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Upstream pollution
prevention and waste
management
CGE686

Learning outcome

To understand the environmental impact of produced water, drilling muds and

drilling cuttings.
To identify the possible ways to minimize the generation of upstream waste.

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Contents

Produced water

Drilling waste mud and cuttings

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Produced water

Produced Water

Also known as
Brine
Saltwater

Sources of this water from an oil reservoir may include flow from
above or below the hydrocarbon zone
within the hydrocarbon zone
injected fluids and additives resulting from production activities
Also known as connote water or formation water

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1. Produced Water

In the production of natural gas produced water is separated from the gas at or
near the wellhead
Additional water is also injected into the reservoir to
Sustain pressure
Achieve greater recovery levels

Produced water production volume

Source: US National Energy Technology Laboratory (NETL), 2015

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Produced water production volume

Water to oil ratio

US National Energy Technology Laboratory (NETL) reports

US 5:1 and 8:1
Worldwide 2:1 and 3:1

BCC research (market research company based in the US)

North America increase in the ratio over next 12 years to 12:1 up to 50:1
(worst condition)

Producers need to pay between $3 and $12 per barrel to dispose of produced
water

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Why produced water is important for

O&G industry?

The cost of managing produced water is a significant factor in the profitability of oil and
gas production.

The cost of constructing treatment and disposal facilities, including equipment

acquisitions
The cost of operating those facilities, including chemical additives and utilities

The cost of managing any residuals or byproducts resulting from the treatment of
produced water
Permitting, monitoring, and reporting costs
Transportation costs.

Once these cost exceeds the value of the hydrocarbon produced from the well, the well is
usually shut down.

Factors affecting production volume

1. Volume of produced water increases for mature fields

2. Method of well drilling

Horizontal well produces more than vertical well at a similar drawdown
Horizontal well produces similar production rate at lower drawdown

3. Location of well

Horizontal well used in homogenous reservoirs - reduce the water

production

4. Different types of completion

Open hole permits testing of drilling zones and avoids drilling into water
But perforated completion method offers better control

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Factors affecting production volume

5. Single zone and commingled

As oil rate decline because of the maturing to the well, other zones are
opened to maintain the production of oil hence, water production
increases

6. Type of water separation technologies

Different methods are used to reduced the costs of lifting and/or water
handling for wells that produced large quantities of saline water.
Such as:
Water shut-off treatment using gelled polymer
Reducing beams pump lifting costs
Power options for reduce electricity costs
Separation technologies

Factors affecting production volume

7. Water injection or water flooding for EOR

Water flooding increase the percentage of water produced
As flood progresses, the volume of required water with suitable chemical
characteristics is necessary.
Because poor quality of treated makeup water enable sealing, clay swelling
and brine incompatibilities.
8. Poor mechanical integrity
Caused by mechanical problems of the casting holes corrosion or wear
Excessive pressure allow unwanted reservoir fluids to enter the casing and
increase water production

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Factors affecting production volume

9. Underground communications near wellbores or reservoirs, increases the

production of water.
Near wellbores channels behind casing, barrier breakdown and
completions into and near water.
Reservoirs coning, cresting, channeling through higher permeability
zones or fractures, fracturing out of zones

Types of
hydrocarbon
produced

Lifetime of
the reservoir

Factors
affecting
characteristics
of PW

Geographic
location of
the field

Geological
formation

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Characteristics of produced water

The major compounds of produced water

Dissolved and dispersed oil compounds
Dissolved formation minerals
Production chemical compounds
Production of solids
Dissolved gases

Dissolved and dispersed oil compounds

Oil is a mixture of hydrocarbon which include

Benzene, toluene, ethylbenzene and xylenes (BTEX)
Naphthalene, phenantherene, dibenzothiophene (NPD)
Polyaromatic hydrocarbons (PAHs)
Phenols

The amount depends on

Oil composition
pH, salinity, total dissolve solids (TDS), temperature
Oil/water ratio
Type and quantity of oilfield chemicals
Type and quantity of various stability compounds (waxes, asphaltenes, fine solids)

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Dissolved and dispersed oil compounds

Dissolved oil compounds concentration depends on pH and temperature

Organic acids (formic acid, propionic acid)
Aromatic compounds BTEX and phenol

Dispersed oil (consists of small droplets of oil suspended in the produced

water)
PAHs, C6 C9 alkylated phenols
Depends on the density of oil, amount of oil precipitation and interfacial
tension

Dissolved formation minerals

1. Anions Na+, K+, Ca2+, Mg2+, Ba2+, Sr2+, Fe2+

2. Cations Cl-, SO42-, CO32-, HCO3-

Affect the water chemistry:

buffering capacity, salinity
and scale potential

3. Heavy metals concentration depends on the age of wells and formation

geology.
Cadmium, chromium, copper, lead, mercury, nickel, silver and zinc

4. Naturally occurring radioactive materials (NORM)

226radium

Barium

& 228radium

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Production chemical components

Chemicals that are added to treat or prevent operational problems.

Production treating chemicals scale and corrosion inhibitors, biocides,

emulsion breakers, antifoam and water treatment chemicals.
Linear alkylbenzene sulfonate (LAS)
Alkyldimethlybenzenylammonium compounds
2-alkyl-1-ethylamine-2-imidazolines

Production solids

Formation solids

Corrosion and scale products

Bacteria
Waxes

Asphaltenes

Inorganic crystalline substances such SiO2, Fe2O3, Fe3O4 and BaSO4 are found in
the suspended solids

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Dissolved gases

CO2
O2

H2S

Natural gas produced water

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Oilfield produced water

Potential pathways to impact the

environment
Spills and Leaks

Discharge to
Surface Water

Underground
Injection

Air Emissions

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Fate and impact of produced water

Large spill can move into surface

water bodies
Salt problem in freshwater
Toxic compounds and oil &
grease can damage aquatic
life

Spills and Leaks

Salt can contaminate soil near

wellheads, pipelines and other
facilities
Kill plants
Damage soil to impact future
growth

Leakage from tanks can enter

groundwater
May enter source of drinking
water

Fate and impact of produced water

Discharge of salty produced
water to fresh water cause
damage to aquatic animals and
plants.

