Contents

y Project Background y Problem Statements y Objective y Literature Review

y Gas hydrates y Natural gas dehydration y Absorption process y Equation of State

y Methodology y References

Project Background
y Natural gas is a mixture of naturally occurring hydrocarbon and non-hydrocarbon gases

found in porous geologic formations beneath the earth s surface.

It occurs with petroleum deposits, principally methane together with varying quantities of ethane, propane, butane, and other gases as well.

y Mostly it is used as a source of fuel and in manufacture of organic compounds.

y Raw natural gas drilled from the offshore platforms contains other gases as well such as

carbon dioxide, nitrogen, hydrogen sulfide, various mercaptans, and water vapour along with trace amounts of volatile organic component (VOC) gases, sand and other compounds as well once it comes out from the underground.

Table 1:Sample of Natural Gas Composition in Malaysia (source: Dan Laudal Christensen, February 2006, thermodynamic simulation of the water/glycol mixture)
Methane: Ethane: Propane: i-Butane: n-Butane: i-Pentane: n-Pentane: n-Hexane: n-Heptane: n-Octane: n-Nonane: n-Decane: Water: Nitrogen: Carbon dioxide Hydrogen sulphide 0.88322 0.06755 0.01995 0.00688 0.00769 0.00388 0.00183 0.00177 0.00132 0.0005 0.00012 0.00005 0.00121 0.00237 0.00166 0

y Natural gases commonly are classified according to their liquids content as either lean or

rich and according to the sulfur content as either sweet or sour.

y Sweet Gas : Contains negligible amounts of H2S, y Sour Gas : Unacceptable quantities of H2S

y This H2S in natural gas when present with water, it could be corrosive. Mainly, the

corrosion products are iron sulphides, FeSX, a fine black powder.

y Water at specific temperature and pressure will formed hydrates with hydrocarbon

y Thus it is important for this natural gas to undergo preliminary natural gas processing in

order to remove either the water ( gas dehydration) or H2Sbefore it being transported using gas pipeline

Figure 1 : Natural Gas Processing (source: Arthur J. Kidnay et. al, 2006, fundamental of natural gas processing)

Problem Statements
y Natural gas that comes from oil wells is not totally pure but there are contaminants or

mixtures in gas
y These mixtures in natural gas can cause problems for the production operation,

transportation, storage and uses of the gas. y -H2S c rr si n y -water hydrates

y Gas hydrates are ice-like clathrate solids that are formed from water and small

hydrocarbons at elevated pressures and at lower temperatures (depends on the equilibrium between hydrocarbon and water contents). This hydrates can caused problems especially in gas transportation in pipelines.

y This hydrates formed as a result of reaction that occurred between hydrocarbons with the

water contents available in the natural gas.

Figure 2 : Pressure-temperature graph for a typical natural gas hydrate. ( source: Production Chemicals for the Oil and Gas Industry)

y The agglomeration of these hydrates in the pipeline may not be the same location as it is

formed. The hydrate can flow with the fluid phase especially the liquid. As the liquid accumulated, the hydrate would also tend to accumulate in the same location.

y These accumulati ns f hydrates will f rm bl ckage that will bl ck the line and damage the

equi ment such as the i eline.

Figure 3: Safety Hazard f r m ving hydrate lugs ( Re-illustrated from the author from Sloan, 2000)

y A: A hydrate lug m ves d wn a fl w line at a very high vel city y B: Where the i e bends, the hydrate lug can ru ture fl w line thr ugh r jectile im act

y Thus it is important for these natural gases to be treated first in the natural gas processing

before it being transported to other places or used as the reactant for other processes. Natural Gas Dehydration :
 Removing water vapor from the gas  Mostly by two (2) methods that is through Absorption or Adsorption

y Mainly research will involved in the simulation process of natural gas dehydration by

absorption using Triethylene Glycol (TEG) as the absorbents medium or liquid desiccants using current Aspen HYSYS 2006 software.

OBJECTIVES
The objectives of the studies are: To compare between current technologies for natural gas dehydration. To study the effect of operating conditions on the efficiency of the process. To investigate the possibility of absorbent modifications. To suggest modification of existing technologies.

y y y y

Scope of studies:
y

focuses on the mechanism of natural gas dehydration by absorption in the aspects of process simulation

y y

Analysis parameters that involved in the simulation

To come out with the best solution of natural gas dehydration process by using the existence technology of natural gas absorption process as the main reference.

