Gas Processing (CHE4403)

Dr Meegalla R. Chandraratne

Different Types of Gases

Gas Processing (CHE 4403)

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 Course Introduction
• This course is designed to cover the fundamentals of the
gas process operations in the petroleum industry.
• An overview of gas processing from gas-oil separation to
final production and transportation as well as gas
properties calculations are included.
• The course focuses on the principles of:
➢ NGL extraction, LPG fractioning, LNG production.
➢ Properties of gas.
➢ Flash separation, oil-gas separation.
➢ Gas processing.
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➢ Gas compression and refrigeration.
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Physical Compounds
• Clathrate, is a chemical substance consisting of a lattice
of one type of molecule trapping and containing a
second type of molecule.
• A type of physical compound, called a clathrate, may be
formed. A gas hydrate is one example of a clathrate.
These compounds are relatively unstable.
• An example of a clathrate is clathrate hydrate, a special
type of gas hydrate in which a lattice of water molecule
encloses molecules of trapped gas.

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 Clathrate Hydrate

Chemical Compounds
• Hydrocarbon: Any compound made of C and H atoms.
• These atoms can combine in a number of ways to satisfy
valence requirements.
• For convenience, these are separated into families (or
homologous) series, each of which is given a name.
• C atoms can link together to form “chains” or “rings”.
• Crude oil and natural gas mixtures consist primarily of
“straight chain” hydrocarbon molecules, the bulk of
which are paraffins.
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 1) Paraffin Series: CnH2n+2
• Hydrocarbons in this series are saturated compounds
because all four bonds are connected either to another C
atom or a H atom, with one such atom for each bond.
• Name of paraffin compounds end with an “-ane”.

CH4 C2H6 C3H8

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1) Paraffin Series: CnH2n+2 (continued)

• Paraffin hydrocarbons are the most stable because all
valence bonds are fully satisfied.
• Most reactions involve the replacement of H atoms with
other atoms; the carbon linkage remains stable.
• Longer chain may be formed, however, the only ones
normally identified by name contain ten or less carbons.
• Just note that in referring to a given paraffin
hydrocarbon, the abbreviation C3 for propane, C4 for
butane, etc. may be used but,
• Statements like “propane plus fraction ( C3+) refer to a
mixture composed of propane and larger molecules. 8

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 Paraffin Isomers
• When paraffin series molecule contains four or more
carbon atoms there are different ways these can be
connected without affecting the formula.
• Compounds which have the same chemical formula but
a different molecular structure are called isomers.
• They posses different physical and chemical properties.
• There are only 2 isomers of butane.

2) Olefin or Ethylene Series (Alkenes): CnH2n

• The olefin group of compounds is a simple straight chain
series in which all the names end in –ene.
• Ethylene (ethene) C2H4 is the simplest molecule in the
series.
• Hydrocarbon in this series combine easily with other
atoms like chlorine and bromine, without the
replacement of hydrogen atoms.
• Since they are so reactive, they are called unsaturated
hydrocarbons.
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 2) Olefin or Ethylene Series (Alkenes): CnH2n
(continued)
• Unlike the paraffin, the maximum bonding capacity of
the carbon atom is not fully satisfied by H or C atoms.
• Two adjacent carbon atoms form a “temporary ”bond (in
the absence of other available atoms) to meet bonding
requirements fixed by valence.
• The structural formula for the olefins uses a double line
to indicate the double C-C linkage, the most reactive
point in the molecule.
• With four or more carbons, isomers also may result from
the position of the double bond.
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3) Acetylenic or Alkyne Series: CnH2n-2

• Acetylene (systematic name: ethyne) is the chemical
compound with the formula C2H2.

• It is a hydrocarbon and the simplest alkyne.

• This colourless gas is widely used as a fuel and a

chemical building block.

• It is unstable in pure form and thus is usually handled as

a solution.

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 3) Alkyne Series: CnH2n-2 (continued)
• There is a triple bond between the carbon atoms.