Discharge of oil & grease and

toxic chemicals can cause
damage to living organism

Discharge to
Surface Water

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Fate and impact of produced water

Underground
Injection

Checking the compatibility of the injected

produced water with the chemicals in the
ground is important to avoid:
Incompatibility of the chemicals can
cause precipitates to form block
pores and require additional
injection pressure

Potential microbial problems that

can lead to the formation of
hydrogen sulphide

Fate and impact of produced water

Air Emissions

Evaporation ponds and pits or mechanical evaporators

can create plumes of vapor that deposit on the ground
downwind of the site.
Salty deposits can harm plants and soil

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Fate and impact of produced water

The main constituent of produced water that causes impact salt

Other constituents can create problems in certain settings
Effects of marine life near production platforms.

Some fish species are attracted to productions

platforms.
Effects of these fishes
Oxidative stress
Altered fatty acid composition
Genotoxicity effects
Reproductive disturbance
These effects are local within 1 -2 km from
point of discharge
However, there is no published study on
human populations or communities.

Produced water management

Employing technologies to minimize
produced water production
Reuse and recycling
If neither of these tiers is practical, disposal
is the final option

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Water minimisation

Reducing the volume of water produced allows

More oil to be produced

Decreases the cost of lifting a heavier fluid to the surface

By minimizing the water, cost saving can be done

Reduced cost of equipment maintenance
Reduced produced water handling and treatment

Environment point of view

Less usage of chemicals for water separation

Less volume of produced water and associated pollutants discharge to the
environment

Technologies to minimize and reuse

produced water

1.
2.
3.
4.
5.

Use a closed-loop drilling fluid system

Drill horizontal wells
Optimize production rate to minimize the influx of water
Mechanically block water from entering the well
Treat the producing formation with polymers that decrease the permeability of
water, while maintaining the permeability of hydrocarbons
6. Use down-hole oil/water separation (DOWS) using hydrocyclone to separate water
and oil inside the well space
7. Seafloor separation technologies
8. Conduct hydrotest of pipelines, equipment and tanks with produced water
construction

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Water minimization technologies

limitations

The effectiveness in mechanically blocking the water from entering the well depends
on the type of reservoir and well construction. Examples of mechanical blocking
Straddle packers
Bridge plugs
Tubing patches
Cement
Chemical treatment polymers are used to shut off water-bearing channel or
fractures within the formation.
DOWS is restricted to type of wells.

Seafloor technologies very expensive.

Produced water re-injection

Onshore, treated produced water can be used for irrigation

Offshore, the primary re-use of produced water is to enhance oil production

water reinjection

Limitations - the produced water must be treated to meet certain quality levels
to
Prevent plugging of wellbore
Prevent plugging of reservoir pores
Prevent system failure

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Produced water re-injection

Factors that limits reinjection

Dispersed oil
Suspended solids
Fatty acids
Dissolved gases
Salts
pH
Temperature

Objective of produced water treatment

De-oiling
Dissolved gas
removal

Soluble
organics
removal
Desalination

Disinfection

Suspended
solids removal

Softening

Miscellaneous:
Removing
NORM

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Can be done via

Physical

Adsorption
Sand filters
Cyclones
Evaporation
Dissolved air
precipitation
C-Tour
Freezethaw/evaporation
Electrodialysis

Chemical

Chemical
precipitation
Chemical oxidation
Electrochemical
process
Photocatalytic
treatment
Fenton process
Treatment with
ozone
Room temperature
ionic liquids
Demulsifier

Biological

Aerobic
Anaerobic

Membrane

Microfiltration (MF)
Ultrafiltration (UF)
Nanofiltraion (NF)
Reverse osmosis (RO)

(Hayes & Arthur, 2004)

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(Hayes & Arthur, 2004)

(Hayes & Arthur, 2004)

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(Hayes & Arthur, 2004)

(Hayes & Arthur, 2004)

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(Hayes & Arthur, 2004)

General PW treatment

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Combination system

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Adsorption

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Adsorption theory

Liquid

Gas/ Vapor

Adsorbed solute: Adsorbate

Solid material: Adsorbent

Definition
Adsorption is a process
whereby a gas or liquid
(adsorbate) accumulates on
the surface of a solid
(adsorbent) to form a
molecular or atomic film.

Adsorption

For produced water treatment, adsorbent used are

Activated carbon
Organoclay
Copolymers
Zeolite
Resins

These are used to remove

Organic compounds
Heavy metals

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ADSORBENT

Shape
Small pellets, beads, granules, cylindrical, powders
Size ranging from 50 m to 1.2 cm

Porous structure
Macropore ( > 500) 50 nm
Mesopore (20 - 500 )
Micropore ( < 20 )
Based on International Union of Pure and Applied Chemistry (IUPAC)
Specific surface area: 300 to 1,200 m2/g

Pores of Activated Carbon

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Schematic of carbon
contactor.

Example: Process flow diagram of TORR

technology.

By EARTH Canada
Corporation.
TORR Total Oil
Remediation and
Recovery

Remove and recover

dispersed oil in water
2m and larger

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MECHANISM:ADSORPTION

MECHANISM: ADSORPTION

Molecules/atoms/ions in a gas or liquid diffuse to the surface of an adsorbent

where:
are held there physically by weak inter-molecular forces (physical adsorption)
they bond chemically with the solid surface (chemisorption)

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MECHANISM: ADSORPTION
Physical adsorption

Van der Waals adsorption

Low heat of adsorption
Non specific

Monolayer or multilayer

No dissociation of adsorbed species.

Only significant at relatively low
temperatures.

Rapid, non-activated, reversible.

No electron transfer.

Chemisorption
Covalent bonds
High heat of adsorption
Highly specific
Monolayer only
May involve dissociation
Possible over a wide range of
temperature
Activated, may be slow and
irreversible
Electron transfer leading to bond
formation between sorbate and
surface.

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MECHANISM: ADSORPTION

Movement of an organic and/or inorganic molecule to a surface site requires

four separate phenomena:
Bulk fluid transport
Film transport
Intraparticle (pore and/or surface diffusion)
Attachment

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MECHANISM: DESORPTION

Adsorption-Saturated-Desorption

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MECHANISM: DESORPTION

Regeneration process:
To recover Adsorbate
To reuse Adsorbent
Bed regeneration method (cyclic system)
Temperature-swing adsorption (TSA)
Pressure-swing adsorption (PSA)

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MECHANISM:TEMPERATURE SWING
ADSORPTION (TSA)

Increase in temperature

Increase in temperature leads to a decrease in the quantity adsorbed

Important note - regeneration temperature does not cause degradation of the

adsorbents
Mechanism passage of a hot purge gas or steam

Important characteristic to treat feeds with low concentrations of adsorbates

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MECHANISM: TEMPERATURE EFFECT

For a single adsorbate:

If the partial pressure remains

constant at P1, increasing the
temperature from T1 to T2 will
decrease the equilibrium
loading from q1 to q2.

