Controlling Hydrate Formation in

Production Lines

Amadeu K. Sum
Associate Professor, Chemical & Biological Engineering

March 23, 2015

JEM 2015 - EBEM

Campinas, SP - BRASIL
 Hydrocarbon Production System
Flow Assurance*: Term used to
describe the design, engineering, and
management for transport of multiphase Separation of
oil/gas/water
fluids in a reliable and stable process.
Gathering Station /
Flow Station
Platform

Depth:
1000s
Production
meters Pipeline(s)
Subsea
Wellhead Separation
Production
Manifold
Flowline

Seafloor temperature 4 C

Produce
Pipeline: 10s km
oil/gas/water
Oil: 6-8 inch
Gas: 10+ inch

*Coined by Petrobras in the early 1990s as Garantia de Escoamento

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Hydrates in Flow Assurance

Hydrate formation in
oil/gas flow lines
#1 problem in flow
assurance (more
severe than wax,
asphaltene, corrosion)

Costly to prevent
($100sM per year)
Costly to remove
(lost production)

Safety concern
Hydrate plug removed from oil pipeline
(pressure buildup)

3
Burning Hydrate

4
Hydrates Fundamentals
gas High P crystal structure
+ +
water Low T

water cages Burning

hydrate

Typical hydrate forming gases:

1 m3 0.9 m3 Methane Nitrogen
Hydrate ~164 m3 Water
Ethane Hydrogen
Gas
Propane Xenon
at STP + Carbon Dioxide Acetone

5
Hydrate Structures and Building Blocks

512 51262 51264 4 35 66 3 51268

(20 H2O) (24 H2O) (28 H2O) (20 H2O) (36 H2O)

Structure I Structure II Structure H

2(512) + 6(51262) / 46 H2O 16(512) + 8(51264) / 136 H2O 3(512) + 2(435663) + 1(51268) / 136 H2O

At least 82% water Inclusion, crystalline compounds

One small molecules per cage Non-stoichiometric compounds

6
Depth and Breadth of Hydrate Research

7
Hydrates in Flow Assurance
flowline
A B
wellhead platform

SPECIFIED CONSTRAINTS DESIRED

Fluid composition Producing

and properties Field topology and conditions fluids
Phase fractions
Thermo conditions Maximize flow
Flow rate NEED TO KNOW Minimize P
Flow regime
Temperature/Pressure profile
Phases distribution, entrainment, emulsification
Hydrate avoidance/management
Hydrate amount, distribution
Hydrate remediation

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Hydrates in Flow Assurance
Are hydrates a problem?

Wellhead

Platform

9
Hydrate Control Approaches
Hydrate Avoidance Hydrate Management
(no entry in hydrate domain) (operate with risk in hydrate domain)

Hydrate Hydrate
Domain Domain
Pressure

Pressure
Hydrate Hydrate
Free Free
Temperature Temperature

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 Hydrate Management Strategies

Thermal Chemical Hydraulic Process No Control

Fluid Gas Operation

Insulation MeOH/EtOH
displacement dehydration within
hydrate
Water cut domain
DEH Glycols Gas sweep
reduction
Natural
LDHI Depressuriz- hydrate
Bundles transport-
(AA, KHI) ation
ability

Heat tracing Salts Compression

Natural
kinetic
inhibition
Dense phase

Modified from K. Kinnari (Statoil)

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 Hydrate Management Strategies

Thermal Chemical Hydraulic Process No Control

Fluid Gas Operation

Insulation MeOH/EtOH
displacement dehydration within
hydrate
Risk based approach Water cut domain
DEH Glycols Gas sweep
reduction
Sound engineering practice/design Natural
LDHI Depressuriza hydrate
Bundles
Understand effect of water and hydrates
(AA, KHI) tion transport-
ability

Heat tracing
in production
Salts
system
Compression
Natural
Need to combine field experience with kinetic
inhibition
Dense phase
laboratory research

Modified from K. Kinnari (Statoil)

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 Hydrates in Flow Assurance
Hydrate Avoidance (inhibitor injection)
Determine hydrate phase stability boundary

