane. These are approximate values at atmospheric pressure. At higher pressures, or
with oxygen, the flammability limits are different. [20]
The term ‘limits of flammability’ assumes that the gas and air are thoroughly mixed. In
practice, LPG escaping into the atmosphere without ignition tends to settle and is often
too rich to burn.
- Dew point: Whereas LPG is stored and distributed in the liquid phase for most
applications; it is normally used in the vapour phase under controlled pressure.
The vapour in a system will be fed under pressure direct from the storage container.
Within the system the temperature must be maintained above the dew point so that the
vapour does not re-condense. [21]

5. CONVENTIONAL LPG PROCESSING TECHNOLOGY
There are several technologies, which have been developed in order to extract LPG from natural
gas liquids (NGL). Some researches and simulations have also been done to find the most
optimum and economic technology. In this project, the conventional LPG recovery process is
studied and assessed in order to evaluate its performance.
Natural gas processing begins at the wellhead. The composition of the raw natural gas extracted
from producing wells depends on the type, depth, and location of the underground deposits and
the geology of the area. The natural gas produced from oil wells is generally classified as
“associated-dissolved,” meaning that the natural gas is associated with or dissolved in crude oil.
Natural gas production without any association with crude oil is classified as “non-associated.”
About 60% of the world supply of LPG comes from associated gas processing, and 40% of the
LPG is produced in oil refineries from crude distillation, fluid catalytic cracking units,
hydrocrackers, etc. The worldwide estimated production of LPG in 2005 was estimated at 250
million tons per year. [21]
5.1. LPG FRACTIONATION PLANT

Most commonly used LPG fractionation system is described in Figure 11. [22]
Figure 11 - LPG Fractionnation Process

Typical LPG Processing includes the following Processes:
5.2. DEETHANIZER
As can be seen from the Figure 11, the stripper bottoms from the extraction plant enter
deethanizer column V-101 near the top. The overhead vapor is partially condensed in deethanizer
condenser E-101 by heat exchange with medium-level propane. Condensed overhead product in
overhead reflux drum V-104 is pumped back to the deethanizer by reflux pump. The non-
condensed vapor, mainly ethane, leaves the plant to fuel the gas system. Heat is supplied to the
column by forced circulation reboiler E-104. The deethanizer column operates at approximately
25 to 30 bar. Typically 98% of the propane in the deethanizer feed is recovered in the bottom
product. The residual ethane concentration is reduced to approximately 0.5 to 1.0 mole % in the
bottom product. The bottom product from deethanizer drains into depropanizer column V-102.
5.3. DEPROPANIZER
Deethanizer bottoms are expanded and enter depropanizer V-102 as mixed-phase feed. The
depropanizer fractionates the feed into a propane-rich product and a bottom product comprised
of butane and natural gasoline. Tower V-102 overhead vapor is totally condensed in the
depropanizer condenser E-102 by cooling water. Condensate is collected in depropanizer column
reflux drum V-105. A part of the condensed overhead product is sent back to the column as
reflux via pump P-103 while the remaining part is withdrawn as a liquid propane product.
Column V-102 reboiler heat is supplied by direct-fired heater H-101. Reboiler circulation is aided
by reboiler circulation pump P-104. The bottom product is sent to debutanizer.
5.4. DEBUTANIZER
The depropanizer bottoms are expanded from approximately and then enter the debutanizer
column as a mixed-phase feed. The column feed is fractionated into a butane-rich overhead
product and natural gasoline bottoms. The columns overhead are totally condensed in the
debutanizer condenser E-103 by heat exchange with cooling water, and condensate is collected in
reflux drum V-106. The debutanizer reflux and product pump P-105 serve the dual purpose of
supplying reflux to the column and allowing withdrawal of column overhead product butane
from the reflux drum. A direct-fired debutanizer reboiler H-102 supplies the column reboil heat,
and debutanizer reboiler circulating pump P-106 aids boiler circulation. [22]
The bottom product leaving the column is cooled in product cooler E-105. A part of the gasoline
product is recycled to the LPG extraction unit and serves as lean oil for the absorber column.
Chapter 2 – LPG Recovery
Technologies
1. INTRODUCTION
The recovery of light hydrocarbon liquids from natural gas streams can range from simple dew
point control to deep ethane extraction. The desired degree of liquid recovery has a profound
effect on process selection, complexity, and cost of the processing facility.
The term NGL (natural gas liquids) is a general term, which applies to liquids recovered from
natural gas and as such refers to ethane and heavier products. The term LPG (liquefied
petroleum gas) describes hydrocarbon mixtures in which the main components are propane, iso
and normal butane, propene and butenes.
Early efforts in the 20th century for liquid recovery involved compression and cooling of the gas
stream and stabilization of a gasoline product. The lean oil absorption process was developed in
the 1920s to increase recovery of gasoline and produce products with increasing quantities of
butane. These gasoline products were, and still are, sold on a Reid vapor pressure (RVP)
specification. Vapor pressures such as 69, 83, 97, 138 or 179 kPa (abs) are common specifications
for gasoline products. [20]
In order to further increase production of liquids, refrigerated lean oil absorption was developed
in the 1950s. By cooling the oil and the gas with refrigeration, propane product can be recovered.
With the production of propane from lean oil plants, a market developed for LPG as a portable
liquid fuel. [22]
In lieu of using lean oil, refrigeration of the gas can be used for propane and heavier component
recovery. The use of straight refrigeration typically results in a much more economical processing
facility. The refrigeration of the gas can be accomplished with mechanical refrigeration,
absorption refrigeration, expansion through a J-T valve, or a combination.
In order to achieve still lower processing temperatures, cascade refrigeration, mixed refrigerants,
and turboexpander technologies have been developed and applied.
With these technologies, recoveries of liquids can be significantly increased to achieve deep
ethane recoveries. Early ethane recovery facilities targeted about 50 % ethane recovery. As
processes developed, ethane recovery efficiencies have increased to well over 90%.
In some instances heavy hydrocarbons are removed to control the hydrocarbon dew point of the
gas and prevent liquid from condensing in pipeline transmission and fuel systems. In this case the
Chapter II – LPG Recovery Technologies Page 33/ 84

liquids are a byproduct of the processing and if no market exists for the liquids, they may be used
as fuel. Alternatively, the liquids may be stabilized and marketed as condensate.
2. LEAN OIL ABSORPTION
The absorption method of NGL recovery is very similar to using absorption for gas dehydration.
The main difference is that, in NGL absorption, an absorbing oil is used as opposed to glycol.
This absorbing oil has an “affinity” for NGLs in much the same manner as glycol has an affinity
for water.
Lean oil absorption is the oldest and least efficient process to recover NGLs. In this process, as
shown in Figure 12, [23] the gas to be processed is contacted in a packed or tray absorption
column (typically operated at the ambient temperature and a pressure close to the sales gas
pressure) with an absorption oil (lean oil), which absorbs preferentially the most heavy
hydrocarbons (C3-C+7) from natural gas. The gas leaves the top of the absorber while the
absorber oil, now rich in heavy hydrocarbons from the gas, leaves the bottom of the absorber
and is expanded to liberate most of the absorbed methane. Rich oil is then sent to a deethanizer
to reject all the methane and part of the ethane absorbed. At the top of this column, additional
cold oil is injected to limit the desorption of ethane and to prevent the desoption of C+3 . Rich
oil then flows to a regeneration column where it is heated to a high enough temperature to drive
the propanes, butanes, pentanes, and other natural gas liquid components to the overhead, and
the regenerated solvent (lean oil) is recycled. [24]
Note that an oil absorption plant cannot recover ethane and propane effectively, where it
requires circulating large amounts of absorption oil, demands attendant maintenance, and
consumes too much fuel. However, an oil absorption plant can be modified to improve its
propane recovery by adding a propane refrigeration cycle for cooling. The liquid recovery
possible in a lean oil plant is typically 99% of the butane and natural gasoline, 65–75% of the
propane, and 15–25% of the ethane contained in the gas [24].
Lean oil absorption plants are not as popular as they once were and are rarely, if ever,
constructed anymore. They are expensive and more complex to operate, and it is difficult to
predict their efficiency at removing liquids from the gas as the lean oil deteriorates with time [25].
They are rarely designed as new plants. Existing lean oil plants are sometimes salvaged,
refurbished, and moved to new locations.