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Bed TSA System

Cycle Steps

1. Adsorption at T1 to
breakthrough

2. Heating of the bed to

T2 (T2 > T1)
3. Desorption at T2

4. Cooling of the bed to

T1
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MECHANISM: PRESSURE SWING

ADSORPTION

Reducing the partial pressure of the adsorbate.

2 ways:
Reduction in the system total pressure
Introduction of an inert gas while maintaining the total system pressure
Cycle time very quick (minutes or second)

Operate PSA close to ambient temperature at a given partial pressure, the

loading is increased as temperature decreased
Popular for performing bulk separation of gases controlled by adsorption
isotherm or adsorption kinetics

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MECHANISM: PRESSURE EFFECT

For a single adsorbate:

Reducing the partial pressure

from P1 to P2 causes the
equilibrium loading to be
reduced from q1 to q2

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Bed PSA System

Each bed operates alternately in 2 half-cycles of

equal duration:
Pressurisation followed by adsorption
Desorption by depressurisation (blowdown)
followed by a purge
Adsorption pressure greater than
atmospheric

Desorption pressure being atmospheric

Pressurisation feed gas

Purging effluent (non-adsorbed) product gas

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Operation Modes: Stirred Tank (Batch)

Powdered adsorbent e.g. activated carbon particle diameter less

than 1 mm
Main application removal of very small amounts of dissolved,
large molecules e.g. colouring agents
Spent adsorbent removed by sedimentation or filtration

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Operation Modes: Cyclic Fixed Bed

(Batch)

Adsorbent particle size 0.05 cm to 1.2 cm

Optimal particle size bed pressure drop & solute transport rate
Main application removal of organic compounds from water
Spent adsorbent regenerated at high temperature

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Operation Modes: Continuous

Countercurrent

Need to circulate solid adsorbent as moving bed to achieve steady

state operation
Difficult in regenerating adsorbent when heavier HC presents

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THEORY: EQUILIBRIUM RELATIONS

Concentration of a solute
in a fluid phase
T, P

Data is plotted as
adsorption isotherms

Concentration of a
solute in a solid phase

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Adsorption isotherms
q, kg adsorbate / kg adsorbent

Usage of adsorption isotherm

To select suitable adsorbent
To select separation process

c, kg adsorbate / m3 fluid
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Adsorption Isotherms

The relationship between the concentration of solute in fluid phase and its
concentration on the solid.

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Types of Isotherms: Linear

Linear Isotherm
Similar to Henrys law:

q = Kc (12.1-1)
c : concentration (fluid is liquid)

p : partial pressure (fluid is a gas)

q : mass, moles or volumes of adsorbate per unit mass or per unit

surface area of adsorbent
K : an empirical, temperature-dependent constant

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Types of Isotherms: Freundlich

q Kc n

K = Freundlich constant
n = constant

Determined
experimentally

c = equilibrium concentration
The dimensions for K depends on the value of
n.
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Types of Isotherms: Langmuir

Assumptions:

qc
q 0
K c

K, q0 = constant

c = equilibrium concentration

Monolayer coverage on adsorbent

No interactions between adsorbent molecules

All adsorbate molecule/adsorbent interactions are the same

Only a fixed number of active sites available

Adsorption is reversible and reached an equilibrium condition

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Example: Adsorption Isotherms

Batch tests were performed in the laboratory using solutions of phenol in water
and particles of granular activated carbon. The equilibrium data at room
temperature are shown in the table below. Determine the isotherm that fits the
data.
(kg

phenol/m3

0.322

solution)

0.117
0.039

0.0061
0.0011

(kg phenol/kg carbon)

0.150
0.122
0.094

0.059
0.045

Refer to Geankoplis C. J. Transport Processes and Separation Proces Principles, 4th80Edition

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Solution

1. Rearrange the isotherm equation to become a linear equation.

2. Plot the graph

3. The suitable isotherm is when the plot is a straight line.

Graph was plotted on log graph paper.

Suitable isotherm is Freundlich isotherm
where
Slope, n = 0.229
Constant, K = 0.199
Adsoprtion isotherm equation is
q = 0.199c0.229

BATCH ADSORPTION

Used when quantities to be treated are of small amount.

Isotherms and material balance are needed.
Material balance on the adsorbate:
qF M + cF S = q M + cS

where:
qF = initial concentration of solute on the solid
q = final concentration at equilibrium
M = amount of adsorbent, kg
S = volume of feed solution, m3

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Example: Values of q and c at equilibrium

A wastewater solution having a volume of 1.0 m3 contains 0.21 kg
phenol/m3 of solution . A total of 1.40 kg of fresh granular activated
carbon is added to the solution , which is then mixed thoroughly to
reach equilibrium. Use the isotherm q = 0.199c0.229, find
a) the final equilibrium values (q & c)

b) the percentage of phenol extracted?

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Solution

Information given:

This intersection gives the

equilibrium value.
q = 0.106 kg phenol/kg carbon
c = 0.062 kg phenol/m3

cF = 0.21 kg phenol/m3
qF = 0 (assumed)

% phenol extracted =

100 = 70.5

q = 0.199c0.229

S = 1.0 m3

M = 1.40 kg carbon

qF M + cF S = q M + cS

0(1.40) + 0.21(1.0) = q(1.40) + c(1.0)

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FIXED BED ADSORPTION

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FIXED BED ADSORPTION

Concentration Profiles
Fluid to be treated passed down through the packed bed at a constant flow rate
Concentration of solute in the fluid phase and of the solid adsorbent phase
change with time and position MTZ

Mass Transfer Zone (MTZ) width and shape depends on:

the adsorption isotherm
flowrate
mass transfer rate to the particles
diffusion in the pores

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Mass Transfer Zone

Adsorption only occurs in a particular
region of the bed, known as Mass
Transfer Zone (MTZ) which moves
through the bed.

