Mari Petroleum Company Limited

BASIC PRINCIPLES
Presenters
Muhammad Asad (TE Petroleum)
Raza Mehdi (TE Mechanical)
Yasra Aslam (TE Chemical)
 www.mpcl.com.pk

BASIC OIL FIELD CHEMISTRY

MATTER

ELEMENTS

COMPOUNDS

MIXTURES
 www.mpcl.com.pk

HYDROCARBON NOMENCLATURE

 Covalent compounds composed of carbon and hydrogen.

 Chains and/or ring structures.
 Separated into families of homologous series.
 www.mpcl.com.pk

HYDROCARBON NOMENCLATURE

 Natural gas and crude oil consist primarily of

“straight chain” hydrocarbon molecules .
 Natural gas consists mainly of methane (CH4),
including ethane, propane, n-butane, i-butane, n-
pentane, i-pentane, hexanes and small quantities of
heptane plus components.
 Natural gas also includes contaminants of carbon
dioxides, nitrogen, and smaller quantities of
hydrogen sulfide, water vapor, and oxygen.
 www.mpcl.com.pk

PARAFFIN COMPOUNDS

 Most of the hydrocarbons of concern fall in the paraffin series

 General Formula: CnH2n+2
 Saturated Hydrocarbons
 Most stable .
 www.mpcl.com.pk

FLUID ANALYSIS

 Well fluid is usually analyzed by using chromatographs.

 www.mpcl.com.pk

MOLECULAR WEIGHT & APPARENT

MOLECULAR WEIGHT

 For pure components , molecular weight is defined

as the sum of atomic weights of all the combining
elements.
 For multi component mixtures, apparent molecular
weight is used to account for the contribution of
individual molecules which is in proportion to their
relative quantity in the mixture.
 www.mpcl.com.pk

GAS SPECIFIC GRAVITY & DENSITY

 Density of gas: “Mass per unit volume of gas”

 Because gas is compressible, its density depends on
pressure and temperature.
 Gas density can be calculated from gas law for real
gas with good accuracy:

 Specific Gravity: “ The ratio of the density of the

gas to the density of air at standard conditions of
temperature and pressure”
 www.mpcl.com.pk

 The density and specific gravity of gas may be

related to molecular weight by the following
equations:
 www.mpcl.com.pk

IDEAL GAS EQUATION OF STATE

 Any equation correlating P, V and T is called an “equation of state.”

 The “ideal gas law” describes most real gases at low pressure and high
temperature.
 It is valid up to pressures of about 60 psia (500 KPa)(4 bara).
 www.mpcl.com.pk
NON IDEAL GAS EQUATION OF
STATE

 Many PVT equations have been developed to describe non ideal, real
gas behavior.

 Some of the more common equations of state that attempt to define

the relationship between V, T and P for the real gases follow:
 Van der Waals

 Redlich–Kwong (RK)
 Peng–Robinson (PR)
 Benedict–Webb–Rubin (BWR)
 www.mpcl.com.pk

COMPRESSIBILITY FACTOR

 The ideal gas law corrected for non-ideality is

defined as:

 where Z, the compressibility factor, is the

thermodynamic property for modifying the ideal gas
law to account for behavior of real gases

 It is a measure of how much the thermodynamic

properties of a real gas deviate from those expected
of an ideal gas.
 www.mpcl.com.pk

 There are three regimes that affect the

compressibility factor:
 The value of Z tends toward 1 at low pressures
 The value of Z is less than 1 at intermediate
pressures
 The value of Z is greater than 1 at high pressures
 www.mpcl.com.pk

CRITICAL PROPERTIES

 CRITICAL POINT:
 For pure components: the maximum pressure and
temperature at which a two-phase, vapor-liquid system
can exist.
 For mixtures: pseudocritical values are calculated to
account for the contribution of individual molecules
which is in proportion to their relative quantity in the
mixture.
 www.mpcl.com.pk

REDUCED PROPERTIES

 The principle of corresponding states indicates that

any pure gas at the same reduced temperature, Tr,
and reduced pressure, Pr, should have the same
compressibility factor.
 The reduced temperature and pressure are defined as:

 For multi component systems such as hydrocarbon

mixtures, pseudo-reduced properties are used.(using
pseudocritical properties)
 www.mpcl.com.pk

PSEUDO-CRITICAL PROPERTIES WHEN

GAS COMPOSITION IS NOT KNOWN

 In the absence of gas

composition data (mole % of
each component) pseudo-
critical properties can be
determined by using
correlation based on gas
gravity.
 www.mpcl.com.pk