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Typical Hydrate Phase Diagram
Hydrates are a mixture by definition,
but their phase behavior is the same as a simple component

Lw-H-LHC
Lw-LHC
H-LHC
Lw-H
I-Lw-H

H-V-LHC
Q2
Pressure

Pressure
Lw-H
I-H

I-Lw-H
I-H

Q1 Lw-V Q1 Lw-V
I-Lw-V

I-Lw-V
I-V I-V

Temperature Temperature

Quadruple point Q1 Quadruple point Q2

I-Lw-H-V Lw-H-V-LHC

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Gibbs Phase Rule

F=CP+2

F: degrees of freedom (intensive variable)

C: number of components
P: number of phases

Example:
2 components, 2 phases :: F = 2
4 components, 3 phases :: F = 3

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Typical Hydrate Phase Diagram
Methane+Propane Mixture

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Hydrate Avoidance: Inhibitor Injection
Most common THI (thermodynamic Hydrate Inhibitor):
Methanol (MeOH), Ethanol (EtOH), Monoethylene glycol (MEG)

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Hydrate Avoidance: Inhibitor Injection
Most common THI (thermodynamic Hydrate Inhibitor):
Methanol (MeOH), Ethanol (EtOH), Monoethylene glycol (MEG)

18
Hydrate Avoidance: PAST to PRESENT

Focus on hydrate phase equilibrium boundary

Under which conditions will hydrates form?

If hydrates can form, how can they be inhibited?

Thermodynamic hydrate inhibitions (methanol, MEG)

Insulation

Direct Electrical Heating

Hydrate Avoidance works!

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Hydrates in FA: PRESENT to FUTURE

Impractical ($$ and logistic) to completely avoid hydrates

Must live with hydrates
Management of hydrates
chemical treatment
monitoring
remediation

Must have good knowledge of

how, when, where, how much
hydrates are formed

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Hydrate Management
Hydrate Remediation
How to safely remove a hydrate plug

Need to establish pressure communication in the flowline

Two-side depressurization
One-side depressurization
Electrical heating
Coil tubing
Chemical treatment

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Heat of Formation/Dissociation (Hd)
Latent heat of transformation for hydrates
Formation: exothermic
Dissociation: endothermic
Must input heat to remove hydrate plug in pipelines!

Latent heat depends upon guest and occupancy

HL+G
CH4: 54.2 kJ/mol
C 2H 6: 71.8 kJ/mol
C 3H 8: 129.2 kJ/mol

Values are per mole of guest

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Hydrate Management
Hydrate Remediation

after 1 hrs after 2 hrs after 3 hrs

Hydrate plug dissociation is predominantly radial, as opposed axial

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Hydrate Management
Hydrate Remediation
Hydrate plug dissociation/removal

Free Free
water water
Hydrate Hydrate Ice layer
core core (if T < 0C)
Pipe wall Pipe wall
(Tambient) (Tambient)

Partial dissociation (create annulus)

Allow for pressure communication and chemical treatment

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Hydrate Management
Hydrate Remediation
Need to determine plug location and displacement

Pup Hydrate
Ffriction FP
plug
Pdown

Lup Ldown

If plug dislodges, how far/

fast will it travel?
Can the pipeline burst?

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Hydrate Management
Model Hydrates in Multiphase Flow
Gas, Oil, Water (free, emulsified, dispersed)
Entrainment Hydrate Growth Agglomeration Plugging

Gas

Oil

Water

Emulsification/ Growth Co/Ad-hesion Deposition

Dispersion
Jamming/
Nucleation Rheology Aggregation
Bedding

Must account for each phenomenon combined with

multiphase flow

26
Hydrate Management
Model Hydrates in Multiphase Flow
Gas, Oil, Water (free, emulsified, dispersed)
Entrainment Hydrate Growth Agglomeration Plugging

Gas

Oil

Water

Emulsification/ Growth Co/Ad-hesion Deposition

Dispersion
Jamming/
Nucleation Rheology Aggregation
Bedding

Must account for each phenomenon combined with

multiphase flow

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Hydrate Grows at the Interface