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Breakthrough Concentration Curve

1.0
c/c0

At t2;
At tb;

t1

0.5
0

At t1;

mass-transfer
zone

H1

t2

tb

t3

H2
Height of adsorption bed, H

H3

HT

Typical solute conc. profiles for fluid as a function of distance through the bed at increasing times t1, t2
and tB from start of the flow through bed.
no part of bed is saturated

the bed is almost saturated for a distance H1. At H2 the bed is still clean. The region H1 and H2 is the
mass transfer zone, where adsorption takes place.

the leading point of mass transfer zone just reach the end of the bed. This is called breakthrough
point.
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Breakthrough Concentration Curve

1.0

mass-transfer
zone

c/c0

0.5
0

t1

t2

t3

break point,
cb
t4

tb

cd

t6

Ratio of outlet solute concentration to inlet solute concentration in the fluid as a function of time from the
start of flow. The S-shaped curve is called the breakthrough curve.
Prior to tb, the outlet solute concentration is less than the maximum allowable of c/c0 between 0.01 to
0.05.
At tb this value is reached. The adsorption step should be discontinued.

If the adsorption step is allowed to be continued for t>tB , the outlet solute concentration would be
observed to rise rapidly, eventually approaching the inlet concentration as the outlet end of the bed
became saturated.
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Breakthrough Concentration Curve

Important points:

Break point (tB)

cout/cF is often taken as 0.01 to 0.05

Most bed capacity is used at the break point

Mass transfer zone: Region where most of
the concentration change occurs.

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Evaporation

Evaporation

Evaporation

Vapor from boiling liquid is removed

Remains concentrated solution

Properties which affect the processing methods :

Concentration in the liquid
Solubility
Temperature sensitivity of materials
Foaming or frothing
Pressure and temperature
Scale deposition and materials of construction

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Concentration in the liquid

Liquid feed to an evaporator is relatively dilute.

As evaporation proceeds, the solution may become very

concentrated.
Adequate circulation and/or turbulence must be present to keep
the heat transfer coefficient from becoming not too low.

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Solubility

As solutions are heated and the concentration of solute

(salt) increases, the solubility limit of the material in the
solution may be exceeded and crystals may form.

May limit the max concentration in solution which can be

obtained by evaporation.

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Temperature sensitivity of materials

Temperature-sensitive materials such as food & biological

materials such as milk, vegetable extracts may degrade at
higher temperature.
Degradation is a function of temperature & time.

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Foaming or frothing

Some solutions form a foam or froth during boiling (eg. Food

solutions such as skim milk, some fatty acid solutions)
Entrainment losses occur - suspended droplets of liquid are
carried in the escaping vapor

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Pressure & Temperature

The higher the operating pressure of the evaporator, the higher

the temperature at boiling.
To keep the temperature low in heat-sensitive material, its
often to operate under 1 atm pressure

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Scale deposition

Some solutions deposit solid materials on the heating surfaces

due to the products decomposition or decrease in solubility.
May decrease the overall heat transfer coefficient and the
evaporator must be cleaned.

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Materials of construction

Evaporators are made of steel (carbon steel). However, many

solutions attack ferrous metal and/or contaminated by them.

Use special material (nickel, stainless steel, aluminium), however

its expensive

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Evaporation

The basic factors that affect the rate of evaporation are the:
rate at which heat can be transferred to the liquid
quantity of heat required to evaporate each kg of water
maximum allowable temperature of the liquid
pressure at which the evaporation takes place
changes that may occur in the solution during the course of the evaporation
process

Methods

Once-through sensitive materials (food industry)

Circulation used in oil and gas industry and others

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Type of evaporators used in oil and gas

Type of evaporators used in oil and gas

Vapor compression evaporation

Vertical tube evaporators

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Benefits of evaporation for produced

water treatment

Eliminate physical and chemical treatments so no chemical sludge is produced

and costs of waste and life cycle is lowered.
Require less maintenance materials and maintenance labor.
Reduce the amount of produced water de-oiling required.

Increase Once Through Steam Generators (OSTG) feed-water quality and

improve OSTG reliability.
OSTG used for heavy oil recovery processes.
Produces high pressure steam for injection into geological formations
containing heavy oil.
The heat given by the condensing steam fluidizes the heavy and allow the
oil/water mixture to be brought to the surface.

Heat and mass balance for single effect

evaporators
Feed F, TF , xF , hF

Saturated Steam S, Ts , Hs

F, L, S = mass flow, kg/h

T = temperature,
x, y = solids content, mass fraction
H = vapor enthalpy, J/kg
h = liquid enthalpy, J/kg

Vapor V, yV T1, HV

V is pure solvent,
yV = 0

Condensate S, TS, hs

Concentrated liquid L, T1, xL, hL

Refer to Geankoplis C. J. Transport Processes and Separation Proces Principles, 4th Edition

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Heat and mass balance for single effect

evaporators

Important basis of calculation

S is assumed to leave the evaporator at TS

(saturation temperature) with enthalpy hs.
Therefore, steam gives only its latent heat,

=
(1)
V is in equilibrium with L, the
temperatures are the same (T1)
T1 at the concentrated liquid side is at
boiling point with a saturation vapor
pressure of P1
Assume that the system is at steady state
rate of mass in = rate of mass out

Heat and mass balance for single effect

evaporators
Material balance

Overall material balance: F = L+V (2)

Balance on the solute (solids): FxF = LxL (3)

Heat balance

Total heat entering = Total heat leaving

Heat in feed + Heat in steam = Heat in concentrated liquid

+ Heat in vapor + Heat in condensed steam
Assume no heat lost via radiation or convection

Fhf + SHs = LhL + VHV + ShS

simplified using equation (1)

Fhf + S = LhL + VHV (4)

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Heat and mass balance for single effect

evaporators
Heat transfer to evaporator

Heat transfer to evaporator

q U AT UA(Ts T1 ) (6)

q = S(HS hS) = S (5)

Latent heat of steam can be found in steam

tables

If the enthalpies of the feed and products are

not available, approximations can be made via
Latent heat of evaporation of 1 kg mass of
water solution can be obtained from steam
table using the temperature of the boiling
solution, T1.
Heat capacities of liquid feed, cpF and
product, cpL

q = heat transferred per unit time

U = overall coefficient of heat transfer

A = heat transfer surface

T = temperature difference between the two

streams

Example

A continuous single-effect evaporator concentrates 9072 kg/hr of a 1.0 wt% salt

solution entering at 311.0 K (37.80C) to a final concentration of 1.5 wt%. The
vapor space of the evaporator is at 101.325 kPa (1.0 atm abs) and the steam
supplied is saturated at 143.3 kPa. The overall heat transfer coefficient, U = 1704
W/m2 K.
Calculate:

a) The amount of vapor (V) & liquid product (L)

b) The heat transfer area required (A)
Assume cpF is of water = 4.14 kJ/kg.K

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Solution for (a)

Information that we have:

Material balance:

xF = 1.0 wt% = 0.01

FxF = LxL

F = L+V 9072 = L+V

F = 9072 kg/h

9072(0.01) = L(0.015)

xL = 1.5 wt% = 0.015

L = 6048 kg/h

V = 3024 kg/h

Solution for (b)

FhF + S = LhL + VHV

?

