Gas Hydrates Challenges in Oil and

Gas Industry
Prof Bahman Tohidi
Centre for Gas Hydrate Research
Institute of Petroleum Engineering
Heriot-Watt University, Edinburgh, EH14 4AS, UK
Contact: Prof Bahman Tohidi, Tel: +44 (0)131 451 3672, Fax: +44 (0)131 451 3127,
Email: B.Tohidi@hw.ac.uk, www.pet.hw.ac.uk/research/hydrate
What Are Gas Hydrates?
Crystalline solids wherein guest
(generally gas) molecules are trapped in
f d f h d b d d cages formed from hydrogen bonded
water molecules (host)
They are formed as a result of physical
combination of water and gas molecules
Unlike inorganic hydrates (e g Unlike inorganic hydrates (e.g.,
CuSO
4
.5H
2
O) the ratio between water
and gas is not constant
Hydrogen Bonding
O
O
O
O
O
O
Hydrate Structure and Thermodynamics
The necessary conditions:
Presence of water or
ice ice
Suitably sized gas/liquid
molecules (such as C
1
,
C
2
, C
3
, C
4
, CO
2
, N
2
,
H
2
S, etc.)
Suitable temperature
and pressure conditions
P
Hydrates
No Hydrates
Temperature and pressure
conditions is a function of
gas/liquid and water
compositions.
T
y
Hydrate phase boundary
The Gas Hydrate Structures
Water molecule
Methane, ethane,
carbon dioxide.
6
cage
Propane, iso-butane,
natural gas.
5
12
5
12
6
2
5
12
6
4
Structure I
Structure II
3
16 8
2
Gas molecule
(e.g. methane)
Methane +
neohexane, methane
+ cycloheptane.
4
3
5
6
6
3
Structure H
2 1
5
12
6
8
Hydrates in Subsea/Permafrost Sediments
0
275 285 295 305 315 325 335 345 355
T/K
0
275 285 295 305 315 325 335 345 355
T/K
5
10
15
20 P
/
M
P
a
0
5
10
15
20
25
30
35
P
/
M
P
a
D
e
p
t
h
5
10
15
20 P
/
M
P
a
0
5
10
15
20
25
30
35
P
/
M
P
a
D
e
p
t
h
hydrates
no
hydrates
hydrates
25
30
35
275 285 295 305
T/K
25
30
35
275 285 295 305
T/K
hydrates
no hydrates
Zone of Gas Hydrates in Subsea
Sediments
273 283 293
Temperature / K
0
Hydrothermal
Sea Floor
D
e
p
t
h
/
M
e
t
r
e
500
1000
Hydrate Phase
Boundary
Gradient
1500
Zone of
Gas Hydrates
in Sediments
Geothermal
Gradient
The Sediments are saturated with water
Zone of Hydrates in Permafrost
273 283 293
T / K
0
263
Geothermal
Gradient in Permafrost
Depth of Permafrost
Phase
Boundary
Zone of
Gas Hydrates
in Permafrost
Geothermal
Gradient
D
e
p
t
h
/
M
e
t
r
e
500
1000
Gradient in
Permafrost
Permafrost
1500
The Sediments are saturated with water
Hydrate Formation in Porous Media
Hydrates
Water
Gas Bubble
Grains
50 Microns
Gas Hydrates in Marine Sediments
Hydrate Stability Zone in Sediments
Bottom simulating reflector at the base of hydrate stability,
Blake Ridge (after Shipley et al., 1979)
Methane Hydrate Discoveries
Methane Hydrates
Natural Gas (135)
Oil (142)
Coal (498)
Gas Hydrates (2171 for 15% recovery factor)
Future Energy Sources (10
9
TOE)
Y. Makogon SPE 77334
Carbon Balance
Hydrate Formers and Structures
Ar
Kr
N
2
4
6
(CH
2
)
3
O
C
3
H
8
sII
Hydrogen Hydrates
O
2
CH
4
Xe; H
2
S
5
CO
2
7
C
3
H
8
i-C
4
H
10
n-C
4
H
10
B
sII
sII
sII (double) CO
2
C
2
H
6
C-C
3
H
6
Benzene
Adamantane
Methyl Cyclopentane
8 Cyclo octane
sI
sII (double)
sH (double)
History of Gas Hydrates
Scientific curiosity (1810)
Hindrance to hydrocarbon production (1934) Hindrance to hydrocarbon production (1934)
Potential source of energy (1960s)
Some of the current issues:
Storage and transportation of natural gas and hydrogen, CO
2
capture
and storage, source of energy, wellbore integrity in hydrate bearing
di t b l d lid t ti l h d i d t d illi sediments, subsea landslides, potential hazard in deepwater drilling,