Hydrate growth on
water droplet in
contact with another
hydrate particle
(CyC5 hydrate)

28
Hydrate Growth at Interfaces
Formation in the bulk

saturated oil water water

water saturated gas

oil

hydrate hydrate hydrate

Formation on the wall/surface

saturated oil gas

hydrate

water hydrate
surface surface

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Hydrate Formation Rate
gas gas gas
Induction time: metastable system

hydrate Growth can be limited by:

water water water Intrinsic growth kinetics
(limited by rate of formation/
driving force)
Mass transfer (limited by contact
of gas and water)
Heat transfer (limited by removal
of heat from system)

CH4 solubility in water: ~ 1:4000

CH4 in hydrate: ~ 1:6

CH4 hydrate Hf = +54.2 kJ/mol

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Hydrate Management
Model Hydrates in Multiphase Flow
Gas, Oil, Water (free, emulsified, dispersed)
Entrainment Hydrate Growth Agglomeration Plugging

Gas

Oil

Water

Emulsification/ Growth Co/Ad-hesion Deposition

Dispersion
Jamming/
Nucleation Rheology Aggregation
Bedding

Preventing agglomeration is key to avoid plugging

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Hydrate Interfacial Interactions

Natural oil chemistry

Injection of LDHIs (AA/KHI)
Hydrate: oil-wet (dispersed in oil) or
water-wet (dispersed in water, may
attach to wall)

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Crude Oil Prevents Water from Jumping
onto Hydrate Particle

500 m 500 m

Hydrate-Water Droplet in Pure Hydrate-Water Droplet in

Cyclopentane (2.7C) 5 wt% crude oil (2.7C)
Video begins after 1 minute; Video begins after 30 minutes;
spans 5 minutes spans 15 minutes

After 45 minutes of contact, NO adhesion with crude oil

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 Cohesion Force for Hydrate Particles
16
Experimental temp. = 1C

14 D
Cohesive Force [mN/m]

3.5wt.%
12 NaCl (A)
2wt.% 400 m
3 hours
Ethanol (B)
10
2wt.%
Methanol (B)
8 2wt.%
Pure MEG (A)
6 CyC5 1wt.%
D
NaCl (A)
4
15 min. 400 m
1 hour
2
0 1 2 3

Time [Hours]
Measurements performed in the Micromechanical Force Apparatus
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 Interfacial Properties of Hydrate Particles
Physical and Chemical Interfacial Properties
6
200 m 200 m
Mineral

Normalized Cohesion Force (mN/m)

5 Oil

4 1 wt%
Fiber Unconverted Span80
water
Upper 3
particle
1 wt%
PPG
Water Hydrates 2
0.6 wt%
bridge Nap. Acid
1.3 wt%
1 Caratinga
Lower
particle
0

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Hydrate Agglomerate Diameter - dA
Force balance between inter-particle and shear forces

2 dA - hydrate agglomerate diameter

( ! $
3 f +
dA dP - hydrate particle diameter
4 f
Fa *1 # & -
! dA $ *) max " dP % -,
- hydrate particle volume fraction
# & =0
" dP % ( ! dA $
3 f + max - maximum packing fraction (= 4/7)
dP 0! *1 # & -
2
f - fractal dimension
*) " dP % -,
Fa - interparticle force (Fa/R = 50 mN/m)
0 - oil viscosity
- shear rate

Solve for dA - hydrate agglomerate diameter

(Camargo and Palermo, 2002)

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Effective Hydrate Volume Fraction
Particle volume fraction + entrapped fluid fraction

( 3 f ) dA
d A
eff =
d P dP

dA - hydrate agglomerate diameter

dP - hydrate particle diameter
- hydrate particle volume fraction
f - fractal dimension

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 Relative Viscosity
Relative viscosity between oil and hydrate slurry
Relative viscosity is a function of
particle volume fraction and size
attractive force, shear rate, and viscosity

1 eff
r = 2
- effective particle volume fraction
eff max - maximum packing fraction (= 4/7)
1 r - relative viscosity
max