Figure 12 - PFD of an Oill Absorption Plant
3. SOLID BED ADSORPTION
This method uses adsorbents that have the capability to adsorb heavy hydrocarbons from natural
gas. The adsorbent may be silica gel or activated charcoal. Activated alumina cannot be used in
the presence of heavy hydrocarbons, which foul the adsorbent [25]. Note that the design of an
adsorbent-based system for heavy hydrocarbon removal is more complicated than that of a
system for the removal of water only.
For instance, different grades of adsorbent may be required, and the system must also be
designed to accommodate the adsorption of more than one component.
The adsorption process required for removing heavy hydrocarbons is shown schematically in
Figure 13 [26]. The process is continuous with respect to the gas but cyclical with respect to the
adsorbent bed because the latter must be regenerated when it becomes saturated with
condensate.
Regeneration is accomplished by passing heated recycle gas through the bed. The condensate is
recovered from the regeneration gas by cooling, condensation, and phase separation. To recover
a large fraction of the hydrocarbons, while limiting the volume of adsorbent, it is preferable to
use a relatively short cycle time, about 1 hour. In practice, this cycle time may vary within a fairly

wide interval, between 20 minutes and several hours, depending on how hydrocarbon rich the gas
[27].
This process is appropriate for relatively low concentrations of heavy hydrocarbons. It can also
be appropriate if the gas is at a high pressure. In this case, refrigeration processes become
ineffective and separation by adsorption may offer the only way to obtain the required
specifications [30].
Adsorption processes are easy to start up and to operate at high turn down (changes in
throughput) and so are useful for variable and “on–off” operation. However, the adsorption beds
are heavy in weight and expensive. This process option is not often used but may be considered
in special applications, such as hydrocarbon dew point control in remote locations.
Figure 13 – PFD of a Solid Bed Adsorption Plant

4. MEMBRANE SEPARATION PROCESS
Refrigeration and cryogenic plants traditionally have been used for NGL recovery. These plants
have high capital and operating costs. Moreover, they contain numerous rotating parts and are
complicated to operate. The membrane separation process offers a simple and low-cost solution
for removal and recovery of heavy hydrocarbons from natural gas. [27]
Gas permeation membranes are usually made with vitreous polymers that exhibit good
diffusional selectivity. However, for separation to be effective, the membrane must be very
permeable with respect to the contamination to be separated, which passes through the
membrane driven by pressure difference, and it must be relatively impermeable to methane [28].
Membrane Technology & Research Inc. has developed and comercialized a new membrane-
based process for the gas processing industry. The enabling technology of this process is a unique
type of rubbery membrane, which is now being applied to the separation of C+3 hydrocarbons
from methane in gas processing. The new membrane based process is well suited for NGL
recovery and dew point control for associated gas and may also be used to debottleneck existing
gas processing plants. Figure 14 shows a schematic of a membrane separation process for NGL
recovery [25].
Figure 14 - PFD of a Membrane Separation Process
As shown, the separation process is based on a high-flux membrane that selectively permeates
heavy hydrocarbons compared to methane. These hydrocarbons permeate the membrane and are

recovered as a liquid after recompression and condensation. The residue stream from the
membrane is partially depleted of heavy hydrocarbons and is then sent to a sales gas stream.
5. REFRIGERATION PROCESSES
Figure 15 [28] shows the phase behavior of a natural gas as a function of pressure and
temperature. Obviously any cooling outside the retrograde condensation zone will induce
condensation and yield NGL. Retrograde condensation phenomenon has an important
application in NGL production.
Some plants operate at inlet pressures above the critical point and thus revaporize NGLs when
the temperature drops below the retrograde temperature. It is therefore important to know where
we are on the phase envelope.
Refrigeration processes are used at many different temperature levels to condense or cool gases,
vapor, or liquids. This section discusses several refrigeration processes for NGL recovery.
Figure 15 - Thermodynamic pathways of different NGL Recovery Technologies

5.1. Mechanical Refrigeration
Mechanical refrigeration is the simplest and most direct process for NGL recovery. Mechanical
or external refrigeration, as shown in Figure 16 below, is supplied by a vapor-compression
refrigeration cycle that usually uses propane as the refrigerant and reciprocating or centrifugal
types of compressors to move the refrigerants from low to high pressure operating conditions.
As shown in the same Figure, the gas-to-gas heat exchanger recovers additional refrigeration by
passing the gas, leaving the cold separator countercurrent to the warm inlet gas. The temperature
of the cold gas stream leaving this exchanger “approaches” that of the warm inlet gas.
Economically, this approach can be as close as 5◦F. The chiller in Figure 16 is typically a shell and
tube, kettle-type unit. The process gas flows inside the tubes and gives up its energy to the liquid
refrigerant surrounding the tubes. The refrigerant (often propane) boils off and leaves the chiller
vapor space essentially as a saturated vapor.
When water is present in a natural gas processed by refrigeration, hydrate formation is prevented
either by dehydration of the gas or by injection of a hydrate inhibitor. If the processing
temperature is relatively low, the gas is usually dehydrated before the refrigeration step. [29]
Figure 16 - PFD of mechanical separation process
If not, injection of an inhibitor (usually methanol or glycols) upstream of the gas-to-gas heat
exchanger is often the simplest and most economical solution [26].
In this case, ethylene glycol is injected at the inlet of the gas-to-gas exchanger and/or chiller to
prevent hydrate formation, or freeze up, in these exchangers with the latter being more common.
Freeze up will partially block exchanger tubes, thus increasing pressure drop and decreasing heat
exchange. The weak glycol solution, containing absorbed water, is separated in the cold separator,

re-concentrated, and recycled. A mechanical refrigeration process is adopted when sizeable
amounts of condensate are expected. This process may also lead to the recovery of liquefied
petroleum gas, where for LPG recovery up to 90%, a simple propane refrigeration system
provides refrigeration at temperatures to −40◦F [24]. There are many straight refrigeration
process schemes, which vary according to all the design variables, such as gas composition,
process pressure, and LPG recovery objectives. A detailed discussion is given by Russell [25]
5.2. Self-Refrigeration
As opposed to external refrigeration, in the self-refrigeration process (Figure 17), the inlet gas is
precooled against the treated gas (through the gas to gas exchanger) and subsequently cooled
further by isoenthalpic expansion (Joule–Thomson expansion) through a valve, resulting in heavy
hydrocarbons and water to condense. In this process, the nonideal behavior of the inlet gas
causes the gas temperature to fall with the pressure reduction. The temperature change depends
primarily on the pressure drop. [27]
Figure 17 - PFD of Self-refrigeration Process
The condensed liquids are then removed in one or more separators to meet the vapor pressure
and composition specifications. The gas from the low temperature separator (LTS), now
satisfying the sales gas specification, is reheated against the incoming feed. Generally, treated gas
must be recompressed to sales pipeline pressure if it has been expanded to a lower pressure.
Thus, this process is most favored when the raw gas is produced at a very high pressure and can
be expanded to sales-line pressure with no recompression.