separation of oil and gas, global climate change
Potential gas production from hydrates (2016)
Important Properties
Capture large amounts of gas (up to 15 mole%)
Remove light components from oil and gas
Form at temperatures well above 0 C
Generally lighter than water
Need relatively large latent heat to decompose
Exclude salts and other impurities
Result from physical combination of water and gas p y g
Hydrate composition is different from the HC phase
Large amounts of methane hydrates exist in nature
Friend or Foe?
Foe
Pipeline blockage
Global climate change Global climate change
Subsea landslides
Deepwater drilling and production (hydrate formation, wellbore
integrity, casing collapse, etc)
Friend
Source of energy
Gas storage and transport Gas storage and transport
Climate change
CO
2
capture, transport, and storage
Phase change materials
Foe: Dangers to Deepwater Production
The consequences of an The consequences of an
uncontrolled gas blowout
Well Clean-up and Testing
Foe: Gas Hydrates and Seafloor Stability
S b l d lid Subsea landslides
can generate tsunamis
Foe: Gas hydrates and Seafloor Stability
Subsea Land Slides
Dissociation of
marine gas hydrates
is believed to be
responsible for huge
subsea landslides.
Some scientists Some scientists
explain the
mysteries of
Bermuda triangle
with gas hydrates.
Foe: Oil and Gas Exploitation
Drilling operation
Gas hydrates formation could cause serious operational and
safety problems. Some of the scenarios are:
Drilling operation
Long tie-backs and deepwater
production
Gas expansion and cooling
effect
Start up and shut down
Well clean-up and testing p g
Logging operation
WAG (Water Alternating Gas)
Injection
Processing
Avoiding Hydrate Problems
Water removal (De-Hydration)
Increasing the system temperature
Insulation
Hydrates
Wellhead
conditions
Insulation
Heating
Reducing the system pressure
Injection of thermodynamic inhibitors
Methanol, ethanol, glycols
Using Low Dosage Hydrate Inhibitors
Ki ti h d t i hibit (KHI)
P
r
e
s
s
u
r
e
Downstream
conditions
Kinetic hydrate inhibitors (KHI)
Anti-Agglomerants (AA)
Various combinations of the above
Cold Flow/HYDRAFLOW
No Hydrates
Temperature
Avoiding Hydrate Problems-Dehydration
Avoiding Hydrate Problems-Temperature
Hydrates
Wellhead
conditions
P
r
e
s
s
u
r
e
Reducing Heat Loss, or
Increasing Temperature
Temperature
No Hydrates
L
w
-L
HC
-H-V
Downstream
conditions
Avoiding Hydrate Problems-Pressure
No Hydrates
Hydrates
Wellhead
conditions
P
r
e
s
s
u
r
e
Reducing System Pressure
Generally not used as a
preventive measure
Only used in hydrate plug
Temperature
L
w
-L
HC
-H-V
Downstream
conditions
removal
Avoiding Hydrate Problems-Thermodynamic
Inhibitors
No Hydrates
Hydrates
Wellhead
conditions
P
r
e
s
s
u
r
eThermodynamic Inhibitor
Injection
Limitations:
- water cut
- cost (CAPEX and OPEX)
- environmental impact
Temperature
L
w
-L
HC
-H-V
Downstream
conditions
p
- flow regime
- operational difficulties
- other problems
Avoiding Hydrate Problems-Kinetic Hydrate
Inhibitors (Generally accepted view)
Hydrates
Upstream
conditions
1600
1800
2000
16
18
20
Induction Time
T &P
P
r
e
s
s
u
r
e
No Hydrates
L -L -H-V
Downstream
conditions
T
0
200
400
600
800
1000
1200
1400
1600
P
/
p
s
i
a
0
2
4
6
8
10
12
14
16
T
/
o
C
P/psia
T/C
T
min
& P
max
Temperature
No Hydrates
L
w
-L
HC
-H-V
0 500 1000 1500 2000
Time/min
Induction time should be longer than the residence time!