• This satisfies the valence requirements but the carbon

linkage is very weak.

• Therefore, Acetylene is even more reactive than olefins.

• Acetylene not only is unsaturated, it is also unstable

chemically.

• In the liquid state is explosive if subjected to a sudden

shock.
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4) Diolefins Formula CnH2n-2

• Same formula as acetylene but contain two double
linkages.
• They normally are named by replacing the –ane for
paraffin by –diene.
• Diolefins are primarily of concern in petrochemical
plants. Butadiene is possibly the most interesting and
useful since it is a primary ingredient in synthetic rubber
compounds.
• It has the formula:
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 Associated Gas
• Associated gas is a mixture of petroleum gases that range
from methane to butane and traces of liquid condensate,
heavy hydrocarbons (pentane to heptane).
• The gas is called associated because it is produced from an
oil well, dissolved in the oil.
• It is separated from the oil by liquid gas separator in the
degassing station.
• The gas contains non-hydrocarbon gases such as CO2 and
H2S as well as some water.
Component C1 C2 C3 i-C4 n-C4 i-C5 n-C5 C6 C7+
Mol % 27.52 16.34 29.18 5.37 17.18 2.18 1.72 0.47 0.04
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 Typical Process of an Associated gas

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Non-Associated Gas
• Gas occurring alone as natural gas, not in solution or as
free gas with oil or condensate.

• The gas contains small fractions of C7+ compounds.

• It contains mainly methane and ethane. It may also
contains impurities such as CO2, H2S and water.

Dry gas component C1 C2 C3 C4 C5 C6 C7+

Mol % 96.0 2.0 1.0 0.5 0.5 - -

Wet gas component C1 C2 C3 C4 C5 C6 C7+

Mol % 90.0 3.0 2.0 2.0 1.0 0.5 1.5
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 Wet and Dry Gas
• Natural gas is often found dissolved in oil at the high
pressures existing in a reservoir.
• It can be present as a gas cap above the oil. Such natural
gas is known as associated gas. There are also reservoirs
that contain gas and no oil. This gas is termed non-
associated gas.
• Associated gas usually contains some light liquids and
hence is sometimes called “wet gas.”
• Non-associated gas coming from reservoirs that are not
connected with any known source of liquid petroleum, is
“dry gas.” 19

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Sour and Acid Gas

• Sour gas is natural gas or any other gas that is corrosive
due to significant content of H2S.

• Natural gas is considered sour if there are more than 5.7

milligrams of H2S per cubic meter of natural gas (4 ppm).

• Natural gas that contain less amounts of H2S is called

"sweet gas."

• Acid gas is any gas that contains significant amounts of

acidic gases such as CO2 or H2S.

• Thus, CO2 by itself is an acid gas but it is not a sour gas.

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 Gas Sweetening
• Before a raw natural gas containing H2S and/or CO2 can be
used, the raw gas must be treated to remove those
impurities to acceptable levels, commonly by an amine
gas treating process.

• The removed H2S is most often subsequently converted to

by product elemental sulphur in a Claus process or it can
be treated in a WSA (wet sulphuric acid) process unit
where the by product is sulphuric acid.

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Acid Removal by Absorption

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 LNG, LPG and NGL

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What is LNG?
• Liquefied natural gas (LNG) is natural gas that has been
super cooled to -2600 F (-1620 C).
• At that temperature, natural gas condenses into a liquid.
When in liquid form, natural gas takes up to 600 times less
space than in its gaseous state, which makes it feasible to
transport over long distances.
• In the form of LNG, natural gas can be shipped from the
parts of the world where it is abundant to where it is in
demand.
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 What is LNG?
• LNG is an energy source that has much lower air
emissions than other fossil fuels, such as oil or coal.

• LNG is odourless, colourless, non corrosive and non-

toxic. Its weight is less than one half that of water
(430 kg/m3 to 470 kg/m3).

