GAS HYDRATES

PRESENTED BY

Sergio Nicols Badillo Jaimes

2112451

Vctor Alejandro Clavijo Salazar

2101326

Diego Fernando Cordero Cuadros 2111363

UNIVERSIDAD INDUSTRIAL DE SANTANDER

INGENIERIA DE GAS.

TOPICS

INTRODUCTION

WHAT IS THIS

CRYSTAL STRUCTURES HYDRATES

HYDRATE FORMATION

WATER CONTENT IN NATURAL GAS

PREDICTION OF TERMS HYDRATE FORMATION

METHODS USED TO PREDICT HYDRATE FORMATION

HOW HYDRATES ARE INHIBITED

TYPES OF INHIBITORS

HOW WATER CONTENT IS CALCULATED IN A SWEET

AND SOUR GAS.

INTRODUCTION

GAS HYDRATES
It is a complex and stable solid crystal.

Water Molecule

Hydrogen Bridge

Cavities

Gas molecule
Low molecular weight

Gas hydrates are very important as they can be generated in

conditions of common pressure and temperature in gas
transportation or oil production
These can block pipes, equipment and instruments, thus
restricting flow.

Methane
The most common
hydrates for the
gas industry are
composed of water
and the following
molecules

Ethane
Propane
Butane

The most common

hydrates for the
gas industry are
composed of water
and the following
molecules

CONDITIONS FOR THE FORMATION OF A

GAS HYDRATE.

STRUCTURES OF THE HYDRATES

There are two types of hydrates. These are classified by type
of organization of the molecules forming the crystal structure

Fuente: Natural Gas Hydrates - John J. Carroll

STRUCTURE TYPE I
Is the simpliest crystal structures: It has 46 water molecules
It has two types of cages:

Dodecahedron

Tetrakaidecahedron

Dodecahedron (Small cage)

It is a polyhedron with 12 faces, where each face is a regular
pentagon.

Fuente: Natural Gas Hydrates - John J. Carroll

Tetrakaidecahedron (Longer cage)

Is a polyhedron with 12 faces, where 12 are pentagons and 2
are hexagons

Fuente: Natural Gas Hydrates - John J. Carroll

FORMING HYDRATES COMMON TYPE I

STRUCTURE TYPE II
It is a bit more complex than the previous: It has 136 water
molecules.
It has two types of cages:

Dodecahedron

Tetrakaidecahedron

Dodecahedron (Small cage)

It is a polyhedron with 12 faces, where each face is a regular
pentagon.

Fuente: Natural Gas Hydrates - John J. Carroll

Hexakaidecahedron (Large cage)

Polyhedron with 16 faces, where 12 are pentagons and 4 are
hexagons.

Fuente: Natural Gas Hydrates - John J. Carroll

FORMING HYDRATES COMMON TYPE II

Fuente: Natural Gas Hydrates - John J. Carroll

Fuente: Natural Gas Hydrates - John J. Carroll

HYDRATE FORMATION

Hydrate
formation

WATER CONTENT OF GAS

The capacity of a gas stream to hold water vapor is:

A function of the gas composition

Affected by the pressure and temperature

of the gas

Reduced as the gas stream is compressed

or cooled

METHODS OF DETERMINING THE WATER

CONTENT OF GAS

For

a Sweet Gas

McKetta and Wehe correlation

= gravity correction factor for water content

= salinity correction factor for water content
The McKetta-Wehe chart is not applicable to sour gas.

EXAMPLE

Determine the saturated water content for a sweet lean

hydrocarbon gas at 150F and 1,000 psia, for a gas with 26
molecular weight and in equilibrium with a 3% brine
W = 220 lb/MMscf
Cg = 0.98
W = (0.98)(220) = 216 lb/MMscf
Cs = 0.93
W = (0.93)(220) = 205 lb/MMscf

Sour Gas Correlations

Weighted-Average Method
Below 40% acid gas components

SRK Sour Gas Correlations

The hydrocarbon portion of the gas was methane.
CO2 had 75% of the water content of H2S at the
same correlations

Correlations are used:

In dehydration calculations

To determine how much water, if any, will

condense from the gasinvolves considerations of
disposal, corrosion/erosion and hydrate inhibition

EXAMPLE

Determine the saturated water content of an 80% C1, 20% CO2

mixture at 160 F and 2000 psia. The experimentally determined
water content was 172 lb/MMscf

Weighted-Average Method
WHC = 167 lb/MMscf
WCO2= 240 lb/MMscf
W = (0.80)(167) + (0.20)(240)
= 182 lb/MMscf

SRK Sour Gas Correlations

Effective percent of H2S=%CO2*0,75+%H2S
W = 0.49 bbl/MMscf
W= (0.49)(350) =172 lb/MMsc

PREDICTION OF OPERATING TEMPERATURE

AND PRESSURE
Wellhead Conditions
Temperatures at the wellhead increases as the flow rate
increases and the pressure decreases.
Flowline Conditions
The cooling of a gas in a flowline due to heat loss to the
surroundings (ground, water, or air).