Latent heat of
condensation at
Ts

Latent heat of
evaporation at T1

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Solution for (b)

Find hF & hL

Find

T1 = choose the boiling point of water

because the salt solution is dilute.

From steam table at 143. 3 kPa (given)

hF = cpF(TF T1)

hs = 461.3 kJ/kg

TF = 311 K (given)

Since the evaporator pressure is at

101.325 kPa (1 atm), T1 = 372.2 K (100C)
= 4.14(311 373.2) = -257.5 J/kg

hL = CpL(T1 TBP)

TS = 383.2 K (100C)
Hs = 2691.5 kJ/kg
= 2230.2 kJ/kg

TBP = T1 hL = 0

Solution for (b)

Find HV

It is the latent heat at T1 = 372.2 K

(100C)
Hs = 2676.1 kJ/kg
hs = 419.04 kJ/kg

Find S

Fhf + S = LhL + VHV

9072(-257.5) + S(2230) = 6048(0) + 3024(2257)

S = 4108 kg steam/h

= 2257 kJ/kg

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Solution for (b)

Find q
q = S

q = 2 544 000 W

Finally, find A

q U AT UA(Ts T1 )

A = 149.3 m2

Steam Economy

Capacity = no. of kilograms of water vaporized per hour

Economy = no. of kilograms steam fed to the unit per hr
Steam economy = Capacity /Economy (kg vaporized water/kg steam used)
steam economy =

3024
= 0.736
4108

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Effects on processing variables

1. Effect on feed temperature

Higher feed temperature reduces the size of heat transfer area

Because if the feed temperature is above boiling point, additional vaporization is
obtained (flashing of the entering hot feed)

2. Effect of pressure

Reducing the pressure will increase the T

Resulting in decrease of heating surface area and cost of evaporator

3. Effect of steam pressure

Higher steam pressure, increases T

Resulting in decrease of heating surface area and cost of evaporator

Non dilute solutions

SOLUTIONS ARE NOT DILUTE,

HENCE..

THERMAL PROPERTIES OF THE SOLUTION IS DIFFER

CONSIDERABLY FROM THOSE OF WATER.

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BOILING POINT RISE & DUHRING

DIAGRAM

For a given pressure, the boiling point of an aqueous solution is higher than that
of pure water. The increase in boiling point over that of water is known as the
boiling point rise (BPR)

BPR = Boiling point of water at a given pressure Boiling point of solution (refer
Duhring Diagram)

NaCl-Water System

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Example

If the boiling point of water at

25.6 kPa is 65.6C,

1. What is the boiling point of

30% NaOH?
79.5C

2. What is the boiling point rise?

13.9C

Boiling point of water (0 C)

NaOH-Water System

PW Management Options for O&G

Industry

Injection

Injection of produced
water into the same
formation from which
the oil is produced or
handle to another
formation.

Discharge

Reuse in oil and gas operation

Treatment of produced
water to meet onshore
Consume in beneficial use
Treat the produced
or offshore discharge
water to meet the
regulations.
quality required to use Produced water
it for usual oil and gas treatment to meet to
fields operations
quality required for
beneficial uses such as
irrigation , rangeland
restoration, cattle and
animal consumption,
and drinking water.

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2. DRILLING FLUID

The key to making the rotary drilling system work is the ability to circulate a fluid
continuously down through the drill pipe, out through the bit nozzles and back
to the surface.
Purpose of Drilling Fluids

1. Cooling and lubrication. As the bit drills into the rock formation, the friction
caused by the rotating bit against the rock generate heat. The heat is dissipated
by the circulating drilling fluid. The fluid also lubricates the bit.

2. Cuttings removal. An important function of the drilling fluid is to carry rock

cuttings removed by the bit to the surface. The drilling flows through treating
equipment where the cuttings are removed and the clean fluid is again pumped
down through the drill pipe string.

2. DRILLING FLUID

3. Suspend cuttings. There are times when circulation has to be stopped. The
drilling fluid must have that gelling characteristics that will prevent drill cuttings
from settling down at the bit. This may caused the drill pipe to be stuck.

4. Pressure control. The drilling mud can be the first line of defense against a
blowout or loss of well control caused by formation pressures.
The hydrostatic head produced by the mud in psi is = 0.052 x G x H
where G = density of mud in ppg

H = depth of the hole in feet.

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2. DRILLING FLUID

This hydrostatic head will counter the formation pressure in order to avoid a
blowout while drilling. For example, lets say a well is being drilled in a salt-water
basin (pressure gradient of 0.465 psi/ft), the pressure in the formation at 10,000
feet would be expected to be:
10,000 x 0.465 = 4,650 psi

The weight of mud required to counter this pressure is calculated as follows.

P = 0.052GH

4,650 = 0.052 x G x 10,000

G = 8.94 ppg

2. DRILLING FLUID

5. Data source. The cuttings that the drilling mud brings to the
surface can tell the geologist the type of formation being drilled.

6. To wall the hole with impermeable filter cake. This will give a
temporary support to the wall of the borehole from collapsing
during drilling.