• Natural gas is the world’s cleanest burning fossil fuel

and it has emerged as the environmentally preferred
fuel of choice.
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Natural Gas Composition

• The primary component of natural gas is methane (CH4),
the shortest and lightest hydrocarbon molecule.
• Natural gas as a fossil fuel also contains heavier gaseous
hydrocarbons such as ethane (C2H6), propane (C3H8) and
butane (C4H10), as well as CO2 and sulphur containing
gases in varying amounts.
• Fossil natural gas also contains in varying amounts and
is the primary market source of Helium, a non-
renewable and valuable resource.
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 Natural Gas Composition
• Methane (CH4) 80-95 %
• Ethane (C2H6) 5-15 %
• Propane (C3H8) and Butane (C4H10) < 5 %

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Heating Value
• Natural gas is mainly used as a fuel.
• Quantities of natural gas are measured in:
➢ Normal cubic meters (Nm3)(at 0 °C and 1 atm).
➢ Standard cubic meters (Sm3)(at 15.6 °C and 1 atm).
➢ Standard cubic feet (scf) [at 60 °F (15.6°C) and 30” Hg].
• The gross heat of combustion of one Nm3 of commercial
quality natural gas is around 39 MJ (≈10.8 kW hours), but
this can vary.
• In U.S. units, one scf of natural gas produces around
1000 BTU.
• The actual heating value when the water formed does not
condense is the net heat of combustion and can be as much
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as 10% less.
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 What is LPG ?
• Liquefied petroleum gas (LPG) is a flammable mixture of
hydrocarbon gases used as a fuel in heating appliances and
vehicles.
• It is increasingly used as an aerosol propellant and a refrigerant,
replacing chlorofluorocarbons in an effort to reduce damage to
the ozone layer.
• Varieties of LPG bought and sold include mixes that are primarily
propane C3H8, mixes that are primarily butane C4H10 and mixes
including both C3H8 and C4H10, depending on the season - in
winter more C3H8, in summer more C4H10. Propane vaporizes
down to -42 °C. Butane will not vaporize below 0.4 °C. So, below
freezing a butane gas supply stops working. Butane is cheaper.
• At normal T and P, LGP is a gas. LPG is heavier than air. 29

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What is LPG ? (continued)

• Propylene and butylenes are usually also present in small
concentration.
• A powerful odorant, ethanethiol, is added so that leaks can be
detected easily. The international standard is EN 589. In the US,
thiophene or amyl mercaptan are also approved odorants.
• It is increasingly used as an aerosol propellant and a refrigerant,
replacing chlorofluorocarbons.
• Blended of pure, dry isopropane (R-290a) and isobutane (R-600a)
have negligible ozone depletion potential and very low global
warming potential and can serve as a functional replacement for
R-12, R-22, R-134a and other CFC or hydrofluorocarbon
refrigerants in conventional stationary refrigeration and air
conditioning systems. 30

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 Environment
• As a low carbon and low polluting fossil fuel, LPG is
recognized by governments around the world for the
contribution it can make towards improved indoor and
outdoor air quality and reduced greenhouse gas
emissions.

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Storage

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 What is NGL?
• Natural Gas, the source of Natural Gas Liquids is a natural
mixture of gaseous hydrocarbons found in the ground or
obtained from specially driven wells.
• The composition of natural gas varies in different parts of
the world. Its chief component, methane, usually makes
up from 80% to 95% its composition.
• The balance is composed of varying amounts of ethane,
propane, butane and other liquid hydrocarbon
compounds.
• NGL includes ethane, propane, butanes, pentanes and
condensate, all of which can be extracted from gas plants.
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What is NGL?
• Propanes and Butanes can also be extracted during crude
oil refining.
• Ethane is used as petrochemical feedstock to produce
ethylene and petrochemical building blocks.
• Propane is a heating and transportation fuel also used as
petrochemical feedstock making ethylene and propylene.
• Normal Butane is a refining blend stock for gasoline and is
also used as a petrochemical feedstock.
• Isobutane is a refining feedstock for alkylation, MTBE and
TAME manufacturing and a component of gasoline octane
blends. 34