Calculation of Temperature and Pressure at the Wellhead

Calculation of Flowline Downstream Temperature

Td = flowline downstream temperature

Td=lowline downstream temperature,F

D=flowline OD, ft.

U=heat transfer coefficient BTU/hr/ft

L=flowlinelength, ft.

Q=gas flow rate, MSCFD

Cp=specific heat factor, Btu/MCF/

E=2.718

Tu=upstream gas temperature,F

Tg=ground temperature,

TEMPERATURE DROP CORRELATION

Used

when gas composition is unknown

Used

for a first approximation

Yields

reliable results but affected by liquids

Requires

correcting for hydrocarbon liquids

EXAMPLE

Determine the Temperature Drop across a Choke A well

with a flowing tubing pressure of 4000 psi and 20 bbl of
hydrocarbon condensate and a downstream back pressure
of 1000 psi
P=4000psi-1000psi= 3000psi
T=80F

HYDRATE PREDICTION CORRELATIONS

VAPOR-SOLID EQUILIBRIUM CONSTANTS

1.

2. Determine the equilibrium constant, K, for each

component where

Assume hydrate formation temperature

Where
Yi =Mol fraction of each component in the gas on a water free
basis
Xi =Mol fraction of each component in the solid on a water
free basis

 3.

Calculate the ratio,Yi/Ki for each component

4.

Sum the values of Yi/K

5.

Repeat steps 14 for additional temperatures

until

EXAMPLE

Calculate the pressure for hydrate formation at 50F for a

gas with the following composition

EXAMPLE

Determine the Hydrate Formation Temperature Using

Pressure-Temperature Correlations. 0.6 specific gravity gas
operating at 2000 psia.

Solution: From pressure-temperature curve intersect

2000 psia and 0.6 specific gravity curve and read 68F.

Hydrate Predictions for High CO2/H2S

Content Gases

Baille & Wicherts method

EXAMPLE

Estimate the hydrate formation temperature at 610 psia of a

gas with the following analysis using Baille & Wicherts
method
TH = 63.5 2.7 =
60.8F

HOW IS INHIBITED THE HYDRATE

The first method to deal with ice was with salt.

Glycol solution sprayed on airplanes for take-off in order to deice them.

Polar solvents, such as alcohol, glycol, and ionic salts are

known to inhibit the formation of gas hydrates.

They do not prevent hydrate formation, they inhibit it.

Temperature reduction or pressure increasing.

Minimum concentration to avoid hydrate formation.

Fuente: Natural Gas Hydrates - John J. Carroll

FREEZING POINT DEPRESSION

Depression of the freezing point is commonly used to estimate the

molar mass of a sample.

T= T depression (C) R=Universal gas constant (8.314 J/mol K)

Tm= pure solvent melting point (K)

Fuente: Natural Gas Hydrates - John J. Carroll

Fuente: Natural Gas Hydrates - John J. Carroll

THE HAMMERSCHMIDT EQUATION

W= inhibitor concentration (%w)

THE NIELSENBUCKLIN EQUATION

the equation was developed for use with methanol

It is actually independent of the choice of inhibitor
involves only the properties of water and the concentration of the
inhibitor.
It can be used for any inhibitor, where the molecular weight of the
solvent is substituted for MM

A NEW METHOD

The new equation should have the NielsenBucklin (and hence

the Hammerschmidt) equation as a low concentration limit.

It should have a firm basis in theory such that it can be

extrapolated to conditions where no data exist.

The new equation is a little difficult to use, especially if the temperature

depression is given and the required inhibitor concentration must be
calculated.

METHODS COMPARISON

COMMENT ON THE SIMPLE METHODS

They predict the depression of hydrate temperature; dont predict

actual hydrate formation conditions.

Begin with methods to predict hydrate formation in absence of

inhibitor.

These correction factors cannot overcome a poor original prediction.

Is safe to neglect the effect of pressure on the inhibiting effect.

COMMENT ON THE SIMPLE METHODS

T depression independent of nature of hydrate former and type of

hydrate formed.

Result obtained is a temperature difference, not an actual temp.

Advanced models include the effect of pressure and type of hydrate.

Relatively low molar mass is advantageous for an inhibitor.

LOSSES HC CONDENSATE

METHANOL: In aromatic-rich condensate, methanol losses can be

5 times those in paraffinic condensate.

EG: TEG losses to the condensate are just as small as for EG

INJECTION RATES: Low rates and high pressures

LOW DOSAGE HYDRATE INHIBITORS

(1) kinetic inhibitors

(2) anticoagulants

They dont lower T, they lower its effect.

KHI reduces the rate of hydrate formation, It inhibits its

development for a certain time.

KHI Delays hydrate formation and growth such there is enough

time to transport fluids to destination.

AA only prevents the accumulation of hydrate into a plug.

The hydrate stays in a slurry, which can still be transported and will
not plug the line.

BIBLIOGRAPHY

Natural Gas Hydrates - John J. Carroll