Test Conditions: Minimum Temperature & Maximum Pressure!!!
Avoiding Hydrate Problems-Anti-Agglomerants
Hydrates
Upstream
conditions
T &P
P
r
e
s
s
u
r
e
Downstream
conditions
T
T
min
& P
max
Temperature
No Hydrates
L
w
-L
HC
-H-V
190
200
210
45
50
50
60
P
T
torque
Avoiding Hydrate Problems-Anti-Agglomerants
P
/
b
a
r
80
90
100
110
120
130
140
150
160
170
180
T
/
o
C
5
10
15
20
25
30
35
40
T
o
r
q
u
e
/
N
.
c
m
10
20
30
40
50 torque
t i m e/h r .
0 2 4 6 8 10 12 14 16 18 20 22 24 26 28 30
P
/b
a
r
70
80
90
100
110
120
130
140
150
160
170
180
190
200
210
T
/ o
C
0
5
10
15
20
25
30
35
40
45
50
T
o
r
q
u
e
/N
.c
m
0
10
20
30
40
50
60
P
T
torque
Water/condensate/gas system (30% water) with 1% AA.
Hydrate formation, but very little increase in torque.
t i me/h r .
0 2 4 6 8 10 12 14 16 18 20
70
80
0 0
New Approaches in Preventing Gas
Hydrate Problems: Cold Flow
No heating
No insulation
All i / ti h d t f ti b t ti Allowing/promoting hydrate formation, but preventing
their agglomeration
Providing seeds
Using Anti-Agglomerants
Natural inhibitors
Mechanical means
A combination of the above
Several Institutions are working on Cold Flow
SINTEF-BP
CSIRO/IFP
ExxonMobil
Heriot-Watt (HydraFlow)
Heriot-Watt HYDRAFLOW: Concept
Convert all or most of the vapour phase into hydrates
(add water if necessary)
Prevent hydrate blockage by AA and/or natural Prevent hydrate blockage by AA and/or natural
inhibitors and/or mechanism of hydrate formation
Transport hydrates as slurry
Separate some of the free liquid phase (and chemicals)
and recycle (Loop Concept)
Dissociate hydrates and recover the gas/hydrocarbon Dissociate hydrates and recover the gas/hydrocarbon
(or transport the gas in the form of hydrates, e.g., dry,
hydrates in water or hydrates in oil slurries)
HYDRAFLOW: Loop Concept
Circulating liquid phase plays the role of
carrier fluid
Gas from Well-1 is converted into
hydrates
The same process will continue for other
wells
Hydrate slurry is transported to the host
facilities
Hydrates, oil and some water are
separated separated
A suitable fluid mixture is re-circulated
using a single phase pumpon the host
facilities
HYDRAFLOW: Potential Benefits
Reducing/eliminating
Gas hydrate risks
Slugging
Wax
Pipeline pigging requirement
Reducing pipeline costs
Bare pipes, no heating
No need for subsea and/or multi-phase pumps
New Approaches: Hydrate Safety Margin
Monitoring and Early Detection Systems
Hydrate Safety Margin
Monitoring
Determining the actual amount of salt and
e
Wellhead
conditions
Over
inhibited
Under
inhibited
g
inhibitor (Methanol, Glycol, Ethanol, KHI,
and AA) from downstream measurement
Eliminating/reducing risk of human error or
equipment malfunction
Automation, adjusting the inhibitor
injection rates
Detecting Early Signs of Hydrate
Formation
P
r
e
s
s
u
r
e
No Hydrates
Temperature
Downstream
conditions
Formation
For most systems the initial hydrate
formation may not result in pipeline
blockage
Detecting the early signs of hydrate
formation could result in reducing gas
hydrate blockage risks
Hydrate risk
Low safety margin
Safe/optimised
Over inhibited
Blockage Removal
It is not possible to prescribe a general procedure for hydrate
blockage removal, as each case needs to be investigated
carefully by a multi-disciplinary team carefully by a multi-disciplinary team
Gas hydrate blockage in the pipeline has some differences with
in-situ hydrates.
