Ahmed Abdala

May 18, 2016

Lecture contents

What is a hydrate?

Kidnay 8.3, GPSA 20-9

The contradiction of hydrocarbon hydrates

Conditions for hydrate formation

Kidnay 8.3.2, GPSA 20-13

Prevention of hydrate formation

Kidnay 8.3.3, GPSA 20-1

Gas Hydrates
Ice-like crystalline molecular complexes
Mixture of water and suitably sized 'guest' gas
molecules

The water (host) molecules, upon hydrogen bonding, form

lattice structure (cage) with several interstitial cavities
The guest gas molecules can occupy the lattice cavities
When a minimum number of cavities are filled, the
crystalline structure will become stable

Solid gas hydrates will form, even at temperatures

well above the freezing point of water to ice
When gas hydrates dissociate (melt)

The crystalline lattice breaks down into

water and gas is released

http://www.pet.hw.ac.uk/research/hydrate/hydrates_what.cfm

Hydrate Structure

Hydrate structure depend on the guest gas (hydrate forming gas)

Methane, ethane, propane, isobutene, CO2, H2S, mixture of methane and neohexane or methane and
cyclopentatne

The cage is formed by water molecules arranged in structure with number of rectangular,
pentagon, or hexagon faces, or combination of them
The hydrate crystal consists of minimum number of cages

Structure I
Structure II
Structure H

Gas hydrate dichotomy

Asset
Energy Source
Dense energy storage

Solution
Desalination
CO2 capture

Trouble making

Plugging of pipelines and equipment

Gas hydrates as energy source

http://feel.postech.ac.kr/research/gas_hydrate/

Methane hydrate exists on the

sea floor (deep ocean) or
under the permafrost layer of
arctic
Carbon reserve in methane
hydrates is equivalent to all
other carbon sources
Currently no proven
technology for recovery
Risk of sudden (uncontrolled)
release of methane, global
warming effect
Sea floor stability upon release
of methane
https://www.youtube.com/watch?v=U46XOoU0DrM

https://www.youtube.com/watch?t=110&v=HTNcv_LGh38
6

Location of methane hydrate deposits

https://www.youtube.com/watch?t=110&v=HTNcv_LGh38

https://www.youtube.com/watch?v=U46XOoU0DrM

Ayhan Demirbas, Methane Gas Hydrate, Green

Eenergy and Technology Series, Springer, 2010

Hydrates for acid gas removal and seawater desalination

CO2 capture
Desalination
Acid gas removal

http://feel.postech.ac.kr/research/gas_hydrate/

Robert W. Bradshaw, et al, Desalination Utilizing Clathrate Hydrates, (LDRD Final Report), Sandia Lab, 2008
8

Hydrate Problems

Hydrates may plug gathering line transporting

water-saturated gas from well-head to central
treating station if temperature drops below
hydrate formation temperature

Temperature could drop due to

J-T effect at the wellhead
Heat loss from flow lines

Hydrate Formation: Conditions and Problems

Hydrate
formation
conditions

Presence of free or
liquid water (T< dew
point)
Low temperature
High pressure

Hydrate
formation
acceleration

Agitation (turbulence)
Pressure pulsations
Hydrate crystals (seeds)
Suitable sites for crystal
formation

Operational
problems

Complete or partial
blocking of flow line
Fouling and plugging of
heat exchangers
Erosion of expanders

10

Prediction of Hydrate Formation Conditions

The conditions (T, P) at which hydrates could

form depends on the gas composition
It can be estimated by several methods:

Sweet Gas

Sour gas with low CO2 and H2S concentration

GPSA charts, experimental

Katz gas-gravity method
Katz equilibrium constant method

Sour Gas

Baillie and Wicherts charts for sour gas

Equation-of-state approaches

11

GPSA Chart: Experimental Method

For Sweet Gas
Pure components C1, C2,
and C3 and C2/C3
mixture (70/30)
To the left and above each
curve is the hydrate
formation zone
Larger gases are easier to
form hydrates (lower
pressure or higher
temperature) compared
to small gases

12

Katz Gas-gravity Method

The hydrate formation

temperature or
pressure is red from
one graph using the gas
specific gravity

Simple method
Good for natural gas
with SG of 0.7 or less
Not accurate for natural
gas with SG 0.9-1.0
Should be used as a first
approximation only

13

Katzs Equilibrium-Constant Method

It utilizes vapor-solid
equilibrium constant
KVS

y
xs

Not good for pure

components, only for
mixtures
K-values are red from
charts for different pure
components
The hydrate formation
conditions are computed in
a manner similar to the
dew-point calculations:
y
x