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 Gas Processing by Countries and Regions
Exercise:
• Which country has the largest gas reserves, (if possible,
give values in million ft3)?
• Which gulf country has the largest reserves of natural
gas (if possible, how much gas in ft3)?
• Which country has the largest amount of natural gas (if
possible, how much gas in ft3)?
• Which country consumes the largest amount of natural
gas and how much?
• Which country in the middle east consumes the largest
amount of natural gas?
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Natural Gas Typical Process

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 Properties of Gases

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Energy and Specific Heat (quick review)

• 1 calorie is the amount of energy (or heat) needed to
raise the temperature of 1 g of water at 14.5°C by 1°C.
• Calorie - metric unit; 1 cal = 4.184 J (SI unit).
• Specific heat is the amount of heat needed to raise the
temperature of 1 g of a specific substance by 1°C.
• Heat(cal) = Mass(g) x Change in Temperature(°C) x
specific heat (cal/g °C).
Example: Taking a bath might use about 95 kg of water. How
much energy (in calories) is needed to heat the water from a
cold 15 °C to a warm 40 °C. (specific heat of water is 1 cal/g °C).
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 Calorific Value (CV)
• The CV is a characteristic of each substance (what does
this mean?).
• CV of natural gas is the “heating value” (amount of heat
gives off) when natural gas is burnt.
• CV is measured in units of kJ/kg, MJ/kg, kJ/m3 or MJ/m3
(metric), BTU/lb or BTU/ft3 (British).
• The CV of a fuel is important because it is important to
know how much heat will be provided when a specific
fuel is burnt (in boilers, heaters etc.).
• Basically it is a measure of the heat liberated on burning
a unit mass or volume of the fuel. 39

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Calorific Value (CV) (continued)

• There is usually a minimum heating value of the natural
gas (in MJ/m3) to meet the gas sales contracts.
• When heavy hydrocarbons are removed from natural
gas, the CV in MJ/m3 is actually reduced. Why?
• Also when there is an excess of nitrogen and/or carbon
dioxide in natural gas, the CV is lowered. Why?
• Note that: CV is the negative of the standard heat of
combustion (heat liberated on burning a unit mass).
➢ Typical CV, Gasoline = 44000 kJ/kg,
Natural gas = 54000 kJ/kg
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 Calorific Value (CV) (continued)
Flow rate Unit of fuel gas:
• The quantity of a gas is expressed in terms of standard
cubic meter (Sm3) [15.6 °C (60 °F) and 1 atm].
• The flow rate is Sm3/ day (or hour or min).
• Another unit is Nm3/day [i.e. at 0 °C and 1atm].

Exercise 1: Flow rate

If the flow rate of a gas is 3000 Sm3/h, what will the
flow rate be in Nm3/day.
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Calorific Value (CV) (continued)

Exercise 2: Flow rate
a) If the flow rate of a gas is 3000 Sm3/h, what will the
flow rate be in scf/day?
b) A plant flare is measured as 3000 Sm3/hr. If the gas is
flaring at an out side temperature of 35°C and 1 atm
(i.e. actual condition), what is the volumetric flow rate
in m3/day.
c) If the flared gas has a heating value (CV) of 8000kJ/m3,
how much heat energy is wasted per year?

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 Calorific Value (CV) (continued)
• CV for different components can be found in tables or
calculated using the heat of reaction (i.e. combustion
reaction) based on heat of formation.
• Keep in mined that CV is the same as the heat of
combustion per mol.
• The calorific value for a gas mixture is calculated as
follows: 𝐶𝑉 = σ 𝑦𝑖 𝐶𝑉𝑖 .