ADJUSTED PSEUDO-CRITICAL PROPERTIES

 To account for the effect of acid gases,

Wichert and Aziz equations are used to adjust
pseudo critical properties.
www.mpcl.com.pk
 www.mpcl.com.pk

DETERMINATION OF
COMPRESSIBILITY FACTOR
USING REDUCED
PROPERTIES
www.mpcl.com.pk
 www.mpcl.com.pk

COMPRESSIBILITY FACTOR
FOR DIFFERENT SPECIFIC
GRAVITY
www.mpcl.com.pk
 www.mpcl.com.pk

API GRAVITY

 The American Petroleum Institute gravity, or API gravity, is a

measure of how heavy or light a petroleum liquid is compared
to water: if its API gravity is greater than 10, it is lighter and
floats on water; if less than 10, it is heavier and sinks.
oAPI = (141.5/SG)−131.5

 Light crude oil

 Any crude oil with API gravity of over 31.1 degrees falls into
the light crude oil category.
 Medium crude oil
 Oils with API gravity falling between 22.3 and 31.1 degrees are
classed as medium crude oils.
 Heavy crude oil
 Heavy crude oils have API gravity of under 22.3.
 Extra heavy oil
 Also referred to as bitumen, extra heavy crude oils have API
gravity of below 10.0 degrees
 www.mpcl.com.pk

Specific Gravity without Phase

Change and with Phase Change
www.mpcl.com.pk
www.mpcl.com.pk
 www.mpcl.com.pk

VISCOSITY

 Defined as resistance to flow.

 Dynamic property.
 It is a number that represents the drag forces
caused by the attractive forces in adjacent fluid
layers.
 Units:
1. centipoise (cp).
2. dynes/cm2.
3. lbm/ ft-sec.
 www.mpcl.com.pk

VISCOSITY

 Two expressions of viscosity.

1. Dynamic(absolute ) viscosity
2. Kinematic viscosity.

 Kinematic viscosity = (Absolute viscosity)/

(Density).

 Units:
Kinematic Viscosity = Centistokes.
Absolute Viscosity = Centipoise.
 www.mpcl.com.pk

GAS VISCOSITY

 Gas viscosity is usually low as compared to liquids

because of large distances between molecules.
 If composition of gas is unknown then gas viscosity
can be determined by fig 3-17.
 Specific gravity of gas at specific conditions should
be known.
 Disadvantage:
1. It doesn’t make corrections for H S, CO and N2.
2 2

2. It is an approximate correlation and give less

accurate results.
www.mpcl.com.pk
 www.mpcl.com.pk

LIQUID VISCOSITY

 If viscosity of liquid is known at one

temperature then fig 3-18 can be used to
determine the viscosity at another
temperature.
 In case of pour point and cloud point issues
curve B should be used.
www.mpcl.com.pk
 www.mpcl.com.pk

LIQUID VISCOSITY

 If laboratory data is not available then

correlations exist that relate viscosity and
temperature, given the oil gravity.
µ= 10X-1.
 µ = oil viscosity, cp,
 T = oil temperature, 0F,
 x = y(T)(−1.163),
 y = 10z
 z = 3.0324 – 0.02023G,
 G= oil gravity, at 60 oF.
 www.mpcl.com.pk

TEMP. EFFECT ON VISCOSITY

 Viscosity changes with change in temperature.

1. Gas viscosity increase with increase in

temperature.
2. Liquid viscosity decrease with increase in
temperature.
 www.mpcl.com.pk

Phase Behavior

 Phase defines any homogeneous and physically distinct part

of a system that is separated from other parts of the system by
definite bounding surfaces
 Factors important to the physical behavior of molecules are
 Pressure
 Temperature
 Intermolecular forces
 We separate substances into three classifications:
 Pure substance (single-component systems)
 Two substances
 Multicomponent.
 www.mpcl.com.pk

System Components

 Natural gas systems are composed primarily of the lighter

alkane series, Methane and Ethane comprising 80% to 90% of
volume of the mixture.

 The intermediate-weight hydrocarbons (pentane through

decane) exist as volatile liquids at atmospheric conditions

 Natural gas systems can also contain non-hydrocarbon

constituents, including hydrogen sulfide (H2S), carbon
dioxide (CO2), nitrogen (N2) and water vapor mostly as
contaminants.
 www.mpcl.com.pk

Single-Component Systems

 Depending on the component’s pressure and temperature,

it may exist as a vapor, a liquid, or some equilibrium
combination of vapor and liquid.