If the gas must be recompressed, the process is penalized by the recompression horsepower
requirement.
Note that the extent of cooling in this process is often limited by the hydrate formation
temperature at the prevailing pressure unless a hydrate inhibitor, such as methanol or glycol, is
injected upstream of the gas-to-gas heat exchanger. In this case, the wet glycol and hydrocarbon
condensate are heated and separated in a three-phase separator. Glycol can be regenerated in a
stripper. Because glycol shows some affinity for hydrocarbons, the off-gas from the glycol
stripper often contains BTX [28]
If the objective is to recover ethane or more propane than obtainable by mechanical refrigeration,
a good process can be self-refrigeration, which is particularly applicable for smaller gas volumes
of 5 to 10 MMCFD [24]. The self-refrigeration process may also is attractive if the inlet gas
pressure is very high. It is important that the reservoir pressure remain high for the intended life
of the plant. Low-pressure inlet gas favors a cryogenic refigeration plant or straight refrigeration
process (if the gas is very rich).
5.3. Cryogenic Refrigeration

When insufficient pressure is available to attain the required dew point with the self refigeration
process, cryogenic refrigeration can be considered. Cryogenic refrigeration processes traditionally
have been used for NGL recovery. These plants have a higher capital cost but a lower
operational cost.
Moreover, they contain numerous moving parts and are complicated to operate [30].
In the cryogenic or turboexpander plant, the chiller or Joule–Thomson (JT) valve used in two
previous processes, is replaced by an expansion turbine.
As the entering gas expands, it supplies work to the turbine shaft, thus reducing the gas enthalpy.
This decrease in enthalpy causes a much larger temperature drop than that found in the simple JT
(constant enthalpy) process.
The turbine can be connected to a compressor, which recompresses the gas with only a small loss
in overall pressure. This results in a higher treated gas pressure, which can be increased to the
pipeline specification by a second compression step.
Although there are variations in the design of expander plants, most expander plants have the
same basic process flow as shown in Figure 18.
The inlet gas is first cooled in the high-temperature, gas-to-gas heat exchanger and then in the
propane chiller. The partially condensed feed gas is sent to a separator. The liquid from the

separator is fed to the demethanizer, and the gas is cooled further in the low-temperature gasto-
gas exchanger and fed into a second cold separator. Gas from the cold separator expands
through the expansion turbine to the demethanizer pressure, which varies from 100 to 450 psia.
The turbo expander simultaneously produces cooling/condensing of the gas and useful work,
which may be used to recompress the sales gas. Typically 10 to 15% of the feed gas is condensed
in the cold separator, which is usually at −30 to −60◦F. The expander lowers the pressure from
the inlet gas value (600 to 900 psia) to the demethanizer pressure of 100 to 450 psia.[24]
Figure 18 - PFD of a cryogenic refrigeration process
Typical inlet gas temperatures to the demethanizer are −130 to −150◦F, sufficiently low that a
great deal of the ethane is liquefied. The demethanizer is a low temperature distillation column
that makes a separation between methane and ethane. Methane and components lighter than
methane, such as nitrogen, are the principal products in the vapor near the top of the column,
whereas ethane and heavier components, such as propane, butanes, and heavier hydrocarbons,
comprise the principal components in the bottom product of the column. The molar ratio of
methane to ethane in the bottom product is typically 0.01 to 0.03. Because the outlet of the
expander is usually two-phase flow, the liquid produced in the expander serves as reflux for the
demethanizer [25]. The bottom product from the demethanizer is fractionated further to produce
pure product streams of ethane, propane, butanes, and natural gasolin. The bottom product
temperature is often below ambient so that feed gas may be used as the heat transfer medium for
the reboiler. This provides additional refrigeration to the feed and yields higher ethane recovery,
typically 80% .[28].The top product from the demethanizer, after heat exchange with the inlet
gas, is recompressed to pipeline pressure and is delivered as the sales gas.

Cryogenic processes can only be applied if the gas pressure after expansion is sufficiently high for
condensation of the heavier components to take place. However, if the gas arrives at low
pressure (say less than 725 psi), external mechanical refrigeration must be used to cool it to the
specified temperature. In addition if the NGL content of the feed gas is relatively low [less than
2.5 to 3 gallons per Mcf (GPM2], self-refrigeration (gas-to-gas heat exchanger) usually suffices.
However, for moderately rich feeds (>3 GPM), mechanical refrigeration should be considered to
obtain high ethane recovery most economically [30]
Note that in this application, the attainable hydrocarbon dew point specifications are very good,
but similar to the self-refrigeration process, upstream dehydration of the gas is required to
prevent hydrate formation.
Solid bed dehydration upstream of the plant is a proven technique for preventing hydrate
formation. Sometimes, small quantities of methanol or glycol can also be injected upstream of the
expander.
Cryogenic refrigeration process is generally the most technically advanced type of NGL recovery
used today. This combines high recovery levels (typically allowing full recovery of all of the
propane and heavier NGLs and recovery of 50% to more than 90% of the ethane) with low
capital cost and easy operation [28]
This is less attractive on very rich gas streams or where the light NGL product (C2 and C3) is not
marketable, whereas for gases very rich in NGL, simple refrigeration is probably the best choice.
Within the liquids recovery section of the gas processing plant, there are both operating cost and
operating flexibility issues that directly impact the processing cost. While it is easily recognized
that the efficiency of the selected liquids recovery process is an important factor in the processing
cost, the flexibility of operating the process to either recover or reject ethane without sacrificing
efficiency or propane recovery is often the critical factor [30].
As the industry matured and the demand for more efficient ethane recovery increased, several
new and very clever designs have been developed.
 Choice of Refrigerant
Any material could be used as a refrigerant.
The ideal refrigerant is nontoxic, noncorrosive, has Pressure-Volume-Temperature (PVT) and
physical properties compatible with the system needs, and has a high latent heat of vaporization.
The practical choice reduces to one, which has desirable physical properties and will vaporize and
condense at reasonable pressures at the temperature levels desired.

In general, the lower practical limit of any refrigerant is its atmospheric pressure boiling point. It
is desirable to carry some positive pressure on the chiller to obtain better efficiency in the
compressor, reduce equipmentsize, and avoid air induction into the system. Propane is by far the
most popular refrigerant in gas processing applications. It is readily available (often manufactured
on-site), inexpensive, and has a “good” vapor pressure curve. It is flammable but this is not a
significant problem if proper consideration is given to the design and operation of the facility [5]
Desired properties for refrigerants are nearly the same as for any other thermal-enregy transport
fluid (heating fluids included)[15]
- Large thermal capacity and density (to minimize flow-rate).
- Wide temperature margin (to avoid decomposition or freezing).
- High thermal conductivity (to lower residence time).
- Low viscosity (to lower pumping needs).
- Compatibility with piping materials and joints.
- Safe (non-flammable, non-toxic).
- Adequate economic and environmental constrains.
Besides, for primary refrigerants used to generate cold by vaporization, additional and most
important properties are:
- Appropriate vapour pressure values, related to the intended application. Critical

temperature is above the ambient Tcr> T amb.
- Large vaporization enthalpy.
- Small isentropic coefficient ( to avoid too much heating in the compressor).
 Types of refrigerants
There are several possible classifications of refrigerant fluids. [15]
By purpose, two kind of refrigerant fluids can be distinguished:

- Primary refrigerants, which are the working fluids of a refrigeration machine, e.g. n-
butane, R134a, CO2. They get heat from the load and, after some further processes, they
give off heat to the sink.
- Secondary refrigerants, which are auxiliary fluids used to transport the low temperature
effect to more convenient places, and they may be chilled water down to 0°C, or
antifreeze fluids: glycols, brines, etc.

By hydrocarbon numbering system, the general rule is R-xyzC, with the common initial R
standing for ‘refrigerant’, xyz being a 3-digit number related to the particular molecule, and C
being character to extend the identification.
By chemical type (IUPAC):

- CFC: chloro-fluoro-carbon compounds
- HCFC: hydro-chloro-fluoro-carbon
- HFC:hydro-fluoro-carbon
- HFO:hydro-fluoro-olefin
Besides, natural refrigerants are air, water, ammonia, CO2.

Chapter 3 – Maâmoura &
Baraka Field Presentation
1. INTRODUCTION
This chapter presents a general overview of Maamoura and Baraka onshore treatment plant.
First, we will describe its location, then a description of the treatment units will follow, and finally
we will state the required product specifications.
2. GEOGRAPHIC LOCATION
Maamoura and Baraka onshore treatment plant is located, approximately 13 Km northwards
from Nabeul at 1.8 Km from that cost as shown in the following Figure 19:
Figure 19 - Field location
3. PLANT DESCRIPTION
The reservoir fluid from shore is exported to the Treatment Plant via tow independent pipelines,
10” is the sealine from Maamoura platform and 12” is the sealine from Baraka. The reservoir
fluid delivered to the Treatment Plant is subject to the following treatments:
- High pressure separation in two slug catchers (finger type) to separate water and liquid
hydrocarbons from the gas.
Chapter III – Maâmoura & Baraka Field Presentation Page 47/ 84