(Mills, P. J., de Physique Letters, 1985)

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Hydrate Management
Chemical injection of Low Dosage Hydrate Inhibitors (LDHIs)

Anti-Agglomerants (AAs)
Used in oil systems
Effective for low water cut system (< ~40%)
Quaternary ammonium salts
Used in low concentration, ~1-2 wt%
Convert all (most) water to hydrate
Prevent hydrate particles from agglomerating
Good for high temperature, shut-in and restart of line
Significant environmental concerns on disposal

39
Anti-Agglomerant in Pipeline

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Hydrate Management
Chemical injection of Low Dosage Hydrate Inhibitors (LDHIs)

Kinetic Hydrate Inhibitors (KHIs)

Water soluble chemicals
Used in oil and gas systems
Used in low concentration, ~1-2 wt%
Allow initial hydrate crystal to form, prevent growth
Limited to low subcooling (T < ~10 C)
Not for shut-in and restart operation
Significant environmental concerns on disposal, water
quality

41
Chemical Structures for Some KHIs

Mechanism for how these

KHIs work is unknown

42
Hydrate Formation and Subcooling
System need to be subcooled
for hydrates to form
(metastability due to liquid-
solid transition)
subcooling
KHIs tend to extend time
system stay in metastable
conditions

Mechanism hypothesis: KHI

adsorbs on crystal surface

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 Hydrate Management for Shut-in/Restart

Steady state flow

(dispersed water droplets)

Unstable emulsion No-Touch time Stable emulsion

Free water formation

Coalescence
Within hydrate stability zone

Thin shells

Free water
Larger water droplets
with thin hydrate shell
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Hydrate Management for Shut-in/Restart
Oil Phase separation after long shut-in
Thin hydrate layer Thin hydrate layer on the free water
Very slow process (no shear)
Water

Free gas Systematic opening of valve

bubbles
Introduction of gas bubbles from well
Occluded Rapid formation of hydrates
water

Free water conversion to hydrates

Gas bubbles conversion to hydrates
Rapid plug formation before hot fluids
Hydrate Plug
from wellhead reach the plug location

45
45
45
Hydrate Management
Model Hydrates in Multiphase Flow
Gas, Oil, Water (free, emulsified, dispersed)
Entrainment Hydrate Growth Agglomeration Plugging

Gas

Oil

Water

Emulsification/ Growth Co/Ad-hesion Deposition

Dispersion
Jamming/
Nucleation Rheology Aggregation
Bedding

46
Hydrate Deposition (Gas systems)
Gas / Gas Condensate (no free water)
Buildup Annulus Growth Sloughing Plugging

Gas

Condensate

Deposition on
Initial surfaces occurs
slowly over long
periods of time
Porous Deposit

CH4 Hydrate in a gas-saturated systems Annealed Deposit

at 100 bar (cold surface at 0.5 C)
47
Hydrate Deposition from Gas Phase

CH4 vapor saturated with water (no free water) at 30C

P = 100 bar, Tcold = 0.5C

1 inch

Condensed water immediately converted to hydrates

Porous hydrate anneals to become hard deposit

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Hydrate Deposition from Gas Phase

How to prevent/minimize hydrate deposition on

surfaces?
Remove all water from gas (near impossible)
Keep surface warm (insulation, heating)
Coat inside surface (hydrophobic coating)
Periodically scrap surface (pigging)

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 Conceptual Model for Hydrates in
Multiphase Flow

Gas, Oil, Water (W/O and O/W Emulsions, Free)

Entrainment Hydrate Growth Agglomeration Plugging

Gas

Oil

Water

Emulsification Growth Co/Ad-hesion Deposition

Nucleation Rheology Aggregation Jamming

Each phenomenon studied separately

50
Particle Jamming in Flowing Systems

Three Ingredients:
Dense particle flow
Flow restriction
do/dp = R is small

Variables:
Particle size/shape
Restriction size/shape
Fluid velocity
Stable 2D Arch Stable 3D Dome Particle concentration