 Vapor - Pressure line

represents the locus of
temperatures and pressures
at which vapor and liquid
exist in equilibrium.
 www.mpcl.com.pk

Critical Point and Triple Point

 The critical point (C) is the point at which the intensive,

properties of the liquid and vapor phases become identical.
This point marks the end of the vapor pressure line and
identifies the critical Pressure and critical temperature of the
pure component
 Water: 647.096 K(373.946 °C), 22,060 kPa (217.7 atm )
 Methane: 190.8 K(82.3 °C), 4,640 kPa(45.79 atm )

 The triple point (T) is the point where liquid, gas, and solid
phases exist at equilibrium.
 Water: 273.16 K (0.01 °C) 0.611657 kPa (0.00603659 atm)
 Methane: 90.68 K (−182.47 °C) 11.7 kPa (0.115 atm)
 www.mpcl.com.pk

Multicomponent Systems

 Natural gas systems are not pure substances. Rather,

they are mixtures of various components
 A mixture exhibits a phase envelope as shown in
figure

 Bubble Point Line

 Dew Point Line
 Cricondenbar
 Cricondentherm
 www.mpcl.com.pk

Lean Gas Systems

 For most natural gas systems, the reservoir temperature is

higher than the cricondentherm.
 For a lean or dry gas, the usual transition from reservoir
conditions to surface conditions does not intersect the phase
envelope. The gas is produced without a phase change.
 www.mpcl.com.pk

Rich Gas Systems

 The gas is sufficiently rich in intermediates and heavier

components so that surface conditions fall within the phase
envelope. Such a gas is called a rich or wet gas.
 The term “wet,” in this context, does not refer to the water
content of the gas rather condensate.
 www.mpcl.com.pk

Retrograde Systems

 If the reservoir temperature is less than the cricondentherm

but greater than the critical temperature, and the reservoir
pressure is initially above the phase envelope, the reservoir
fluid enters the two- phase region by forming liquid as the
pressure decreases. As pressure decreases further, the liquid
re-vaporizes and the mixture again enters the gas phase
region.

 True retrograde reservoirs have the characteristic of forming

liquid as pressure decreases at constant temperature
www.mpcl.com.pk
 www.mpcl.com.pk

Application of Phase Envelopes

 Proper analysis of many petroleum problems requires

knowledge about the phase envelope. Behavior of a reservoir
fluid during production is determined by the shape of its
phase diagram and the position of its critical point.
 VOLATILE www.mpcl.com.pk
BLACK OIL RETROGRAD WET GAS DRY GAS
OIL
RESERVOIR E RESERVOIR RESERVOIR RESERVOIR
RESERVOIR
Retrograde gas
Low-shrinkage High-shrinkage
condensate - -
crude oil. crude oil.
reservoir.
Tres < Tc<Tcric Tres < Tc<Tcric Tc < Tres<Tcric Tc < Tcric<Tres Tc < Tcric<Tres

Separator
Separator Separator Separator Separator
condition lies
condition lies condition lies condition lies condition lies
out of the
with in phase with in phase with in phase with in phase
phase envelope
envelope envelope envelope envelope

Initial
Initial Initial producing
Initial producing
producing GOR GOR between
producing GOR GOR above
of 2000 3300 and -
B/W 2000 and 5000
SCF/STB or 150,000
3300 SCF/STB SCF/STB.
less. SCF/STB.

Stock-tank oil
Stock-tank oil Stock-tank oil Stock-tank oil
gravity lies
gravity of 35 gravity of 40 gravity lies B/W
B/W 40 and 60 -
API or heavier API or heavier 40 and 60 API
API
 www.mpcl.com.pk
VOLATILE
BLACK OIL RETROGRAD WET GAS DRY GAS
OIL
RESERVOIR E RESERVOIR RESERVOIR RESERVOIR
RESERVOIR
Stock-tank oil Stock-tank oil
The liquid can
color that is is deeply
be lightly Stock-tank
very dark, black colored (usually
colored, brown, liquid is usually -
with a greenish brown, orange
orange, greenish, water-white
cast or sometimes
or water-white.
or brown green)
Reservoirs Reservoirs
exhibit an exhibit an
initial oil initial oil
formation formation
- - -
volume factor volume factor
of 2.0 reservoir greater than 2.0
BBL/STB or reservoir
less BBL/STB
The
The The composition
composition of
composition of of heptanes
heptanes plus
heptanes plus plus will be less - -
will be B/W
will be higher than 12.5 mole
12.5 to 30 mole
than 30 mole % %
%
 www.mpcl.com.pk

Phase Diagram of typical Black Oil Reservoir Phase Diagram of typical Volatile Oil Reservoir
 www.mpcl.com.pk

Phase Diagram of typical Retrograde Reservoir

 www.mpcl.com.pk

Phase Diagram of typical Wet Gas Reservoir Phase Diagram of typical Dry Gas Reservoir
 www.mpcl.com.pk

FLASH CALCULATIONS

 The amount of hydrocarbon fluid that exists in

the gaseous phase or the liquid phase at any
points at the process is determined by a flash
calculation.