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2. DRILLING FLUID

Three basic types of DF are :

1)
Water Based Mud ( WBM) - water or brine (salt solution) as base
fluid/continuous phase. This is the most common drilling mud used in
oil drilling.
2)
Oil Based Mud (OBM) - crude oil or diesel or mineral oil as based
fluid/continuous phase.
Serve a wide range of application, some of which cannot
currently be performed by other DF
OBM is highly inhibitive, resistive to contaminants,
temperature and pressure. Its also highly lubricious, non
corrosive and flexible
3)

Pneumatic Based (PBM) - air, foam or natural gas as base fluid

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TYPES OF DRILLING FLUIDS - Examples

Non-water
based
Water
based

Pneumatic

Diesel oil
Mineral oil
Synthetic Fluid

Colloidal clay
Clay and polymer
Polymer
Dry gas
Mist
Foam
Gasified Mud

DRILLING FLUID COMPOSITION

Composition of a typical bentonite gel water based mud ,density

1300kg/m3. Components added to 1 barrel of water : (bbl=barrel,
pps=pounds per barrel); CMC :(carboxymethylcellulose)

Component
Water
Bentonite
Caustic soda
Soda ash
High viscosity cmc
Low viscosity cmc
Barite

Quantity
1 bbl
20 ppb
0,5 ppb
0,5 ppb
1,5 ppb
3,5 ppb
160 ppb

Mass(kg)
159
9,1
0,23
0,23
0,68
1,59
72,58

Volume(L)
1588,99
9,07
0,22
0,10
0,47
1,09
17,28

%mass
65,33
3,73
0,9
0,9
0,28
0,65
29,82

%volume
84,92
4,85
0,12
0,5
0,25
0,58
9,23

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DRILLING FLUID COMPOSITION

Composition of a typical oil based mud density 1318 kg/m3 , salinity 22.5%, oil to
water ratio 65:35. components combine to give a total volume of one barrel.(bbl:
barrel; ppb:pounds per barrel; gpb: gallons per barrel)
Component

Quantity

Base fluid
Viscosifier
Emulsifier 1

0,5 bbl
5 ppb
0,8 ppb

Lime
Water
CalCl2
Barite

5 ppb
0,30 ppb
30,2 ppb
167,9 ppb

Emulsifier 2

0,4 ppb

Mass(kg)
64,63
2,26
2,89

Volume(L)

1,49

2,26
47,15
13,70
76,15

%mass

83,31
1,40
3,02

30,37
1,08
1,38

1,00
47,22
3,35
18,16

1,08
22,50
6,54
36,34

1,51

0,71

%volume
52,40
0,88
1,90
0,95

0,63
29,70
2,11
11,42

DRILLING FLUID DESIGN

Synthetic Based Mud ( SBM)

The goal of SBM (also called pseudo OBM) is to provide an alternative
to OBM, without the toxicity and less environmental impact
The base fluid is a man made non aqueous liquid with different
molecular structure to the raw material it is manufactured with.
Common base oil are Saraline and Sarapar (of Bintulu SMDS) and
Petrofree (palm oil ester based product)
Currently PCSB using Sarapar 147 as a base fluid for SBM

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ADDITIVES

Various thickeners are used to influence the viscosity of the fluid, e.g. xanthan
gum, guar gum, glycol, carboxymethylcellulose (CMC), polyanionic cellulose
(PAC), or starch.

Deflocculants are used to reduce viscosity of clay-based muds; anionic

polyelectrolytes (e.g. acrylates, polyphosphates, lignosulfonates or tannic
acid derivates such as Quebracho are frequently used.
Some other common additives include lubricants, shale inhibitors, fluid loss
additives (to control loss of drilling fluids into permeable formations).
A weighting agent such as barite (specific gravity =4.3) or ilmenite (spec. gr. 4.5)
is added to increase the overall density of the drilling fluid.

ENVIRONMENTAL IMPACT OF DRILLING FLUIDS

Drilling wastes deserve special attention. The volume of drilling wastes usually ranges
from 1,000 to 5,000 m3 for each well. Such wells can number into dozens for one
production platform and many hundreds for a large field.
As a result of many technological operations and procedures, drilling muds and cuttings
are saturated with hundreds of very different substances and compounds.

It is their discharges into the sea that pose one of the main ecological threats during
offshore oil production.
In particular, many countries express concern regarding biocides, which are used to
suppress microflora in the drilling and other circulating fluids.

The list of such compounds includes over one hundred names. The most widespread
biocides used in the oil and gas production practice include sodium salts of hypochlorite,
formalin releasers, and glutaraldehyde as well as biguanidine and quaternary
ammonium, and a number of other compounds.

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ENVIRONMENTAL IMPACT OF DRILLING FLUIDS

The composition of some compounds is not always known. Some biocides are highly toxic. Many
countries either discourage (for example, in case of carbamates and thiocarbamates) or prohibit
(for example, in case of dichlorophenols and pentachlorophenates) their use by the offshore oil
and gas industry.
Drilling discharges also contain many heavy metals (mercury, lead, cadmium, zinc, chromium,
copper, and others) and NORM (Uranium, Thorium, Radium etc) that come from components of
both drilling fluids and drilling cuttings.

Drill cutting discharges effect on benthic system around platform.

Base Oil detected in sediment up to 2km from drilling site
Less than 300 m (substantial)
500-1000 m (significant)
Up to 2 km (traces)
Similar concentrations after 8 yrs survey (low degradation).
Oil accumulated deeper in sediment (0-30cm surveyed).

Method to evaluate the environmental

impact of drilling fluid

By using BIOASSAY.

Placing chosen organism placed in the drilling fluid at

different concentration.
Use LC50 to determine the toxicity
LC50 ( lethal concentration ) : standard measure of the
toxicity of the surrounding medium that will kill half of the
sample population at specified time. It is measure in
micrograms (or milligrams) of the material per liter, or parts
per million (ppm), of air or water

138

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Drilling Waste Management

Operators must achieve a balance between

1. Minimizing environmental impact

2. Maintaining borehole stability
3. Maximizing drilling efficiency

Drilling waste management

140

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DRILLING CUTTINGS MANAGEMENT

Recently, a technology was developed to remove the drilling

wastes, especially cuttings, by reinjecting their slurry into a
geological formation. This gives some hope to achieving zero
discharge of oil-containing wastes during offshore oil and gas
production.
Some other measures (such as slim-hole drilling) to reduce
discharges, particularly in environmentally sensitive locations, are
being investigated by the industry.

Minimising drilling fluids

Some of the techniques include pipe wipers and vacuuming of spills on the rig
floors
Pneumatic drilling (air, air/water)

Developing variations of fluids that are less toxic and easily to bio treatment.
Drilling practice that reduce the generation of drilling waste.
- Directional drilling

- Drilling smaller diameter holes

- Drilling techniques that use less frilling fluids

142

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Reuse of drilling cuttings

Road spreading
One use of cuttings is to stabilize surfaces that are subject to erosion, such as
roads or drilling pads.
Reuse of Cuttings as Construction Material
Need to be treated to render the cuttings more innocuous
Used for
fill material,
daily cover material at landfills,
aggregate or filler in concrete, brick, or block manufacturing.