- Low pressure separation in a three-phase separator to separate gas/oil and water.
- Gas compression.
- Gas sweetening, including MDEA regeneration system.
- Gas dehydration, including TEG regeneration system.
- Gas hydrocarbon dew point control with propane refrigeration unit.
- Wobbe index control with nitrogen injection.
- Produced water treatment.
In addition, the following facilities are installed in Treatment Plant:
- Fuel gas system.
- Electric power distribution system.
- Service water system.
- Nitrogen generation and distribution system.
- Utility and instruments air system.
- Flaring system.
- Pig receiving facilities for the sea lines.
- Storage tanks for oil, LPG and treated water.
- Loading arms provided with appropriate flow metering system for oil and LPG.
- Fire and gas detection system.
- Fire fighting systems.
- Open and closed drain system.
- Control building hosting the plant controls system.
- Emergency power generator for vital items of the plant.
4. PRODUCT SPECIFICATIONS
The facilities are designed to receive the offshore fluids and produce sales gas, stabilized oil and
Butapro I (A mixture of propane and butane).
The gas is exported to STEG network via a dedicated 10” GASLINE, the stabilized oil and the
LPG are exported by trucks.
In the outlet of the Treatment Plant a fiscal metering station is installed to measure the flow rate
and monitor the gas composition.
The waste water associated to hydrocarbon production is stored, after adequate treatment, into a
water tank for disposal by trucking.
4.1. SALES GAS SPECIFICATIONS
Sales gas specifications are summed up in the figure 20 below:
Figure 20 - Sales Gas Specifications
4.2. BUTAPRO SPECIFICATION

Besides sales gas, Maâmoura & Baraka field is producing Butane-Propane mixture for
commercial purposes, with a Relative Vapor Pressure below 11.5 Kg/cm 2, at 50°C.
5. CONTROL UNITS FOR SALES GAS

5.1. HYDROCARBON DEW POINT CONTROL
Accurate HCDP data will assist in controlling gas processing. Good processing will prevent shut-
ins, help to maintain pipeline integrity and prevent hydrate formation which could damage in-
stream devices such as compressors, valves, sample probes and orifice plates. [17]
In order to meet sales gas specification, Sweet and Dried gas is routed to Hydrocarbon Dew-
Point System for reducing the calorific value of the gas. Dew point control system has the duty to
reduce drastically the condensable hydrocarbons.
The dew point of hydrocarbon and water are controlled to ensure safety operations, security of
supply and complying with contractual specifications including: [18]
- Efficient utilization of line pack

- Recovery of natural gas liquids
- Prevention liquid hydrocarbon slugging in a pipeline
- Minimization of pressure drop
- Avoiding corrosion.
A formal definition of HCDP (Figure 21) can be stated as the temperature at which hydrocarbon
condensates first begin to form when natural gas is cooled at a constant pressure.

A working definition is the temperature at which hydrocarbon condensates first begin to form a
visible deposit on a surface, when the gas is cooled at a constant pressure.
When a rich gas field is developed the gas must be processed before it is ready to be sold to
pipeline gas. The competitive producer/processor must remove the heavier components in order
to supply high quality gas to the market. [17]
A common way to remove heavy gas components is to chill the gas so the heavy components
condense and drain away. A likely undesirable result is a lower Btu product which can reduce the
market value for their customer. [17]
Figure 21 - HDCP Unit
The figure 22 above shows the retrograde dew point reduction after processing:
Figure 22 - Retrograde phase envelope for Natural Gas

5.2. WOBBE INDEX CONTROL
The wobbe index (WI) or wobbe number is an indicator of the interchangeability of a fuel gases
such as natural gases, LPG and refinery gas and it is frequently defined in the specifications of gas
supply. The wobbe index is used to compare the combustion energy output of different
composition fuel gases. [19]
The wobbe number is calculated as follows:
W= HHV /√D
Where:
HHV = high heating value
D= gas density
The Nitrogen Unit is producing nitrogen for Wobbe index control. Generally speaking, a gas in
the preferred ranges of HHV and wobbe index will burn without combustion problems such as
flame lifting, flashback, excessive NOx and CO, or yellow tipping, Figure 23 shows the preferred
Wobbe index region and the consequences of operation in objectionable ranges. [19]
Figure 23 - Combustion properties as a function of HHV and Wobbe Index
5.3. HYDRATE FORMATION CONTROL

Hydrate formation causes many operating problems, such as partial or complete blocking of
pipelines, chokes, valves and instrumentation, fouling and plugging of heat exchangers, erosion
of expanders, etc... [20]

The plant equipment and piping must be monitored carefully to verify that hydrates do not form
in the lines or equipment. If the pressure inside the Cold Separator drops quickly, there may be
hydrates in the cold sections. Inhibitor injection ahead of the gas chiller is required on CPF.

Chapter 4 – Detailed Case
Study & Simulation
1. INTRODUCTION
Refrigeration systems are commonly found in the natural gas processing industry and in
processes related to the petroleum refining, petrochemicals, and chemical industries.
Refrigeration is used to cool gas to meet a hydrocarbon dew point specification and to produce a
marketable liquid.
In this chapter, we will construct, run, analyze and manipulate the existing propane refrigeration
loop simulation.
2. PROCESS DESCRIPTION
The propane refrigeration system supplies propane refrigerant to the Propane Chiller (340-HA-
003) and the LPG Stripper Overhead Condenser (211-HA-006). Propane gas from the users is
routed to the Propane Receiver (400-VN-001) to remove the entrained liquids. It is then
compressed to 16 Bara by Propane Compressors (400-KA-001 A/B). The Compressors are oil
flooded two stage screw compressors. The discharged propane gas is condensed through the
Propane Condenser (400-HC-001 A/B). Condensed liquid propane is sent to the propane Surge
Drum (400-VA-001) and then it is flashed and routed to the Propane Economizer (400-VA-001).
Vapor will be separated from liquid in the economizer and convoyed to the second stage
compression to repeat the cycle while the separated liquid refrigerant from the bottom of
economizer will submit a second expansion before entering the Propane Chiller and the LPG
Stripper Overhead Condenser at a reduced temperature (due to the Joule-Thomson cooling
effect over the letdown valves)
Dry gas from the TEG outlet coalesceris routed to Gas/Liquid Exchanger (340-HA-001) and the
Gas/Gas Cooler (340-HA-002) where it is precooled using cold gas and LPG from cold
separator (340-VA-001). The gas is cooled in the tube side of Propane Chiller and routed to the
cold separator where gas is separated from liquid, passed through gas/gas cooler and the
Sweet/Sales Gas Exchanger before going to sales.
Hydrocarbon liquids from the cold separator bottoms are heated through the Gas/Liquid
Exchanger and then fed to the LPG Stripper (211-VE-001). The overhead gas from the top of
the LPG Stripper is partially condensed via propane refrigerant through the LPG stripper
Overhead Condenser before going to the LPG Overhead Accumulator (211-VA-005). Gas from
LPG Overhead Accumulator is heated up through the Gas/Propane Exchanger (400-HA-001)
before it is recycled back to the main compressors. Liquid from the LPG Overhead Accumulator
is recycled to the top tray of the LPG Stripper. Refer to Figure 24 for a simplified PFD.
Chapter IV – Detailed Case Study & Simulation Page 54/ 84

Figure 24 - Simplified PFD of CP Maamoura & Baraka field refrigeration unit
3. PROCESS EQUIPMENTS
Process equipment include:
Shell and tube heat exchangers

The shell and tube heat exchanger consists of a shell, usually a circular cylinder, with a large
number of tubes, attached to an end plate and arranged where two fluids can exchange heat
without coming in contact with one another.
Refrigerant Chiller and LPG Stripper Overhead condenser are shell and tube exchange
Refrigerant chiller 340-HA-003

The process gas flows inside the tubes and gives up its energy to the liquid refrigerant
surrounding the tubes. The refrigerant boils off and leaves the chiller vapor space essentially as a
saturated vapor.