They are initially porous and permeable unlike in-situ hydrates
They may transfer pressure but limited in the transfer of flow
During their formation some free water have been trapped
between hydrate crystals
Natural Gas-Water
t = 31 hrs, P=54.9 bar, T=3.4 C
t = 94 hrs, P=53.0 bar, T=3.2 C
t = 142 hrs, P=52.1 bar, T=3.2 C t=142 hrs, P=52.1 bar, T=3.2 C
Blockage Removal Through Heating
The objective is
to move the
Hydrates
system outside
hydrate stability
zone.
The system could
be in L -H-V or H-
P
r
e
s
s
u
r
e
Initial
conditions
Final
conditions
be in L
w
-H-V or H-
V equilibria.
Temperature
No Hydrates
L
w
-H-V
Blockage Removal Through Heating
It is often difficult to locate a
pipeline hydrate plug to begin
heating
Hydrates
heating.
Heat must be supplied with caution,
beginning from the end and
progressing toward the middle of
the plug.
If a hydrate plug is dissociated in
P
r
e
s
s
u
r
e
No Hydrates
L
w
-H-V
Initial
conditions
Final
conditions
y p g
the middle, the pressure might
increase suddenly, resulting in
equipment failure, blowouts, or
hydrate projectiles in pipelines.
Temperature
No Hydrates
Blockage Removal Through Depressurisation
The objective is to move the
system outside the hydrate stability
zone
Hydrates
L
w
-H-V
zone.
A common misconception is that
depressurisation alone can cause
hydrate dissociation, forgetting
about the role of latent heat of
dissociation.
When the system is
P
r
e
s
s
u
r
e
No Hydrates
Initial
conditions
Final
diti
y
depressurised, some hydrates
remove heat from surrounding and
dissociate, resulting in a reduction
in the system temperature.
Temperature
conditions
273
Blockage Removal Through Depressurisation
The thermal gradient will result in
heat flow through pipe-wall.
Hydrates
L
w
-H-V
Initial
The system temperature could drop
to below zero and ice could form.
The second misconception is that
during depressurisation, the hydrate
plug dissociate at its end(s).
P
r
e
s
s
u
r
e
No Hydrates
Initial
conditions
Final
conditions
p g ( )
In fact although the initial plug
dissociation is at its ends, the hydrate
plug will dissociate radially resulting in
plug dislodge.
Temperature
273
Blockage Removal Through Depressurisation
Q
Hydrate Plug Pipe-Wall
Q
Depressurisation from both ends
projectile
ice formation
The problem with ice formation
low heat transfer
protective layer
ice will dissociate on temperature rise not pressure
reduction
Blockage Removal Through Inhibitor Injection
Inhibitor injection will shift the hydrate phase
boundary to the left, which could result in gas
hydrate dissociation.
However, gas hydrate dissociation will produce
fresh water reducing the concentration of the
inhibitor.
Also gas hydrate dissociation will result in the
release of gas (possible pressure increase) and a
reduction in system temperature.