51
Particle Jamming in Flowing Systems
Jamming Probability Map

(High jamming
risk)

5
(Low jamming
t = 19 s risk)

4
t = 11 s
Restriction P (psi)

3
Particle
No Particles
Accumulation Jamming

2 Survival Probability
Z

1
t = 22 s ln [S( )] = d
0

0
0 5 10 15 20 25 30 Jamming in any
Time (s) geometry
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Hydrate Management
Model Hydrates in Multiphase Flow
Gas, Oil, Water (free, emulsified, dispersed)
Entrainment Hydrate Growth Agglomeration Plugging

Gas

Oil

Water

Emulsification/ Growth Co/Ad-hesion Deposition

Dispersion
Jamming/
Nucleation Rheology Aggregation
Bedding
Each phenomenon studied separately
Multiphase flow & hydrate formation are interdependent

53
Multiphase Flow & Hydrate Interdependence
Slug

Water
Gas
Gas

Oil
Water

Water
Gas Hydrates
Gas

Oil
Water

Hydrate formation = f(LL, WC, mixture velocity, T, P)

CSMFlow: incorporates flow regime in calculations
Effort to understand multiphase flow and its effect on hydrate
formation (and vice-versa)
54
Multiphase Flow & Hydrate Interdependence

Liquid
Hold-up

Distance

Flow characteristics: hold-up, slug length, slug frequency, P

55
Multiphase Flow & Hydrate Interdependence

Liquid
Hold-up

Hydrate

Distance

Flow characteristics: hold-up, slug length, slug frequency, P

56
Fundamental Multiphase Flow Concepts

UG AG, HG
USG

USL
UL
AL, HL

Hold-up: Qi
Ai
Superficial Velocity: USi =
Hi = Apipe
Apipe
USi
Linear Velocity: Ui =
Hi
where i stands for phase (L, G or Hyd)

57
Fundamental Multiphase Flow Concepts

UG AG, HG
USG

USL
UL
AL, HL

Phases hold-up: HG + HL = 1

Mixture velocity: UM = USG + USL

Slip Velocity: US (G-L) = UG UL

58
Fundamental Multiphase Flow Concepts

UG AG, HG
USG
Uhyd Hhyd
USL
UL
AL, HL

Phases hold-up: +1
HG + HL = Hhyd = 1

Mixture velocity: UM = USG + USL + UShyd

Slip Velocity: US (G-L) = UG UL

US (L-hyd) = UL Uhyd
59
Determining Flow Regime and Transitions
F (H L ) = U S H L2 + (U M U S )H L U SL (
F ' (H L ) = U S H L2 + U M
'
) '
U S H L U SL

60
CSMFlow: Unique Tool for Multiphase Flow
Air-Water system (Shoham, 1984)

61
CSMFlow: Unique Tool for Multiphase Flow
Air-Water system (Shoham, 1984)

Slug
Slug Length Distribution
Elongated Bubble
Slug Length Distribution

lognormal
distribution
narrow, skewed
distribution

62
CSMFlow: Unique Tool for Multiphase Flow
Air-Water system (Shoham, 1984)

Slug

Slug Count
Elongated Bubble

Slug Count
Hydrates

Hydrates
No Hydrates

No Hydrates

Consider presence of
hydrates
63
CSMFlow: Unique Tool for Multiphase Flow
Air-Water system (Shoham, 1984)

Slug

No Hydrates
Elongated Bubble

No Hydrates

Hydrates

Hydrates

Hydrates induce changes in

slugging characteristics
64
CSMFlow: Unique Tool for Multiphase Flow
Hydrate Fraction Plays Important Role in Flow Behavior
Slug Count Slug Length Distribution

20% hydrates
20% hydrates

10% hydrates

10% hydrates
5% hydrates

5% hydrates

Can we infer hydrate formation from slugging characteristics?

65
Summary

Hydrate avoidance works! Past, Present and

Future
Hydrate management: live with hydrates
Must know the risk of hydrate formation and
plugging
More challenging production conditions:
much to learn about hydrates

66
THANK YOU!

Questions???

Contact: asum@mines.edu

67