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Heat Content of Light Hydrocarbons

• A large part of crude oil will be used as fuel:
1. Fuel gas
2. Gasoline for engine
3. fuel oil
• The heat of combustion (ΔHc0) is the energy released as
heat when a compound undergoes complete
combustion with oxygen under standard conditions.
• The chemical reaction is typically a hydrocarbon
reacting with oxygen to form CO2, water and heat:
𝑪𝟐 𝑯𝟔 + 𝟑. 𝟓𝑶𝟐 → 𝟐𝑪𝑶𝟐 + 𝟑𝑯𝟐 𝑶 + 𝑯𝒆𝒂𝒕
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 Heat of Combustion
• The heat of combustion is traditionally measured with a
bomb calorimeter. https://www.youtube.com/watch?v=nJOH29SGcCk
• It may also be calculated as the difference between the
heat of formation (ΔH0f) of the products and reactants.
𝑪𝑯𝟒 (𝒈) + 𝟐𝑶𝟐 (𝒈) → 𝑪𝑶𝟐 (𝒈) + 𝟐𝑯𝟐 𝑶(𝒍)
• The enthalpy change for this reaction is measured by
pressurizing a strong metal reaction vessel (called a bomb)
with a mixture of methane and oxygen gas.
• The bomb is immersed in a calorimeter filled with water.
An electrical current is passed through ignition wire (a fine
iron wire), which ignites the wire and the gas mixture.
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Calorimetry to Measure Heat of Combustion

• The heat balance for this calorimeter experiment is:
0 = 𝑞𝑐𝑎𝑙 + 𝑞𝑤𝑖𝑟𝑒 + 𝑞𝑐𝑜𝑚𝑏
• The heat for the calorimeter, 𝑞𝑐𝑎𝑙 , is determined from the
heat capacity of the calorimeter and the temperature
change for the calorimeter experiment.
• Typically the amount of water in the calorimeter is always
the same; therefore 𝑞𝑐𝑎𝑙 includes the heat capacities of the
calorimeter, the water and the bomb itself.
• The burning of the ignition wire releases heat, 𝑞𝑤𝑖𝑟𝑒 and this
heat must be included in the calculations. (This heat is
treated separately, because the amount of ignition wire
used varies from one measurement to the next.)
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 Combustion Experiment
• The heat released by the combustion reaction is 𝑞𝑐𝑜𝑚𝑏 ,
which is related to the molar enthalpy of combustion by
∆𝐻𝑐𝑜𝑚𝑏 = 𝑞𝑐𝑜𝑚𝑏 /𝑛𝑚𝑒𝑡ℎ𝑎𝑛𝑒 .
• Combustion experiments are generally conducted with
large excess O2, so that the fuel is the limiting reactant.
• Combustion reactions are often used to calculate the
molar enthalpies of formation.
• The standard molar enthalpy of combustion for CH4 can
be expressed in terms of the standard molar enthalpies
of formation of the reactants and products.
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Molar Enthalpies of Formation

• 𝐶𝐻4 𝑔 + 2𝑂2 𝑔 → 𝐶𝑂2 𝑔 + 2𝐻2 𝑂 𝑙 + ℎ𝑒𝑎𝑡
0 0 0 0 0
• ∆𝐻𝑐𝑜𝑚𝑏 = 2∆𝐻𝑓,𝐻2𝑂
+ ∆𝐻𝑓,𝐶𝑂2
− ∆𝐻𝑓,𝐶𝐻4
− 2∆𝐻𝑓,𝑂2
0 0
• ∆𝐻𝑐𝑜𝑚𝑏 is measured experimentally; ∆𝐻𝑓,𝑂2
= 0,
because oxygen is a pure element.
• The other molar enthalpies of formation are known
from independent measurements.
• e.g. one could determine the heat of combustion of H2
to obtain the molar enthalpy of formation for water.
➢ For liquid water, ∆𝐻𝑓0 = −285.9 𝑘𝐽/𝑚𝑜𝑙
For gaseous CO2 , ∆𝐻𝑓0 = −393.5 𝑘𝐽/𝑚𝑜𝑙. 48