Blockage Removal Through Inhibitor Injection
Initial
Inhibitor
P
r
e
s
s
u
r
e
Hydrates
Inhibitor
Injection
Dilution
Initial
Hydrate
Phase
Temperature
No Hydrates
L
w
-H-V
Boundary
Case Studies
Hydrates in Gas Lift
Hydrates in Water Injection Lines Hydrates in Water Injection Lines
Hydrates in Onshore Natural Gas Production
Pipeline blockage in the North Sea
Hydrate problem during logging operation
Pipeline blockage after an emergency shut-down
Hydrate problems in GOM
Summary
Gas hydrates are formed as a result of physical combination
of water and suitably sized molecules
There are huge amounts of methane hydrates in subsea There are huge amounts of methane hydrates in subsea
sediments and permafrost regions
They have very interesting properties, with many potential
industrial applications
They had significant impact on the past climate
They have been (and are) a nuisance to oil and gas They have been (and are) a nuisance to oil and gas
industries, in particular in offshore and deepwater operation
Novel technologies/techniques are necessary for addressing
gas hydrate challenges in deepwater and long tiebacks
Contact: Prof Bahman Tohidi, Tel: +44 (0)131 451 3672, Fax: +44 (0)131 451 3127,
Email: B.Tohidi@hw.ac.uk, www.pet.hw.ac.uk/research/hydrate
Gas Hydrate, Flow Assurance and PVT
Research Activities at Heriot-Watt
Contact:
Professor Bahman Tohidi
Director, Centre for Gas Hydrate Research
Institute of Petroleum Engineering
Heriot-Watt University
Edinburgh EH14 4AS, UK
Direct Line: +44 (0)131 451 3672
Fax: +44 (0)131 451 3127
Mobile: +44 (0)776 116 5784
Email: Bahman.Tohidi@pet.hw.ac.uk
http://www.pet.hw.ac.uk/research/hydrate
CENTRE
FOR GAS
HYDRATE
RESEARCH
Gas hydrates in gas, water and gas water interface, as
viewed through the High Pressure Micromodel
Introduction
Heriot-Watt University is a medium size university in
Edinburgh (Capital of Scotland) with some 6,000
students
Institute of Petroleum Engineering (IPE) was form in
1975 and has some 200 MSc, MPhil and PhD students
Some 70% of the IPE income is from research projects
There several big research groups; such as; Hydrates,
Scale, Geophysics, Uncertainty, etc ----
Background and Areas of Activities
Background
PVT and Phase Behaviour of Petroleum Reservoir Fluids
research started in 1978 research started in 1978
Gas hydrate research started in 1986
Centre for Gas Hydrate Research Established in Feb 2001
Centre for Flow Assurance Research (C-FAR) started in 2007
Areas of Activities
Research Research
Consultancy, mostly through Hydrafact (www.hydrafact.com)
Training (open and in-house courses)
Research Interests
PVT and Phase Behaviour of
Reservoir Fluids
Flow Assurance
Gas Hydrates
Wax
Salt (halite)
Asphaltene
Gas Hydrates
P
r
e
s
s
u
r
eHydrates
Wellhead
conditions
Hydrates could block subsea pipelines
Gas Hydrates
Flow Assurance
Gas Hydrates in Sediments
Positive/other Applications of Gas
Hydrates
P
No Hydrates
Temperature
Downstream
conditions
P & T profile and hydrate phase boundary
HYDRAFACT Ltd
HYDRAtes and Flow Assurance Consulting and Technologies
Construction of equipment
Training/short courses Training/short courses
Consultancy
Software (HydraFLASH)
Commercialising novel technologies, e.g.,
Hydrate monitoring and early warning systems Hydrate monitoring and early warning systems
(HydraCHEK)
Software (HydraFLASH)
HYDRAFLOW
www.hydrafact.com
Current J oint Industry Projects
Evaluation of Low Dosage Hydrate Inhibitors
Kinetic Hydrate Inhibitor and Anti-Agglomerant Evaluation
Major new discoveries in the process commercialising the new Major new discoveries, in the process commercialising the new
methodology by Hydrafact (www.hydrafact.com)
One patent has already been filed