LPG Stripper Overhead Condenser
The LPG Stripper Overhead Condenser is shell and tube type. The Propane flows in the shell
side meanwhile the vapour flows in the tube side
The Propane refrigerant, from the Propane Economizer, is used to partially condensate the
overhead vapour from the LPG Stripper by cross exchange in the LPG Stripper Overhead
Condenser. The overhead vapour is cooled to the maximum degree possible, limited by heat
exchanger. Gas from the LPG Overhead Accumulator is heated up through the Gas / Propane
exchanger before it is recycled back to the main compressors.
Refrigerant compressor (340-HA-003)

The refrigerant compressor is a two stage screw compressor, the gas from the propane receiver
enters to the first compression stage and the gas from the propane economizer fed the second
compression stage.
The separate processes experienced by the vapor in passing through the compressor are:[18]
-filling of a cavity with suction gas
-sealing the gas between the rotor and housing
-reducing the volume of cavity to perform the compression
-uncovering the discharge opening to expel the compressed gas to the discharge line
Propane Reclaimer
Propane refrigerant coming from propane compressor could contain small ppm levels of lube
oils. Over time, lube oil can accumulate in the gas chiller.
The Propane Reclaimer on chiller is operated to drain accumulated lube oil from the chiller
shells.
We use the hot oil to boil off refrigerant from the oil, and then the accumulated oil is manually
drained from the Reclaimer pots to Close Drain Header so it is important to drain only oil and
not allow refrigerant vapours to escape.
Propane receiver
Operating at 1.03 bar, is used to gather gas propane from chiller and from LPG OH Condenser,
Overhead propane is sent to propane compressor.

Propane economizer
Propane economizer received propane liquid from Surge drum after being flashed at 4 bar, Vapor
from the economizer is router under pressure control to the second stage suction of the propane
compressor and liquid from the bottom is sent to propane chiller and to LPG OH condenser
through line.
*Refrigerant fluid: Propane

Propane R290 used as a refrigerant has the following characteristics: [22]
Table 1- R290 characteristics
Chemical formula C3 H8
Family Hydrocarbons
Appearance Clear
Vapor pressure at 20°C 7.3 ± 0.2 bar
Boiling temperature at 0.1013 MPa -42.1
Molecular weight (g/mol) 41.1
Density of liquid at 20°C (kg/dm3) 0.500
Density of vapor at 20 °C (kg//dm3) 0.018
Absolute pressure à 20 °C (bar) 8.5
Critical temperature 96.7
Critical pressure (MPa) 4.25
Auto-ignition temperature (°C) 480
4. Unit performance
The refrigeration unit is basically used to control hydrocarbon dew point, NGL production and
fractionation, in order to recover a maximum rate of LPG and heavier components from natural
gas.
Actually, the plant fed about 16000 Sm3/h of dry natural gas at 26 bar with a Butapro contents
of 5.4 % mol, it produces 1400 Sm3/h of sales gas with 3.8 % Content of Buta-pro, and
recovered 15 to 17% of LPG.
The main problem is that the raw gas is refrigerated in the propane chiller by heat exchanging
with the propane refrigerant, the temperature is lowered to about -26°C which turns out to be
not enough to recover all the C3 and C4 fraction.
That being stated, the sales gas contains about 2.6 % of propane which makes the HHV of the
sales gas high and the wobbe index reaches the maximum limit required by the STEG.
5. HYSYS SIMULATION
To simulate the performance of the existing propane refrigeration unit, ASPEN HYSYS software
V7.1 has been used as a simulation tool. This software is commonly used in various fields of
engineering to analyze the behavior of a system and optimize its operation by testing different
solutions and different operating conditions.
5.1. FEED CHARACTERISTICS
Gas from glycol outlet coalescer entering to the chiller has the following composition and
characteristics:
Table 2 - Simulation Feed Composition
Intel gas composition Molar fraction (%) From glycol outlet coalescer
Nitrogen 1.47
CO2 0.48
Methane 73.17
Ethane 15.48
Propane 5.91
i-Butane 1.00
n-Butane 1.52
i-pentane 0.41
n-pentane 0.30
n-hexane 0.17
n-heptane 0.06
n-octane 0.02
H2O 0.01
TEG 0.00
Total 100
Table 3 - Simulation Feed Charecteristics

Inlet gas Characteristics From glycol outlet coalescer
Vapour fraction 1.00
Temperature (°C) 26.7
Pressure ( Bara) 26
Molar flow (Sm3/h) 0.02564
Mass flow (Kg/h) 6948
Vapor Molecular weight 20.54
Vapor viscosity (Cp) 0.01185
Vapor Cp/Cv 1.362
Vapor compressibility 0.9134

5.2. REFRIGERATION UNIT SIMULATION RESULTS
The Hysys PFD of the refrigeration unit on the CPF is shown in the Plan bellow.

5.3. PROPANE REFRIGERATION CYCLE
Figure 25- H-P Diagram of propane
From graphic and linear interpolation on the Propane Mollier Diagram, we can determine P, T
and h values indifferent points of the cycle.
Table 4 - Diffrent state cycle points proprieties
State 1 2 3 3’ (isentrope) 4
P (bar) 1.1 1.1 11 11 11
T (℃) -40.3 -40.3 63.5 50 30
h (kJ.kg-1) 280 540 650 675 280
5.4. THEORETICAL FORMULATION
From the first law of thermodynamics applied to an open system we have:

∆h = W + Q

If compression is reversible and adiabatic (isentropic), the mechanical energy supplied to the fluid
for its compression is (per kilogram of fluid):
Wis = ∆his = his − h2
If we consider that the compression is real but adiabatic, compression work Wreel is given by:
Wreal = h3 − h2
The isentropic efficiency is the ratio of the isentropic compression work and the actual work of
compression:
Wis ∆his
ηis = =
Wreal ∆hreal
In the case where the compression is not adiabatic, the amount of heat released to the external
medium is:
Q = ∆h − W
And the compression work is:
k−1
k P
Wreal = k−1 r Tmin [( Pmax ) k − 1]
min
Where k is the polytropic compression coefficient.

In addition to the effects related to the nature of the compression was the dissipative effects due
to movements of the piston that moves. The mechanical efficiency into account, what is the ratio
of actual compression work on the work absorbed by the compressor Wa :
Wreal
ηm =
Wa
5.5. COOLING CAPACITY

The amount of recovered heat by the refrigerant and transferred by the cold source is called
cooling capacity and is given by:
Q f = qm (h2 − h1 )
COP Calculation
The refrigeration coefficient of performance (COP) real is given by equation (eV16):
Qf h2 − h1
COP = =
Wreal h3 − h2
The coefficient of performance (COP) of Carnot is given by expression :

Tf
COPcarnot =
Tc − Tf
Finally, the ratio of the actual COP / COP Carnot is given by:
COP
η=
COPcarnot
Compression Step—Cycle analysis begins with propane vapor entering the compressor as a
vapor at 1.1 bar and approximately −40°C, where it is compressed to 4 bar, then fed into the
second stage to be compressed to 11 bar at 63.5°C.
From the simulation result, qm = 4461 Kg/h
Wis = ∆his x qm = (his − h2 ) 𝑥 4461= (675 – 540) x4461 = 6.02235 105kJ.kg-1
The real compression work is:
Wréel = qm × (h3 − h2 ) = (650 – 540)x 4461= 4.90710 105kJ.kg-1
Wis ∆his
The isentropic efficiency is :ηis = W = ∆h = 0.81
real real
Condensation Step—The warm gas goes to an air cooler (condenser), where the propane cools
to 30°C, totally condenses, and collects in the propane surg drum(point 3 to point 4 in Figure 26)
This step is simply:
𝑄𝑐𝑜𝑛𝑑 = (ℎ4 − ℎ3)𝑞𝑚 = (650 – 280)x4461 = 16.50570 105kJ.kg-1
Expansion Step—Propane liquid leaves the propane surge drum and flashes through a J-T
valve, where the temperature and pressure drop to −5°C and 4 bar.
Liquid gas mixture is fed to an economizer where the gas fraction is sent to the second stage
compression, and were the remaining liquid fraction is divided into two. Liquid propane fed
respectively the propane chiller and The LPG Overhead condenser, after being expanded again
from 4 bar to 1.1 bar.
No change occurs in the enthalpy, but the temperature drops to the saturation temperature of the
liquid at the expansion-discharge pressure, and h4 = h1 if there are no heat leaks.