LITERATURE REVIEW
Gas Hydrates
y solid crystalline material formed from cages of water molecules containing voids that are

occupied by gas molecules whose presence stabilizes the crystal structure through Van der Waals bonding

Figure 4 : Gas Hydrate structure (source: Dan Laudal Christensen, February 200, thermodynamic simulation of the
water/glycol mixture)

y The hydrogen bonding causes water molecules to align in regular orientations. y The presence of certain compounds in natural gas causes the aligned molecules to stabilize and

solid mixture will precipitate.

Gas hydrates formation requires three conditions which are:

y Right combination of temperature and pressure ( formation is favoured under low temperature

and high pressure)

y Hydrate formers (guest molecules) y Sufficient amount of water

Currently there are three (3) structures of gas hydrates:

y Structure 1 : Type I y Structure 2 : Type II y Structure H: Type H

y All these hydrates structures can be differentiated in the size of cavities and the ratio of

different sizes of cavities

cavities

Figure 5: Cages of water molecules bond building different gas hydrates structures (source: http://www.science.org.au)

Natural Gas Dehydrations

yNatural gas dehydrati n is the r cess f rem ving water va

ur fr m the gas stream t l wer

the dew

int f that gas.

yObjectives f Natural Gas Dehydrati ns: yt

revent hydrate reventi n en

y To avoid any corrosion to ha

y Downstream rocess requirement

Dew oint Used to measured the formation of water condensate ( de ends on hydrocarbon mixture) Gas Dehydrations rocess used to lowered this gas dew oint Decreased the tem erature at which the water va or will condensed

Before Gas Dehydration Process

After Gas Dehydration Process Figure 6: Dew points Depressions ( source: Dr. Mahmood Moshfeghian, Process
Simulation in Gas Conditioning and Processing)

Purpose of Gas Dehydrations :

y To prevent hydrate prevention.

hydrates can plug lines and retard the flow of gaseous hydrocarbon streams.
Reduce effectiveness gas transportation
y To avoid from any corrosion to occurred.

The water vapour will dissolve in hydrogen sulphide in the natural gas to form an acidic solution. This acidic solution will reacts with carbon steel in the pipeline to caused corrosion.
y Downstream process requirements.

presence of water may cause side reactions, foaming, or catalyst deactivation. Consequently, purchasers typically require that gas and liquid petroleum gas (LPG) feedstocks meet certain specifications for maximum water content.

Natural Gas Dehydration by Absorption

y Liquid desiccant dehydrator serves to absorb water va our from the gas stream. y Essentially, glycol dehydration involves using a glycol solution, usually either DEG or TEG, which

is brought into contact with the wet gas stream in a contractor.

Table 2: Glycols used in Dehydration ( source: Kohl and Nielsen (1997) )

y The OH groups in glycol solution has high affinity to water since it will form hydrogen

bonding with the water molecules.

y

It will absorb water from the wet gas. Once absorbed, these glycol particles become heavier and will sink to the bottom of the contactor where they are removed while the gas that are light in density will rise upward to the top of the contactor and will come out as a dry gas.

y Generally, in absorption, net mass is transferred from the vapour to the liquid, resulting in the

recovery of certain components from the vapour feed by the liquid.

y On each stage, the intermediate components distribute themselves between the vapor and

liquid or until: Yi = KiXi, where;

y Ki : the vapour-liquid equilibrium distribution coefficient y Yi : mole fractions in the vapour of component i and y Xi : mole fractions in liquid of component i. y In ideal solutions this relationship simplifies to Raoult s law; y

PYi = pioXi, where;

y P : the stage pressure y Pi : vapour pressure of component i at the stage temperature

PYi = pioXi

y Referring to Raoults law, the vapour pressure of the light components is too high to allow

them to move in any appreciable amounts to the liquid. (If pi is large, Xi must be small to keep their product equal to the partial pressure of i, PYi)

y Conversely, the vapour pressure of the heavy components is too low to allow it to be

transferred significantly to the vapour.

y Hence, in absorption, net mass is transferred from one phase to the other and as for the case of

natural gas dehydration the mass transfer of water vapour is from gas phase (natural gas) to liquid phase (absorbent).

y Figure 7: Absor tion column com osition data from the simulation

y The OH groups in glycol solution has high affinity to water since it will form hydrogen

bonding with the water molecules.

y Thus it will absorb water from the wet gas. Once absorbed, these glycol particles become

heavier and will sink to the bottom of the contactor where they are removed while the gas that are light in density will rise upward to the top of the contactor and will come out as a dry gas.

