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Heriot-Watt University

DEPARTMENT OF PETROLEUM ENGINEERING

COMPOSITION
Adrian C Todd

Introduction

Vary widely in chemical composition.

Depends on location.

Very complex characteristics.

What is Petroleum ?

Petroleum is a mixture of naturally ocurring


hydrocarbons which may exist in the solid,
liquid or gaseous states, depending on the
conditions of temperature and pressure to
which it is subjected. Amyx et al

What is Petroleum ?

In gaseous state
Natural Gas
In liquid state

Condensates

Petroleum oil

Crude oil

In solid state
Tar, Asphalts

What is Petroleum ?

At normal temperature and pressure:

Small molecules will be a gas.

Larger molecules will be a liquid

Larger molecules will be in a solid state.

Classification of Hydrocarbons -

Hager, Dorsey

Marsh gas
Gaseous
Petroleum
Fluid

Hydrocarbons

Natural gas
Crude oil
Mineral tar

Viscous
Bituminous

Asphaltite

Brea
Gilsonite

Solid

Cereous

Coal

Lignite
Subbituminous
Bituminous
Semibituminous
Anthracite
Kerogen

Bitumous shale

Petroliferous

Mineral Wax

Origins of Petroleum

SOURCE

Organic material deposited in sedimentary basins.

Marine life: plants and animals

Land derived: carried by rivers

MECHANISM

Reduction & decarboxylation & thermal cracking petroleum.

Gases

CH4 ( Bacteria)

H2S (Sulphur, sulphates in sediments + sulphates in petroleum)

CO2 (decarboxylation of organic matter, HCO3 & CaCO3 )

N2 (trapped air, organic matter )

Origins of Petroleum

MIGRATION

Primary ( movement of water with oil in solution

Secondary ( buoyancy, capillarity, lithology, earth


movements. )

Origins of Petroleum

TEMPERATURE & PRESSURE

Oil is lighter with depth

100oC all hydrocarbons except CH4, C2H6 &


C3H8 are unstable
200oC all except CH4 are unstable

Reservoir Fluid Composition


Origins

Various hypotheses

Depositional environment

Migration path

Compositions

Vary because of depositional characteristics, age & depth.

Evidence of maturing still taking place.

Within some reservoirs compositional gradient ( e.g. Brent North Sea )

Detailed compositional description essential for refining.

Reservoir Fluid Composition

Composition of crude oil mainly organic compounds, principally


hydrocarbons.
Small amounts of inorganic non-hydrocarbons, e.g. CO 2, S, N2 and
metal compounds.
Hydrocarbons may include the lightest, CH4 to napthenes and
polycylics with high molecular weights.
Appearance: gases, through clear liquids, yellow liquids to a dark
often black, highly viscous material.
Water is always present in pore space. Original depositional
environment.
Physical properties of oil & gas treated independantly of water

Reservoir Fluid Composition

In exploration and production detailed compositional


information is not required.
Descriptions are required in order to predict physical
properties and behaviour of the fluids at different conditions.
Simple descriptions are required to characterise fluids to
predict behaviour.
Two methods:

Black Oil Model


Compositional Model

Compositional Model & Black Oil Model

Compositional model
a multicomponent description in terms of
hydrocarbons.

Black Oil model


a two component description in terms of
produced oil ,stock tank oil, and produced
gas,solution gas.

Compositional Model-Hydrocarbons
Chemistry of Hydrocarbons
Hydrocarbons
Aromatic

Aliphatic

Alkanes
(Paraffins )

Alkenes

Alkynes

Unstable

Cyclic Aliphatics
( Napthenes )

Chemistry of Hydrocarbons
Alkanes or Paraffinic Hydrocarbons
Largest series with open chain molecules and
saturated bonds.
Carbon a valence of 4
Formula

CnH2n+2

Unsaturated hydrocarbons valency of 4


not satisfied- structure is not stable

Chemistry of Hydrocarbons- Isomerism


Above propane there are alternative ways to arrange
branched chains.
They are called isomers.
Isomers. Are substances of the same composition
but with different molecular structure.
Normal Butane

Iso Butane

CH3CH2CH2CH3

CH3CHCH3

B.Pt-31.1oF

CH3
B.Pt-10.9oF

Basic Properties of Common Paraffin


Hydrocarbons

State Properties of Common Paraffin


Hydrocarbons

Unsaturated Hydrocarbons

Unsaturated hydrocarbons have double or triple


bonds between carbon atoms.
Have the potential to add more hydrogen or other
elements.

Therefore termed unsaturated.

Termed olefins

Two types
alkenes
e.g ethylene

CH2=CH2

alkynes
e.g, acetylene

CH-CH

Stable Hydrocarbons

Only stable types

Paraffins

Napthenes

Aromatics

Napthene Series

Formula

CnH2n

Sometimes termed cycloparaffins or


alicyclic hydrocarbons.
Single bonds but carbon chain is closed
and saturated.