Refrigeration Step—The cold propane then goes to a heat exchanger, the chiller/LPG
Overhead condenser, where it cools the process stream by evaporation (point 4 to point 1 in
Figure 25).
Because the propane in the chiller is evaporating, and a minimal heat exchange occurs between
cold propane vapor and the inlet gas, the inlet and outlet propane temperature remains constant.
The propane returns to the compressor suction slightly above −40°C. The heat absorbed by the
propane is simply h2– h1.
The chillers are the kettle type in which propane is on the shell side and the liquid level is
maintained above the tube bundle.
The chiller typically has two zones of heat transfer.
The first is exchange of boiling propane with gas above its dew point and will involve only
sensible heat.
The second zone has condensing vapors from the process stream and boiling propane, which
gives a much higher overall heat-transfer coefficient [4].
To complete the cycle, the propane vapors leave the chiller and go to the suction drum before
being compressed again.
Refrigeration-cycle performance is commonly stated in terms of coefficient of performance

(COP), which is the ratio of the refrigeration obtained divided by the work required. The COP is
then determined by
Qf h2−h1
COP = W = andQ f = qm (h2 − h1 )
real h3 −h2
Qf= 4461 x (540 - 280) = 1.15986 x 106Kj/h
What leads us to

Qf 1.15986 x 106
COP = W = = 2.3636
real 4.90710𝑥105
Tf
COPcarnot = T = -40.3 +273.15/ 30+40.3 = 232.85/70.3 = 3.31
c −Tf
Finally, the refrigeration ratio is given by:
COP
η = COP = 2.3636/3.31 = 0.71
carnot
5.6. OVERALL PROCESS SIMULATION RESULTS
From a comparison between the real conditions and the simulation results, we notice that all the
equipment of the refrigeration unit are performing well.
However, there is a difference in the temperature of the cold separator, which is on reality -26°C
while it have to be cooled down to about -37°C to remove the highest possible fraction of
condensed liquid in the cold separator. The discussed process part is the flowing:
Figure 26 - Cold Separator Process Data
Next figure is a table generated by Hysys it shows us the Temperature of the discussed streams:

Figure 27 - Temperature in Cold separator stream
The composition of the streams should be:
Figure 28 - Composition in Cold Separator
Once the outlet chiller is cooled down to -37 °C, the sales gas contains only 2.5 % of C3, and 0.4
%of butanes comparing, which may significantly decrease the HHV of the sales gas and its
Wobbe index.
Actually the Propane chiller is the most critical part of the process giving the fact that heat
exchange doesn’t reach the desired temperature on the tube outlet.

The inlet gas to the chiller contains 60 ppm of water which may cause hydrate formation.
From the HYSYS results and specially from the hydrate curve of the process gas, we notice that
we are in the area of hydrate formation, a hydrate layer is formed inside the tubes, and freeze up
and lead to a partially blockage of the exchanger’s tubes which cause consequently a decrease in
the heat exchange.
Figure 29 - Hydrates Formation Area
HYSYS identifies the type of hydrate formed into the tube of the chiller, the temperature of the
first hydrate formed and its lower pressure:

Figure 30 - Hydrates Formation Area (Simulation Results)
In our study case and since the hydrate formation depends on the gas composition, HYSYS
results shows that it will form at -9.66°C over1.12 bar.
Gas hydrates are representatives of a class of compounds known as clathrates or inclusion

compounds. Natural gas and crude oil normally reside in reservoir in contact with connate water.
Water can combine with low-molecular weight natural gases to form a solid, hydrate, even if the
temperature is above water freezing point. Hydrates are considered as nuisance because they
block transmission lines, plug blowout preventers, jeopardize the foundation of deep water
platforms and pipelines, cause tubing and casing collapses, and foul process heat exchangers,
valves, and expanders. Hydrates act to concentrate hydrocarbons; 1cuft of hydrates may contain
as much as 180 SCF of gas.
Large natural reserves of hydrocarbons exist in hydrated form, both in deep oceans and in the
permafrost. Evaluation of these reserves is highly uncertain, yet even conservative estimates
indicate that there is perhaps twice as much energy in the hydrated form as in all other
hydrocarbon sources combined. The next chapter is intended to provide the basic information
needed for engineering purposes about hydrates.

In our case we notice from HYSYS results the formation of type II which has a crystalline
structure where water molecules build the lattice and hydrocarbons, nitrogen and CO2 occupy the
cavities. For this type of hydrates C3H8, i-C4H10 and n-C4H10 contribute in its formation.
6. CONCLUSION
In this chapter, we studied the performance of the external refrigeration, 2 stages propane cycle
performing in Maamoura & Baraka field, we calculated all the factors on each refrigeration step,
to finally determine the COP, and the refrigeration ratio.
The HYSYS simulation of the real process confirms that this unit is working well, all the
equipment are performing, but we noticed a probability of hydrate formation onthe propane
chiller, which may decrease heat exchange and deteriorate sales gas / LPG quality.
In the following chapter we will define the optimization axis in order to recover a drier sales gas,
and a higher content of butapro in the LPG final product.

Chapter 5 – LPG Recovery
Process Optimization
1. INTRODUCTION
After a detailed study of the current Process, and using simulation results, we will be trying to
perform the LPG Recovery Process Optimization in the current chapter.
2. CHILLER HYDRATES INHIBITION

Fundamentally, there are four ways to prevent hydrates from forming:
- Reducing the pressure below that of the hydrate formation for the given temperature;
- Maintaining the temperature of the gas flow above the hydrate formation temperature for
the given pressure;
- Reducing the dew point of water vapor in the gas flow below the operating temperature
(drying the gas);
- Introducing various substances (alcohols, electrolytes) into gas flow, which lower the
hydrate formation pressure.
This chapter examines the fourth process of hydrate prevention.
As we stated before, when even a small fraction of water is still present in a natural gas, this
promotes hydrate formation under refrigeration operations, where temperature is relatively low.
In our case study, raw natural gas streaming out of the dehydration unit, have a 60 ppm content
of water,in order to inhibit hydrate formation, the injection of an inhibitor upstream of the
gas/gas heat exchanger and the chiller, is recommended for a simplicity and economical purpose.
Figure 31 - Glycol Injection PFD
2.1. CHOICE OF THE INHIBITOR
Chapter V – LPG Recovery Process Optimization Page 71/ 84

Frequently inhibitors are injected into processing lines as a means of hydrate control by both the
breakage of hydrate hydrogen bonds and the competition for available water molecules. The
more frequently used inhibitors are strong polar fluids, such as methanol, the ethylene glycols,
and ammonia, arranged in order of decreasing usage frequency. Of the above three chemicals, the
uses of methanols and the ethylene glycol are pervasive. While ammonia is more than twice as
effective as methanol, it is only used in cases of severe hydrate blockage, due to the reaction of
NH3 with CO2 in the gas to form plugs of solid ammonium carbonate, bicarbonate and
carbamate. The handling of ammonia is also an important safety consideration.
Methanol: It is widely used as hydrate inhibitor. [23]

It has some disadvantages:
- In LPG pipelines, methanol added as an inhibitor forms propane + methanol and n-
butane + methanol azeotropes, because of this methanol appear in unacceptable levels.
- If we use a corrosion inhibitor on the pipelines, especially if inhibitors are alcohol-based,
methanol dissolved the corrosion inhibitor which leads to some unexpected corrosion
level.
Methanol is volatile substance; we have to pay attention on vapor loss. In practical terms, this
means that more inhibitor must be injected than the amount required mitigating the hydrate
formation theoretically. [23]
Methanol is normally used for flow line plugs. Most frequently than methanol injected in to the
pipelines as a loss, although in gas processing methanol recovery is viable in turbo expander
plant.
Glycols: It has more hydrogen bonding opportunity with water through one more hydroxyl
group than alcohols, it has generally higher molecular weights, which means that it is not volatile,
the commonly used glycols are EG, TEG, propylene glycol.[23]
When dissolved in aqueous solution, it forms hydrogen bond with the water molecules and its
high molecular weight cause them to remain in the liquid phase so they are more recoverable
than methanol. [23]

Table 5 - Main characteristics of some thermodynamic hydrate inhibitors
Inhibitor Methanol EG DEG

Formula CH3OH C2H6O2 C4H10O3
Molecular weight 32 62 106
Boiling point (°C) 64.7 198 245
Vapor pressure at 20°C (kPa) 12.5 0.01 <0.01
Melting point (°C) -98 -13 -10
Density at 20°C(g/l) 792 1.116 1.118
Viscosity at 20 °C) 0.59 21 35.7
According to the table above, we can eliminate the methanol since its boiling point is less than
water boiling point, so that its regeneration is difficult.
The choice is limited now to EG and DEG but EG is normally used in this process for these
reasons:
-It has the lowest molecular weight of the glycols.
-It has a lower viscosity [25]
-Solubility of EG in the liquid hydrocarbon phase is extremely small [24]
2.2. SPRAY NOZZLE DESIGN

To be effective, the inhibitor must be present at every point where the wet gas is cooled to lower
its hydrate temperature. This means that the inhibitor has to be typically sprayed on the tube-
sheet faces of the gas exchangers so that it can flow with the gas through the tubes. As water
condenses, the inhibitor is present to mix with the water and prevent hydrates. Injection must be
in a manner to allow good distribution to every tube or plate pass in chillers and heat exchangers
operating below the gas hydrate temperature. [24]
EG must be sprayed into the wet gas, if intimate mixing of the fine liquid glycol spray and the
natural gas is not achieved, then glycol injection may not prevent hydrate formation. Full cone
spray nozzles are recommended when glycol is injected upstream or over the tube sheet of heat
exchangers.