Hydrate Monitoring and Early Warning System
A number of techniques and prototypes have been developed for
monitoring the hydrate safety margin. Two patents have been
filed. One of the devices (HydraCHEK) is being commercialised by filed. One of the devices (HydraCHEK) is being commercialised by
Hydrafact
A number of techniques have been developed for hydrate early
warning. A patent application has been filed
Organising a field trial
Current J oint Industry Projects
Gas Hydrates and Flow Assurance
Thermodynamics aspects of hydrates, inhibitor distribution, water content,
salting-out, wax, etc
Solid-liquid equilibria in various glycol-water systems
The developed software (HydraFLASH) is ranked the best by Total and it
is being commercialised by Hydrafact
One patent is being filed
Hydraflow: A Wet Cold Flow Solution
Converting most of the gas into hydrates and transporting them as slurry
(hydrates, slugging, wax, downhill pressure recovery, reduction in ( y gg g p y
volumetric flow rate)
A high pressure flowloop has been constructed as well as a unique set of
test facilities.
A patent has been filed which will be commercialised by Hydrafact
Current J oint Industry Projects
PVT and Phase Behaviour of Reservoir Fluids
The lab has been refurbished and equipped with two major Hg-free
equipment (200 C and 15,000 psia) have been purchased
The HPHT (250 C and 30,000 psia) facilities is being equipped with a
salt compatible cell (viscosity, density, three phase IFT)
Slim tube is being added to the existing capabilities
Some of the topics in the current phase of the project: Viscosity (effect of
mud filtrate contamination), IFT at HPHT, Acoustic Characteristics of
Reservoir Fluids, Phase Behaviour of CO
2
-Oil systems, Maximum Carbon
Number in GC Analysis, etc
I f A i A id G I j i Impact of Aromatics on Acid Gas Injection
Project sponsored by the Gas Processing Association
Joint project with Paris School of Mines
Cross-over project between hydrates and PVT project
Current J oint Industry Projects
Impact of Common Impurities on Carbon Dioxide
Capture, Transport and Storage
CO
2
originating from capture processes is generally not
pure and can contain impurities such as:
H
2
O, CH
4
, N
2
, H
2
, NOx, H
2
S, SO
2

The main aim of the proposed project is to investigate the phase

behaviour and properties of CO
2
-rich stream containing impurities
Phase behaviour of Saline water and CO
2
-rich streams
Other Projects
Towards Zero Carbon Emissions: Novel Low
Pressure Molecular Natural Gas/CO
2
/H
2
Storage and Separation using Semi-Clathrates, Storage and Separation using Semi Clathrates,
EPSRC
One patent has been filed
Quantifying and monitoring potential ecosystem
impacts of geological carbon storage, NERC
We are part of a large consortium
Our work is looking into movement of CO in subsea
Hydrates in sediments
Methane hydrate formation
in high pressure glass
micromodel
Our work is looking into movement of CO
2
in subsea
sediments
Analysis of existing oceanographic and seismic
data
Our work is on effect of hydrates on sediment
properties
Resources
Staff/Students
25 member research team with expertise in Chemical,
Mechanical, Electronic and Petroleum Engineering, g g
Geology/Geochemistry, Physics/Geophysics,
Chemistry, Radio-Physics, Polymer with more than 10
nationalities.
Experimental Facilities
More than 40 versatile experimental rigs, operating
from -80
o
C to +350
o
C and pressures up to 2,000 bar
Flow loop (1 dia, 40 m long, 200 bar, Moineau pump) ( g )
in an environmental chamber (-15 to + 20 C)
Software
Comprehensive phase behaviour and hydrate
programme, commercial and research versions
Database
Wax predictive model
Some of the experimental facilities