143

Reuse of drilling cuttings

Restoration of Wetlands Using Cuttings

as a substrate for restoring coastal wetlands

Use of Cuttings for Fuel

Cuttings were blended in at a low rate with coal, the primary fuel source

144

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Disposal

Pre treatment
Reduce the volume of the waste
Reduce the potential hazard of the
waste
Alter the state of the waste
(separate liquid and solid phases)

Disposal methods
Deep well disposal
Disposal liquid waste are injected
into a formation
-produced water, drilling
completion wastes

Evaporation pond
These pond facilitate the reduction
of waste volume through
evaporation
-drilling fluids
Thermal method
Use high temperature furnaces to
reclaim or destroy contaminated
material
-HC contaminated soil

145

Disposal

On-shore
To the sea
Reinjected into the disposal well
Off-shore
the waste fluids would be temporarily stored in earthen pits( on site or off-site
Eventually will be disposed into landfill

146

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Secured landfill diagram

147

Reducing oil waste

Solids must be removed before reusing the drilling mud.

This is to avoid the existence of ultrafine solids content in the mud that will
affect the fluids performance and general stability worn out mud that
needs to be disposed of.
Method to recover base oil from worn out mud.

M-I SWACO RECLAIM technology chemically enhanced solids-removal process

Flocculants used to remove oil-wet solids
Surfactants used to weaken muds emulsion for the flocculants to work
demulsify brine droplets from the mud
Centrifuge to remove the small solids and brine (water)

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CRI Cuttings reinjection

1. Typically cuttings are mixed with seawater
2. Grinded

3. Or other mechanical action to form a stable viscous

slurry
4. Pumped down a dedicated disposal well or through
annulus between casing strings on an active well
5. Forced under pressure into formations

6. Which creates hydraulic fracture in the formation.

7. At the end of the injection program, the well or the

annulus are sealed with cement.

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3. MERCURY

A concern in oil & gas industry. Found in almost all oil and gas
reservoirs
Highest concentrations normally found from reservoirs in South
America, South East Asia, Easter europe
European/African/North American gas sources also contain mercury
Mercury is classified as hazardous substance with limited use
Mercury containing waste classified as hazardous waste
Hazardous waste management requires special license

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3. MERCURY

Origin -HgS (cinnabar or mercuric sulfide) in reservoir or deposits.

Hg0(g) i.e. Elemental mercury is the major Hg containing

compound at reservoir conditions
Major mercury compoundsHg0(g) and HgS(s).
HgS(g) and Hg2(g) negligible.

Organic
mercury
components
concentrations/partial pressures

3. MERCURY

occur

in

LOCATION

ELEMENTAL MERCURY CONCENTRATION (mg/m3)

East Asia

58-193

N Europe

0.01-180

South America
North Africa
Middle East
N America

insignificant

69-119

0.3-130

1-9

0.005-0.04

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3. MERCURY

Corrosion/embrittlement

Precipitation(HgS)

Mechanisms

Plugging of compact equipment

Caused by elemental mercury

Amalgamation

Amalgam (mercury alloy) corrosion

Liquid Metal Embrittlement, LME

Fouling

Poison the precious metal catalysts

Galvanic corrosion

3. MERCURY

Cinnabar is highly toxic

Mercury poisoning via:

exposure to water-soluble forms of mercury
inhalation of mercury vapor, or
eating seafood contaminated with mercury

New health hazard from Hg released to atm undergo bio-methylation reactions

to form highly toxic DMM (dimethyl mercury), an organo-mercury compound
Refer guidelines on mercury mgmt in oil and gas industry 2011

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3. MERCURY

3. MERCURY

Traditional : packed bed with sulfur impregnated activated carbon

Drawback 1: no use for spent carbon
Drawback 2: Landfill not allowed. Only combustion followed by condensation
of mercury
Modern thinking inorganic route i.e using reactive metal sulfides
Hg + MxSy = MxSa + HgS
Advantages : spent material recycled through metal smelters

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3. MERCURY

Further reading
Mercury Removal Project: Issues and Challenges in Managing and Executing
a Technology Project 2007
Challenges in Managing Mercury in Malaysia 2009

4. NATURALLY OCCURRING
RADIOACTIVE MATERIALS
(NORM)

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4. NORM

Naturally occurring radioactive materials such as Radium -226 and Radium-228

are found in the oil sludge as the unwanted by product in the waste stream from
oil and gas exploration activities. The NORM have to be treated at suitable
facilities on-shore for long term storage to reduce volume and minimise
environmental effects.

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5. HAZARDOUS WASTES

5. HAZARDOUS WASTES

GUIDELINES FOR THE APPLICATION OF SPECIAL MANAGEMENT OF SCHEDULED WASTE

GUIDELINES ON STANDARD AND SPECIFICATION OF RECOVERED WASTE OIL IN
MALAYSIA
CODE OF SCHEDULED WASTE
CONTAMINATED LAND MANAGEMENT AND CONTROL GUIDELINES NO. 1: MALAYSIAN
RECOMMENDED SITE SCREENING LEVELS FOR CONTAMINATED LAND

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5. HAZARDOUS WASTES

General Definition - Hazardous Waste refers to residue of business and/or activity containing
hazardous materials which is directly and indirectly able to contaminate and/or damage the
environment, and/or endanger environment, health, performance of human and other creatures
due to its characteristics and/or concentration.
The Railroad Commission (US) has jurisdiction over oil and gas wastes, which include all wastes
generated in association with the following activities:

drilling, operation, and plugging of wells associated with the exploration, development, or production of oil and
gas, including oil and gas wells, fluid injection wells used in enhanced recovery projects, and disposal wells;
separation and treatment of produced fluids in the field or at natural gas processing plants;
storage of crude oil before it enters a refinery;
underground storage of hydrocarbons and natural gas;
transportation of crude oil or natural gas by pipeline;
solution mining of brine; and
storage, hauling, disposal, or reclamation of wastes generated by these activities.