Figure 32 - Spray Nozzle Used in glycol injection
Due to the vapor pressure of glycol, a fine, well- distribute mist is required to obtain adequate
mixing with the gas to ensure optimum results.[26]
Required Ethylene glycol inhibitor concentration:

The theoretical principles of inhibition of hydrate formation have been discussed in several
papers. Hammerschmidt13 proposed the first empirical equation to find the required
concentration of an inhibitor X, in an aqueous solution, for lowering the hydrate formation
temperature by a given amount, (o F):
𝐾𝑋
𝛥𝑇 =
100𝑀 − 𝑀𝑋
From where,
100𝜟𝑻 ∗ 𝑴
𝑋=
𝜟𝑻 ∗ 𝑴 + 𝑲
With:
M = inhibitor's molecular weight,
K = constant, depending on the type of solution.
Experimentally determined values of K and molecular weights of inhibitors are given in Table 6
below.

Table 6 -Physical constants of inhibitors.
Component Molecular weight K-value

Methanol 32 2335
Ethylene Glycol 62.07 2700
Diethylene Glycol 106.12 4000
Triethylene Glycol 150.17 5400
For a 𝛥𝑇 lowering of 40°F ( 40°C)
100 ∗ 40 ∗ 62.07 248280
𝑋= = = 0.48
(40 ∗ 62.07) + 2700 5182.8
The EG has to have a minimum concentration of 0.48 %w in the liquid phase
Inhibitor required in liquid phase:
The quantity of inhibitor required may be calculated by a material balance:
water in outlet stream water in inletstream
Water removed from gas = pureinhibitor ∗ (( )− )
Inhibitor Inhibitor
Consequently,
𝑤𝑜𝑢𝑡 𝑤𝑖𝑛
𝑊𝑔 = 𝐼((100 − ) − (100 − ))
𝑤𝑜𝑢𝑡 𝑤𝑖𝑛
Win: Concentration of inhibitor in the inlet stream
Wout: Concentration of inhibitor in the outlet stream
I: Pure inhibitor required rate
To calculate the amount of water condensed on the chiller per day:
We have ΔW = W out – Win
ΔW = 11.16 ppm= 11.16 mg/kg
While density of gas = 31.46 kg/m3
ΔW = 351.09 mg/m3
Or QH2O = QGas * ΔW
The gas rate is about 16000 m3/h so:
QH2O = 5.617 kg/h = 134.808 kg/day
Mass rate of the inhibitor in water phase:[24]
QEG* (XEG-X) = QH2O* X
Where:
QEG = is Glycol mass rate
XEG = is concentration of Glycol injected (80%wt)
QH2O = water mass rate
X = is Glycol concentration in water phase Mass rate of the inhibitor:
134.808 ∗0.8
QEG= = 539.232 kg/day
0.2
Glycol vaporization losses are generally very small and typically ignored in calculations

3. STUDY OF EG INJECTION PERFORMANCE
3.1. HYSYS SIMULATION
In this part we will simulate the chilling unit after injection of Ethylene Glycol, using the
calculations made in the previous section.
The figure below represents the stream of glycol injected into the tube of the chiller.
Figure 33 - Glycol Stream injected into chiller
We injected 80wt% of Ethylene glycol on the gas stream at ambient temperature and the same
pressure of gas stream with a rate of 540 kg/day.
3.2. HYSYS RESULTS AND DISCUSSION

In order to reduce the temperature of hydrate formation, we injected ED on the gas flow; the
simulation shows that before injection hydrates formation temperature was -9.66 at 1.2 bar.
After hydrates inhibitor injection it is reduced to over -39.38 at 68 bar.
This decrease in the hydrate formation temperature ensures that our gas is out of hydrate
formation zone.

Figure 34 - Simulation Results using Hysys
After injecting the required flow of EG, the hydrate curve is moved to the left, which means that
hydrate formation temperature is decreased. Therefore, our gas going out from the chiller at a
temperature of -39°C at 68 bar has reached water content specifications and so we have avoid
hydrate formation problems.

Figure 35 Shows the hydrate formation curve and hydrate formation utility in the ideal
temperature and pressure of processing.
Figure 35 - Hydrates Formation Curve
3.3. Glycol regeneration principle
In Addition of Glycol injection equipment, a glycol regeneration unit has to be built.

As stated in the following PFD a tipycal EG regeneration unit is designed as follows:
Figure 36 - Typical Glycol Injection / Recovery Unit
The glycol injected into the chiller tubes trapped in the cold separator.
Since the rich glycol solution as a significantly more heavy than the NGL, it forms a bottom layer
in the cold separator.

Through a level control valve, Rich glycol is sent to the reboiler where water is boiled up from
glycol, regenerated glycol(lean glycol) is then ready to be re-injected into the gas stream.
It is recommended that the glycol spray covers the entire tube sheet, to ensure all hydrates
inhibition.
The regenerator in glycol injection system should be operated to produce a regenerated glycol
solution that will have a freezing point below the minimum temperature encountered in the
system. This is typically 75-80 mass %.

4. CONCLUSION
In this chapter, the main purpose was to find a solution to inhibit hydrate formation in the
propane chiller tubes, which causes a film layer reducing the amount of heat exchanged and
hinders us from reaching the desired temperature of refrigeration to recover a maximum of C3
and C4 in the NGL to be fractionated.
The solution found, is to inject Ethylene Glycol as a spray on shell tubes, so it could be mixed
with raw gas and absorb remaining water to avoid plugs formation even under high pressure and
a low temperature.
The second optimization axis is to purge the whole propane loop, and perform the whole process
of conditioning and inerting the loop.
A pure propane should be fed into the propane surge drum, so the lowest temperature of -40 °C
can be achieved in the expansion step.
Checking the thermal insulation of the propane loop, and the connected equipment should also
be performed in order to heat loss.
The application of thermal pipe insulation introduces thermal resistance and reduces the heat
flow.

GENERAL CONCLUSION & PROSPECTS
This study was conducted in order to study the performance of the LPG unit, more precisely the
propane refrigeration part, which is the very first process part, and the more important when it
comes to raw NGL production for LPG recovery and processing
A HYSYS simulation of the refrigeration unit with the real data was done in order to check the
equipment performance. Results provide proof that hydrates are formed in the propane chiller
tubes while all equipment are working well and performing.
We propose to install a spray nozzle in chiller tubes; an economic study should be done for this
purpose to confirm that this new conception is profitable.
This new concept allows us to decrease the hydrate formation temperature; it satisfies the unit
performance and allows reaching the designed temperature of refrigeration to reach Customer
specifications in term of HHV and gain in terms of LPG recovery.
The efficiency of LPG recovery is necessary on Sales gas characteristics, given the low fraction of
heavy hydrocarbons on sales gas makes its HHV lower. This reduces the amount of nitrogen
needed for wobbe index control.
Propane leaks should be controlled and needs a regular maintenance, for economical and safety
reasons.
Propane purity and potential product contamination should be checked by reintroducing a fresh
high purity propane feed in the surge drum.
As a perspective, a possible design and resizing of the Propane chiller and the LPG overhead
condenser, could be taken into consideration.
General Conclusion & Prospects Page 82/ 84