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 Calorific Value (CV) (Exercise)
• The typical vent-gas analysis from the recycled stream of an
oxyhyrochlorination process for the production of
dichloroethane (DCE) is given below:
Component Mol % CV (kJ/mol)
O2 7.96
CO2 + N2 87.6
CO 1.79 283
C2H4 1.99 1411.9
C2H6 0.1 1560.9
DCE 0.54
Estimate the vent gas calorific value?
Combustion reaction:
C2H4 Cl2(g) + 2.5 O2 → 2 CO2 (g)+ H2O (g) + 2HCl (g) 49

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Higher Heating Value (HHV)

• The higher heating value (HHV) (gross calorific value or
higher calorific value HCV) is determined by bringing all
the products of combustion back to the original pre
combustion temperature and in particular condensing
any vapour produced.
• Such measurements often use a temperature of 25 °C.
This is the same as the thermodynamic heat of
combustion since the enthalpy change for the reaction
assumes a common temperature of the compounds
before and after combustion, in which case the water
produced by combustion is liquid. 50

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 Lower Heating Value (LHV)
• The lower heating value (LHV) (net calorific value or
lower calorific value LCV) is determined by subtracting
the heat of vaporization of the water vapour from the
higher heating value. This treats any H2O formed as a
vapour. The energy required to vaporize the water
therefore is not realized as heat.
• LHV calculations assume that the water component of a
combustion process is in vapour state at the end of
combustion, as opposed to the HHV which assumes all
of the water in a combustion process is in a liquid state
after a combustion process. 51

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Lower Heating Value

• For hydrocarbons the difference between HHV and LHV
depends on the hydrogen content of the fuel.
• For gasoline and diesel the higher heating value exceeds
the lower heating value by about 10% and 7%,
respectively, for natural gas about 11%.
• A common method of relating HHV to LHV is:
𝐻𝐻𝑉 = 𝐿𝐻𝑉 + ℎ𝑣 𝑥 (𝑛𝐻2 𝑂,𝑜𝑢𝑡 Τ𝑛𝑓𝑢𝑒𝑙,𝑖𝑛 )
where ℎ𝑣 is the heat of vaporization of water, 𝑛𝐻2 𝑂,𝑜𝑢𝑡
is the moles of water vaporized and 𝑛𝑓𝑢𝑒𝑙,𝑖𝑛 is the
number of moles of fuel combusted. 52

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 Some Heating Values
Component HHV ( MJ/kg) LHV (MJ/kg)
Hydrogen 141.8 121
Methane 55.53 50
Ethane 51.9 47.8
Propane 50.35 46.35
Butane 49.51 45.75
Pentane 45.35
Gasoline 47.30 44.40

• 𝑁𝑒𝑡 ℎ𝑒𝑎𝑡𝑖𝑛𝑔 𝑣𝑎𝑙𝑢𝑒 𝑜𝑟 𝐿𝐻𝑉 = σ 𝑦𝑖 (𝐿𝐻𝑉)𝑖

• 𝐺𝑟𝑜𝑠𝑠 ℎ𝑒𝑎𝑡𝑖𝑛𝑔 𝑣𝑎𝑙𝑢𝑒 𝑜𝑟 𝐻𝐻𝑉 = σ 𝑦𝑖 (𝐻𝐻𝑉)𝑖
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Wobbe Number W0
• The Wobbe number is related to the behaviour of a fuel
in a burner. Two gases with the same Wobbe number
give the same heat release at the burner tip for the
same pressure drop across the burner orifice (Assuming
T and P constants).
• The Wobbe number is a burner compatibility to a given
fuel and is defined as (page 36): 𝑊0 = 𝐺𝐻𝑉/√𝜌.
• Gross heating value (or HHV) divided by the square root
of the relative density of the gas.
• 𝑊0 has a unit of MJ/𝑚3 (SI).
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