 Pressure, temperature and partial pressure are the

factors that determine the amount of gas.
 www.mpcl.com.pk
PROCEDURE OF FLASH
CALCULATIONS
 Procedure:
1. An equilibrium “K” value is assigned to each
component.

1. “K” values are for specific convergence pressure.

2. Convergence pressure is determined on the basis of
binary fluid system.
 www.mpcl.com.pk
DETERMINATION OF MOLES OF
COMPONENT IN EACH PHASE
 If following data is known
1. KN for each component.
2. Ratio of total moles of vapor to total moles of liquid (V/L).
We can find:

Where FN is Total Moles of Component N in a fluid. It is to be assumed.

 www.mpcl.com.pk
STEPS INVOLVED IN
CALCULATION
 If KN for each component can be determined but (V/L)
and F is not known
then
1. Assume F.
2. Estimate the value of (V/L) and calculate VN and LN
value for each component.
3. Sum up to obtain the total moles of gas (V) and liquid
(L).
4. Compare the calculated (V/L) to assumed value.
5. Following formula can be helpful in this
 www.mpcl.com.pk

EXAMPLE
 www.mpcl.com.pk

EXAMPLE
 www.mpcl.com.pk

CHARACTERIZING THE FLOW STREAM

 Molecular Weight of Gas:

It can be determined from weighted
average gas molecular weight.

𝞢( VN x MWN)/ V
 www.mpcl.com.pk

CHARACTERIZING THE FLOW STREAM

 Molecular Weight of Liquid:

The molecular weight of the liquid stream is
calculated from the weighted average liquid
component molecular weight given by
 www.mpcl.com.pk

CHARACTERIZING THE FLOW STREAM

 Gas Flow Rate:

If the flow of inlet stream is known in moles
per day, then the number of moles per day of gas flow
can be determined from
 www.mpcl.com.pk

CHARACTERIZING THE FLOW STREAM

 Once the mole flow rate of gas is known in moles

per day, then the flow rate in standard cubic feet
can be determined by recalling that one mole of
gas occupies 380 cubic feet at standard
conditions. Therefore:
 www.mpcl.com.pk

EXAMPLE
 www.mpcl.com.pk

EXAMPLE
 www.mpcl.com.pk

CHARACTERIZING THE FLOW STREAM

Liquid Flow Rate:

3
 www.mpcl.com.pk

CHARACTERIZING THE FLOW STREAM

 Specific Gravity of Liquid:

3
 www.mpcl.com.pk

CHARACTERIZING THE FLOW STREAM

 Moles Flow rate of Stream:

 If mole fraction of each component in the feed stream is given
but is the mole’s flow rate for the stream is not given. Then for
first approximation we can use this method.

 Assumption:
 It can be assumed that all the oil in the stock tank can be
characterized by C7+ component of stream.
 www.mpcl.com.pk

CHARACTERIZING THE FLOW STREAM

.
1

2
 www.mpcl.com.pk

Approximate Flash Calculations

 www.mpcl.com.pk

Approximate Flash Calculations

 Suppose 300 API with 500 GOR.

1. It is flashed at 1000 psi. (250 ft3/bbl)
2. It is flashed at 500 psi. (125 ft3/bbl)
3. It is flashed at 50 psi. (150 ft3/bbl)
 www.mpcl.com.pk

IMPORTANT PHYSICAL PROPERTIES

 Dew point: the point at which liquid first appears within a
gas sample.

 Bubble point: the point at which gas first appears within a

liquid sample.

 Gross heating value: heat released by combusting of gas

sample with liquid water as a combustion product; also
known as the higher heating value (HHV).

 Net heating value: heat released by combustion of gas

sample with water vapor as a combustion product; also
known as the lower heating value (LHV).
 www.mpcl.com.pk

IMPORTANT PHYSICAL PROPERTIES

 Hydrocarbon Dew Point : It represents the condensation of

a hydrocarbon liquid.

 Water Dew Point: It represents the condensation of liquid

water.

 Reid Vapour Pressure: Vapour pressure at 1000F.

 True Vapour Pressure: Vapour pressure at any

temperature.
 www.mpcl.com.pk

THANK YOU