LIST OF REFRENCES
[1] http://www.exceptionalenergy.com/en_GB/facts-figures/lpg-facts]
[2] Petroleum Fuel Facilities. MIL-HDBK-1022A, Department of defense of the United States,
1999,p. 34.
[3] Richard Turton, Richard C. Bailie, Wallace B. Whiting, Joseph A. Shaeiwitz. Analysis, Synthesis,
and Design of Chemical Processes, Third Edition. Prentice Hall, 2008, pp. 1088.
[4] Tobin James, Shambaugh Phil, Mastrangelo Erin. Natural Gas Processing: The Crucial Link
Between Natural Gas Production and Its Transportation to Market, Energy Information
Administration, Office of Oil and Gas, January 2006.
[5] Rojey A., Jaffret C., Cornot-Gandolph S., Durant B., Jullin S., Valais M., 1997. Natural gas
Production, Processing, Transport. Editions Technip, Paris, France.
[6] Whitman S., Fundamentals of natural gas chemistry
[7] MEHERWAN P. BOYCE., Gas turbine Engineering Handbook. Fourth Edition.
[8] Saxon.F., Tolley’s Basic Science and Practice of gas Service, Gas service technology volume 1,
fourth edition..
[9] Saied Mokhatab., William A. POE., James G. Speight., handbook of natural gas transmission
and processing
[10] Whitney. G., Behrens. C., Energy: Natural gas.
[11] Speight. J., Handbook of industrial carbon processes
[12] P.Gandhidasan., Abdulghani A Al-Farayedhi., Ali AAl-Mubarak., Dehydration of natural gas
using solid desiccants, Mechanical engineering department, King Fahd University of petroleum
and minerals, Volume29, Issue 9, September 2001.
[13] B.K. Sharma., Fuels and petroleum processing including petrochemicals and industrial
organic synthesis.
[14] GPSA, Refrigeration, Section 14, Engineering Data Book, 12th Edition, SI, Volumes I& II.
[15] Martinez I., Thermodynamic basics and applications, Refrigeration, chapter 18, 1992.
[16] Energy efficiency guide for industry in Asia. Electrical energy equipment: refrigeration and
air conditioning. UNEP.
References Page 83/ 84

[17] Herring. J., Hydrocarbon Dew Point is a critical consideration for pipeline operations,
Pipeline & Gas Journal Volume 237, Number 7, July 2010.
[18] Abubakar Abbas Jibrin., GhasemG.Nasr., Dew point control Technologies, Spray research
group (SRG), School of Computing Science and Engineering (CSE), University of Salford, UK..
[19] Coyle D., Felix F., Durr C., Natural gas specification challenges in the LNG industry.
[20] Francis S. Manning., Richard E. Thompson., Oilfield processing of petroleum 1. Natural
gas., 1991., page 58.
[21] Wilbert F. Stoecker., Industrial refrigeration Handbook, Chapter 5: Screw compressors, page
127.
[22] International Institute of Refrigeration, Intergovernmental organization for the development
of refrigeration, Thermophysical properties of refrigerants: Propane.
[23] Chandragupthan B., Girish babuNounchi., Thirkkumaran NT., Jayakanthan D., Jegadeesh
N., Flow assurance – Special focus on hydrate blockage
[24] Halvorsen I.J. Minimum Energy Requirements in Complex Distillation Arrangements. A

thesisfor the degree of Dr.Ing. 2001.
[25] K. Muralikrishna, K.P Madhavan, S.S Shah, Development of Dividing Wall Distillation
Column
[26] Design Space for a specified separation, Trans I.Cheme, 2002, 80, 155.
[27] NDSU Agroculture, 2010. From http://www.ag.ndsu.edu/ndsuag/
[28] OPIC Methodology from http://www.opisnet.com/methodology.asp#nglforwards
[29] ParkashSurinder. Petroleum fuels manufacturing. McGraw-Hill, New York, 2003, p. 3-11.
[30] Peters M. and Timmerhaus K. Plant Design and Economics For Chemical Engineers.
FourthEdition, McGraw-Hill International, 1991, pp. 910.
References Page 84/ 84
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GENERAL INTRODUCTION ............................................................................................................. 12

CHAPTER 1 – NATURAL GAS & LPG FUNDAMENTALS .......................................... 13

1. NATURAL GAS FUNDAMENTAL............................................................................................ 14

1.1. INTRODUCTION ................................................................................................................... 14

1.2. NATURAL GAS ORIGIN AND COMPOSITION ......................................................... 14

1.3. NATURAL GAS PHASE BEHAVIOR ............................................................................... 16

2. NATURAL GAS PROPERTIES ................................................................................................... 17

2.1. MOLECULAR WEIGHT ....................................................................................................... 17

2.3. SPECIFIC VOLUME .............................................................................................................. 17

2.4. SPECIFIC GRAVITY .............................................................................................................. 17

2.5. COMPRESSIBILITY FACTOR ............................................................................................ 17

2.6. GAS VISCOSITY ..................................................................................................................... 18

2.7. HYDROCARBON DEW POINT ........................................................................................ 19

2.8. HEATING VALUE ................................................................................................................. 19

3. NATURAL GAS PROCESSING .................................................................................................. 21

3.1. GAS-OIL SEPARATORS ....................................................................................................... 22

3.2. CONDENSATE SEPARATOR ............................................................................................ 22

3.3. ACID GAS REMOVAL .......................................................................................................... 22

3.4. DEHYDRATION .................................................................................................................... 23

3.5. MERCURY REMOVAL ......................................................................................................... 24

3.7. FRACTIONATION ................................................................................................................. 25

4. LPG PROPRIETIES ........................................................................................................................ 26

4.1. INTRODUCTION ................................................................................................................... 26

4.2. DEFINITION AND PROPERTIES OF LPG................................................................... 26

4.3. LPG APPLICATIONS AND MARKETS ........................................................................... 27

4.4. CHEMICAL PROPERTIES OF LPG .................................................................................. 28

4.5. PHYSICAL PROPERTIES OF LPG.................................................................................... 28

5. CONVENTIONAL LPG PROCESSING TECHNOLOGY .................................................. 30

5.1. LPG FRACTIONATION PLANT ....................................................................................... 30

5.2. DEETHANIZER ..................................................................................................................... 31

5.3. DEPROPANIZER ................................................................................................................... 31

5.4. DEBUTANIZER ...................................................................................................................... 31

CHAPTER 2 – LPG RECOVERY TECHNOLOGIES .................................................... 32

2. LEAN OIL ABSORPTION ............................................................................................................ 34

3. SOLID BED ADSORPTION ........................................................................................................ 35

4. MEMBRANE SEPARATION PROCESS ................................................................................... 37

5. REFRIGERATION PROCESSES ................................................................................................ 38

5.1. MECHANICAL REFRIGERATION .................................................................................. 39

5.3. CRYOGENIC REFRIGERATION...................................................................................... 41

CHAPTER 3 – MAÂMOURA & BARAKA FIELD PRESENTATION .......................... 46

2. GEOGRAPHIC LOCATION ........................................................................................................ 47

4. PRODUCT SPECIFICATIONS .................................................................................................... 48

4.1. SALES GAS SPECIFICATIONS .......................................................................................... 49

4.2. BUTAPRO SPECIFICATION .............................................................................................. 49

5. CONTROL UNITS FOR SALES GAS ........................................................................................ 49

5.1. HYDROCARBON DEW POINT CONTROL ................................................................. 49

5.2. WOBBE INDEX CONTROL ............................................................................................... 51

5.3. HYDRATE FORMATION CONTROL ............................................................................. 51

CHAPTER 4 – DETAILED CASE STUDY & SIMULATION........................................ 53

2. PROCESS DESCRIPTION ............................................................................................................ 54

3. PROCESS EQUIPMENTS ............................................................................................................. 55

5.1. FEED CHARACTERISTICS ................................................................................................. 58

5.2. REFRIGERATION UNIT SIMULATION RESULTS .................................................... 59

5.3. PROPANE REFRIGERATION CYCLE............................................................................ 61

5.4. THEORETICAL FORMULATION .................................................................................... 61

5.5. COOLING CAPACITY .......................................................................................................... 62

5.6. OVERALL PROCESS SIMULATION RESULTS ............................................................ 65