Figure : Schematic diagram of an absorption column

y As for the material balance, since the liquid and gas components do not change phases, their

flow rates will remain constant in the column.

Lx0 +Vyj+1 = Lxj+Vy1

y L : Liquid flow y V: Vapor Flow y x:mole fraction of component in liquid phase y y: mole fraction of component in vapour phase y the composition of the respective component in the vapour phase or liquid phase coming out

from the absorption column can be determine if the balance amount of liquid and vapour entering the absorption column are given.

Equation of State
y First step requirements in simulating a process in ASPEN Hysys that is to choose suitable

package for the fluid involved in the process

y As for the case of natural gas dehydration simulation, the Equation of state used must

able to encompass wide ranges of pressure and temperature in order to represent the PVT behaviour of both vapours and liquids.

Peng-Robinson Equation of State could actually predict better values for both liquid and gas densities. At low temperature and high pressure

y Peng-Robinson Equation of State

y Where -p is the pressure y T is the temperature y V is the molar volume y n is the number of moles y R is the gas constant

METHODOLOGY
Literature Review
Gas Hydrates Natural Gas Dehydrations Absor tion rocess hase Envelopes

Data Collection
Natural Gas Composition Absorption Column arameters Operating Conditions rocess Descriptions

HYSYS Simulation
Absorption Simulation Stripping Simulation Simulation of Recycle Stream Separators Sequencing

Data Gathering from Simulation Results

hase Envelopes Dew oint Depressions

Simulation Result Analysis

Temperature and ressure and Temperature Differentiation towards Rate of Absorption Temperature and ressure and Temperature Differentiation towards Rate of Distillation (Regenaration)

Developing Complete Flowsheet

Improved Rate of Absorption Improve Rate of Regeneration TEG recovery

Report Writting Summarised Analysis Result From Simulation Listing All Related arameters Establish Complete rocess Descriptions

Natural Gas composition before Dehydration process

Natural Gas composition after Dehydration process

Natural Gas composition before Dehydration process for TEG

Natural Gas composition after Dehydration process for TEG

Ghantt Chart
1 Topic Selection Proposal Submission Preliminary Research Work (Basis theory of project) Literature Review Submission of Progress Report Seminar (Oral Presentation) Second Phase Research Work ( Data Gathering for ICON simulation) ICON Simulation Trial Analysis ICON Simulation Result Summarized all analysis data into presentable formed Prepare Presentation Slides Submission Interim Report Oral Presentation Mid Semeter Break/ Hari Raya Holiday 2 3 4 5 6 7 8 9 10 11 12 13 14 15

Key Milestone

Activity Proposal Submission Progress Report Submission Seminar (Oral Presentation) Interim Report Submission Oral Presentation

Date 6/08/2010 3/09/2010 3/09/2010 1/11/2010 1/11/2010

References

y y

Kermit E. Woodcock. Gas, Natural, Vol. 12. pp1: Gas Research Institute Kh. Mohamadbeigy(2008). Studying of the effectiveness parameters on gas dehydration plant.pp1: Research Institute of etroleum Industry Tehran H.K.Abdel-Aal and Mohamed Aggour(2003). etroleum and gas field processes: Marcel Dekker Inc. (2009). roduction Chemical for the Oil and Gas Industry: Taylor and Francis Group Dr. James G. Speight (2006). The Chemistry and Technology of etroleum. 4th Ed: Taylor & Francis Group Myron Gottlib (2003). Natural Gas. Gasoline and other Motor Fuels. Vol 12. pp 1 (2009). What are gas hydrates? http://www.centreforenergy.com/AboutEnergy/ONG/GasHydrates/Overview.asp?page=2 Fouad M. Khoury(2005). Multistage Separation rocesses. 3rd Edition: CRC ress Geankoplis (2003). Transport rocess and Separation rocess rinciples. 4th Ed: earson Education International Fouad M. Khoury(2005). Multistage Separation rocesses. 3rd Edition: CRC ress E.G. LARIONOV*, YU.A. DYADIN, F.V. ZHURKO (2005). hase Diagrams of the Ternary Gas Hydrate Forming Systems at High ressures. art II. Ethane Methane Water System. p1 John M. Campbell (1994). Gas Condition and rocessing. Vol 1: Campbell etroleum Series

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