K 1

si

KVS-chart for Propane

VS

14

Baillie and Wichert Method

A chart generated by
Hysim simulator

Used for

Total acid gases: 1-70%

H2S: 1-50%
H2S/CO2: 1/3 to 10/1

Good agreement with

simulation (within 2
F)
Can also be used for
sweet NG with C3
content up to 10%

Equation-of-State Methods

The hydrates will form when T, P, and chemical

potential of water in the natural-gas, the liquidwater and the solid-hydrate phases are the same
The chemical potential in the hydrate phase is
computed using Platteeuw and van der Waals
methods
CSM has a hydrate program based on SRK EOS

KSV charts similar to Katz charts have been generated

using CSM program

16

Inclass exercise

A Natural gas stream with the following stream is flowing in a pipeline at a

pressure of 400 psia. Estimate the hydrate formation temperature using:
a)
b)
c)
d)

GPSA hydrate charts

Katz gas-gravity method
Katz equilibrium constant method
Baillie and Wicherts charts for sour gas

Which results would you use if you design for hydrate inhibition?
Comp

Mole
Frac

Mole
Wt.

C1

0.784

16.04

C2

0.060

30.07

C3

0.036

44.10

iC4

0.005

58.12

nC4

0.019

58.12

N2

0.094

28.01

CO2

0.002

44.01

Total

1.000
17

Hydrate Prevention

To prevent hydrate formation, we may resort

to:

Operate outside hydrate formation temperature

If practically feasible

Dry (dehydrating) the natural gas

Water dew point should be lower than LET
Ultimate solution

Add of chemicals to suppress the hydrate

formation temperature (hydrate inhibition)

Least attractive option

18

Hydrate Inhibition

Hydrate inhibition is the least attractive

method to deal with hydrates
Cost of chemicals
Reliability of inhibitor injection
Inhibitor interactions with other additives

Proper dosage need to be used to avoid

hydrate formation and maintain cost of
chemicals minimum

19

Hydrate Inhibition Options

No inhibitor
Thermodynamic hydrate inhibitors (THI)

Kinetic hydrate inhibitors (KHI)

Slow/delay hydrate formation

polyvinylpyrrolidone (PVP), and
polyvinylcaprolactam (PVCap)

Anti-agglommerants (Agg)

Change the hydrate formation

condition, Thydrates < LET
Methanol, Glycol

Disperse hydrates
Alcohol cosurfactant

Low Dose Hydrate inhibitor

Mixture of THI and Agg

20

Thermodynamic: Chemical Inhibition

Chemical addition may depress the hydrate or

ice formation temperature
Ammonia and brine are the eldest used chemicals
Glycols and methanol are the current chemicals
of choice

Ethylene Glycol (EG) and diethylene glycol (DEG) are

the most popular glycols
Tri and tetraethylene glycols are too soluble in liquid
hydrocarbon and too viscous

21

Glycols versus Methanol

Methanol can be used at any temperature
Glycols are used at temperatures above 15 F

Glycols have high viscosity and high solubility in liquid HC at

low T
At T > 20 F, DEG is preferred over EG because of its lower
vaporization losses

Depression of Hydrate formation temperature:

DEG

EG

Methanol

Glycols requires spraying into the wet gas

Dilute glycols are separated from the gas,
reconcentrated, and reused
Methanol recovery is not crucial as it can be easily
recovered in a subsequent glycol dehydration unit

22

Glycols versus Methanol

Glycol is usually cheaper when continuous injection
is required or high gas volumes being inhibited
Methanol is used for low gas volumes, temporary
installation, or when hydrate problem is mild
Methanol is always used for long lines (over a mile)
as it offers better protection than glycols
Using methanol injection prior to dehydration unit
may cause:

Co-absorption of methanol and water by the glycol

Corrosion of steel glycol absorption and regeneration
columns
Reduction in the capacity of solid desiccant due to its
co-adsorption
23

Methods Comparison

Cost:

Methanol has low investment cost but high

operating cost
Glycols have higher initial investment cost but
lower operating cost
Line heaters have intermediate investment cost

Operating cost depends on the value of the fuel

consumed

Typically glycols are used when methanol required

injection rate exceeds 30 gal/hr

Glycol cannot attack or dissolve existing

hydrates but methanol can

24

Hydrate blockage removal

Hydrates should be allowed to form

Hydrates is twice as dense as ice, and it
could move inside the pipes with a
speed up to 180 mile/h, which could
lead to pipe line rupture at the bends
or elbows
If plugging happens it could take weeks
to melt the hydrates
To unplug a plugged pipe by allowing
the pipeline warm up by the
surrounding environment, it could take
weeks for the hydrate to melt
Plugged pipelines can by be unplugged
by reducing the pressure on BOTH
SIDES of the plug

It is very danger to reduce the

pressure on one side as hydrate my
accelerates towards the low pressure
causing pipe breakage or unearthing

Offshore Technology Conference (2005) 17572; D.J.