5. HAZARDOUS WASTES

Rustamina et al., 2009

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5. HAZARDOUS WASTES

Hazardous Wastes in Malaysia are governed by

Hazardous Substances Division

Air Division

Water & Marine Division

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6. GASEOUS EMISSIONS

In Oil and gas industry, general categories of direct emissions sources are:

Production of heat, steam, or electricity, whether for use by the company or for sale to other
parties
Combustion in flares and incinerators

Production of work by engines and turbines, for example, to drive pumps or compressors

Physical or chemical process emission such as from gas processing, oil refining, and
petrochemical manufacture

Transportation in company-owned motor vehicles and vessels, such as tank trucks and oil
tankers
Fugitive losses from equipment leaks such as from gas pipeline systems

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6. GASEOUS EMISSIONS

Three main types of gas emissions in oil and gas industry, namely;
1.
2.
3.

Combustion gases consisting of carbon dioxides and minor amounts of carbon monoxide,
nitrous oxide, N2O, SO2 and uncombusted hydrocarbons (methane and VOC)
Hydrocarbons consisting of methane and mainly aliphatic VOCs vented to atmosphere or
escaping from the hydrocarbon processes through fugitive emissions
Releases of halon and other CFC gases from fire fighting and refrigeration systems.

6. GASEOUS EMISSIONS

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6. GASEOUS EMISSIONS

The assumed effect of emitted CFC gases to the depletion of the stratospheric ozone
layer has resulted in the Montreal Protocol (1985)

The Geneva Convention through its three protocols; the Helsinki protocol (1985), the
Sofia Protocol (1988), and the Geneva Protocol (1991), signed by almost all industrial
countries in Europe and North America, imposes obligations on the signature nations
to control and reduce their emissions of SOx, NOx, and VOC.
Norway government introduced a CO2 tax in 1991. This tax is now 0.80 NOK per Sm3
(3.20 USD/1000SCF) natural gas fueled or flared. A similar tax has to be paid for diesel
fuel. (Geir & Novatech, 1994)as for effectively 1 Jan 2013, the amount increased to
0.96 NOK per Sm3 (Environmental and climate considerationsin the Norwegian
petroleum Sector, 2013) to signify the importance of good management on the
gaseous emissions.

6. GASEOUS EMISSIONS

The most commonly reported greenhouse gases are those covered by the Kyoto Protocol:
Carbon Dioxide, CO2
Methane, CH4
Nitrous Oxide, N2O
Hydrofluorocarbons, HFCs
Perfluorocarbons, PFCs
Sulfur Hexafluoride, SF6

In addition to this list, some reporting programs, such as the national inventory reporting Program of the
Intergovernmental Panel on Climate Change (IPCC), include emissions of nitrogen oxides, carbon
monoxide, and non-methane volatile organic compounds when accounting for GHG emissions.
Compounds covered by the Montreal Protocol, such as chlorofluorocarbons and hydrochlorofluorocarbons,
are also sometimes included in GHG emissions inventories. While these compounds are also GHGs, they
currently receive relatively little attention as GHGs because they either have already been or are being
phased out for most applications

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6. GASEOUS EMISSIONS

It is recommended that companies within the petroleum industry account for and report
all significant emissions of each of the six GHGs listed above that fall within their
established organizational and operational boundaries. Virtually all companies within the
industry would be expected to have emissions of CO2 and to a lesser extent CH4 and
N2O since these gases are produced through combustion.

Both CH4 and CO2 are also part of the materials processed by the industry as they are
produced, in varying quantities, from gas and oil wells. Because the quantities of N2O
produced through combustion are quite small compared to the amount of CO2
produced, CO2 and CH4 are the predominant petroleum industry GHGs.

6. GASEOUS EMISSIONS

HFCs, PFCs and SF6 while not as closely associated with the petroleum industry as other
GHGs, may be emitted by various subsectors and operations. HFCs are increasingly used
in refrigeration systems, including virtually all motor vehicle air conditioners.

Both HFCs and PFCs may be used as solvents, and PFCs are used in some fire
extinguishing systems. PFCs are also emitted during the manufacture of aluminum and in
some semi-conductor manufacturing processes.
Sulfur hexafluoride is used in high-voltage electrical equipment and in the production
and casting of magnesium.

Since none of these emitting activities are core parts of the petroleum industry, total
emissions of these gases would be expected to be small. For particular facilities or
businesses in which petroleum industry companies have an interest, however, these
kinds of emissions may be significant.

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6. GASEOUS EMISSIONS

GUIDELINE FOR THE INSTALLATION & MAINTENANCE OF CONTINUOUS EMISSION

MONITORING
SYSTEMS
(CEMS)
FOR
INDUSTRIAL
PREMISES
/FACILITIESVOLUME I
GUIDELINE FOR THE INSTALLATION & MAINTENANCE OF CONTINUOUS EMISSION
MONITORING
SYSTEMS
(CEMS)
FOR
INDUSTRIAL
PREMISES
/FACILITIESVOLUME II

6. GASEOUS EMISSIONS

A large number of alternative reduction measures were identified, assessed and analysed. These measures
were grouped into 4 categories:
a)reduction of the energy demand
b)more efficient energy generation
c)extraction of CO2 from the exhaust gases
d)conversion to an alternative energy carrier

The first categories were evaluated against state-of-the-art technology used in other industries. Gas has
traditionally been a cheap and plentiful resource on the offshore oil and gas production platforms.

Consequently energy utilization has not been optimized as well as in some other industries. The following
measures within category a. and b. were found to contain the most interesting potentials for CO2 emission
reduction;
export gas pipeline optimization
gas turbine waste heat for heating purposes
combined cycle power plants

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6. GASEOUS EMISSIONS

Extraction of CO2 from the gas turbine exhaust gas, followed by disposal in subsurface formations or in
deep sea ocean layers has been proposed by research institutes as an interesting alternative to reduce the
CO2 emissions.

The technology has the potential to almost fully eliminate the energy generated CO2 emissions from
Norwegian offshore oil and gas production. It was therefore decided to evaluate the availability and
feasibility of this technology. The study concluded that technology exists, but the energy and space
requirements are very large, showing that a new and additional CO2 removal platform will be required on
each field if the technology should be applied on existing platforms, unless significant technology
improvements take place.

Hydroelectric power supply from shore, as an alternative to gas fuel, was also investigated. Except for a few
special cases, this alternative was found to be very uneconomic compared to conventional technology.
For the two latter cases, publically available documentation was established that may assist operators in
future evaluation of these reduction measures. Furthermore, the documentation can form a basis for a
constructive dialogue with authorities and other interesting parties.

92