Very stable

Important constituents of crude oil.

Properties similar to paraffins.

Crude oil termed napthenic with high


napthene content

Aromatics

Aromatic series unsaturated


closed-ring
Formula CnH2n-6
Based on the benzene
compound.
Characterised by strong aromatic
odour.
Various compound found in crude
oil.
Closed ring gives greater stability
than open chain compounds.

Aromatic-napthenic crudes

Associated with limestone and dolomite


reservoirs.
Iran, Arabian Gulf and Borneo.
Some crudes described according to relative
amounts of non-paraffin compound.

Paraffinic, Napthenic, Aromatic

Not a reservoir engineering term.

Asphalts

Not a series
Highly viscous to semi-solid brown-black
hydrocarbons.

High molecular weight.

Usually contain sulphur and nitrogen.

May be present in colloidal suspension and


precipitate due to changes in pressure,
temperature and composition.

Non-hydrocarbon compounds

Small in volume, less than 1%,can have significant influence on processing and
quality of products.
Sulphur: and associated products 0.04 - 5 wgt%. Include sulphur and hydrogen
sulphide which is very toxic. Mercaptans. On combustion produce undesirable
SO2and SO3.

Oxygen: and compounds. Up to 0.5%wgt. Cause corrosive products.

Nitrogen: less than 0.1%. Complex compounds. Gaseous reduces thermal quality.

Carbon Dioxide: Very common. Cause of corrosion. Significant impact on fluid


properties.
Other compounds: Metal in low conc.Gases may contain He,H & Hg. Non-oil
produced fluids -water contain minerals which can form scales

Composition Description for Reservoir


Engineers

Main issue in reservoir engineering is physical behaviour and


properties of the petroleum fluids.

Composition has a significant impact on properties and behaviour.

Compositional description is the key to unlocking physical properties.

For the oil refiner the composition is the key to determine the
chemical products which can be extracted or processed from the
material.
Petroleum engineer wants as simple a description as possible to
determine physical properties as a function of T&P.

Composition Description for Reservoir


Engineers
Two models used to describe composition
Black Oil Model
A 2 component description,
where two components are
produced fluids,

stock tank oil and solution


gas.
Associated with this model
black-oil parameters

solution gas-oil ratio


oil formation volume factor.

Compositional Model
Compositioanl description based
on paraffin

series, CnH2n+2

Described up to a limiting C
number. Components greater than
limiting C number are lumped
together as a C+ component

Compositional Model

Isomers, normal and iso are identified up to pentane.


Non paraffinic compounds assigned to next higher paraffin according to
volatility.
All material above limiting C number are termed C+ fraction. e.g. C7+ for a
limiting C6 and C10+ for limiting C9.
C+ fraction is unique and characterised by apparent molecular weight
and specific gravity.
Some fluids complex, Paraffin description may not predict behaviour,
may required to identify Napthenic and Aromatic compounds. PNA
analysis.
Perhaps the case for gas condensates at high T&P.

Compositional Model
Reservoir fluid

C1 C2 C3 C4 C5 C6 C7+

Gas at surface conditions

Oil at surface conditions

Distribution of compounds a function


of pressure, temperature and
composition

The Uniqueness of the Reservoir


Reservoir Behaviour

Reservoir Development
Plan

Dynamic

Early agreement to
reservoir description
speeds development

Unique & Static


Also includes reservoir fluid
description

Reservoir Description

Compositional Model

Improved chemical analysis makes it possible to analyse


up to a C value of C29.
Although this leads to good description, associated
computer effort during prediction modelling is considerable.
Reduced number of components obtained by grouping
various C number compositions.

Reduced to 4 or 5 components.

These are described as pseudo components.

General Analysis

Since reservoirs are unique they also exist at different P&T.


Common basis and conditions used for describing quantities
of fluids.
Surface conditions-14.7psia (101.3KPa) and 60 oF (298K).
GAS - Standard cubic feet, SCF or standard cubic meter
(SCM).

LIQUID - stock tank barrels,STB(cubic metres (STM 3)

Relative gas to oil. GOR SCF/STB

General Analysis - density

Many oil types


API, American Petroleum Institute, classified
oils based on density based on a linear scales
hydrometer.
141.5
Degrees. API
131.5
o
SpecificGravity @ 60 F
Specific gravity relative to water @ 60oF

Classification of Reservoir Fluids

Reservoir Fluid
Types

Crude oil + dissolved gas

Condensate Gas
Heavy hydrocarbons dissolved

Near Critical One Phase Fluid


(Light oil or condensate fluid)

General Analysis

Refractive Index

Another indicator of density of produced oils.

Ranges from 1.39 to 1.49.

Heavier crude higher the refractive index.

Fluorescence

Measured by its colour under ultraviolet light

Often used on cuttings during drilling.


2o - 10o API
10o - 18o API
18o - 45o API
45o - above API

non-fluorescent to dull brown


yellow brown to gold
gold to pale yellow
blue -white to white.