Bilyeu & T.X. Chen

25

Next Lecture:
Hydrate Inhibition Design

26

Design Procedure
The minimum required mass flow rate of hydrate
inhibition chemical can be calculated as follow
1. Fraction of inhibitor in the aqueous phase

a)

Hammerschmidt correlation:

Inhibitor
KH
MW

a)

EG DEG MeOH
4000 4000
62

2335

106

32

xi weight fraction of pure inhibitor in the aqueous phase

T desired depression of hydrate formation, F
Mw molecular weight of inhibitor
KH hammerschmidt constant for inhibitor

Nelson and Bucklin (for methanol solution

temperature as low as -160 F)

xi mole fraction of water in the aqueous phase

27

Design Procedure

The amount of water to be

condensed form the gas phase,

WG=[Winlet conditions-Wrequired hydrate

conditions]
Water content of the gas
stream can be estimated using
McKetta Wehe or other
methods

Amount of inhibitor solution to

be added, S
S Q sW G

xi
x 0 x i

Qs is the gas flow rate, MMscfd

x0 is the inhibitor initial
concentration, mass fraction
Mcketta-Wehe

28

Aqueous Glycol Freezing Behavior

The outlet glycol concentration
as calculated by
Hummerschmidt or Nelson and
Bucklin correlationw may not be
of practical use due to the freeze
of the aqueous glycol solution
For glycols concentration 6080%, freezing is not possible at
any temperature
Therefore, it is recommended to
maintain the inlet and outlet
glycol concentration at this range
In such case, Wout will be
determined selected from the
no-freeze range

29

Vapor-Phase inhibitor Losses

Glycols have very low vapor pressures and
accordingly vapor-phase losses are minor
Methanol, however, is very volatile and vapor-phase
loses are significant
Methanol vapor phase
loses can be estimated
in terms of lowest
temperature in the
hydrate inhibition
system (the new
hydrate formation
temperature) and the
corresponding
pressure

31

Glycol Unit Operation:

Glycol Injection:

Glycol must be injected ahead of cooling vessels

(HXER, choke, expander, or chiller)
For heat exchanger, glycol maybe sprayed directly onto
the tube bundle instead of ahead of the exchanger

Glycol-water-oil separation:

Allow residence time of about 30 min (for T 30-40 F)

If no foaming or emulsion problems exist, 20 mins may
be sufficient
Separation at higher temperature (80-100 F) is
recommended to lower the viscosity and promote
settling
32

Glycol Unit Operation

Glycol losses:

Glycol solubility in hydrocarbon liquids increase with

Solution in liquid hydrocarbon

Vaporization and entrainment in the exit gas
Decomposition and carry over from the regenerator
An increase in glycol molecular weight
An increase in temperature
An increase in concentration of the glycol in the aqueous mixture

Corrosion inhibition

Solid particles must be removed by installing a full-flow filter

Corrosion inhibitors may affect the emulsion stability and thus the
glycol-water-oil separation
Since the degradation products are acidic, maintaining the pH at 7.2
minimizes corrosion

33

Hydrate Inhibition Example

15 MMscfd of a sweet water-saturated

natural gas with SG of 0.8 is to be cooled
from 100 F and 700 psia to 30 F.
i.
ii.
iii.

iv.

At what temperature will hydrate form?

How much water will be removed from the
gas?
How much EG solution (gal/hr) must be
added to prevent hydrate formation. Assume
that the EG is injected as a 75 wt.% ?
How much methanol is required?
34

S Q sW G

xi
x 0 x i

42

CO2 vent
Sulfur
Recovery
Solid
Sulfur
Acid Gas
Removal

Compression

Dehydration

Water

Oil

Gas to
Pipeline

Condensate
Recovery

Recompression

Condensate

Water

Phase
Separation

Solids

Raw Gas

43

Gas Hydrates

http://www.pet.hw.ac.uk/research/hydrate/hydrates_what.htm

Gas Hydrates

www.hydrafact.com

Hydrates

Hydrates
+ Ice

Ethane

47