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HYDRATES AND HYDRATE PREVENTION

H2O CONTENT OF
MOISTURE-SATURATED GASES

EP 20266_a_A_ppt_04 H2O CONTENT OF MOISTURE-SATURATED GASES

COURSE OUTLINE


INTRODUCTION

H2O CONTENT ESTIMATION METHODS


CASE OF SWEET GASES
CASE OF ACID GASES
USE OF SIMULATION PROGRAMS

WATER DEW CURVE OF A NATURAL GAS

ON SITE MEASUREMENT OF WATER CONTENT

EP 20266_a_A_ppt_04 H2O CONTENT OF MOISTURE-SATURATED GASES

2009 - IFP Training

INTRODUCTION ORIGINS OF WATER

All fluids at reservoir conditions are water saturated


Therefore water is always present in oil and gas effluent: in VAPOR phase, and often also
in LIQUID phase

Liquid water: either production water or condensation water


Forms with CO2 and H2S corrosive products
Reduces the capacity of transport of the pipelines

Liquid (or vapour) water:


Forms hydrates with C1, C2, C3, iC4, CO2, H2S, N2, typically at pressures > 10 bar and
temperature < 25C

2009 - IFP Training

EP 20266_a_A_ppt_04 H2O CONTENT OF MOISTURE-SATURATED GASES

COURSE OUTLINE


INTRODUCTION

H2O CONTENT ESTIMATION METHODS


CASE OF SWEET GASES
CASE OF ACID GASES
USE OF SIMULATION PROGRAMS

WATER DEW CURVE OF A NATURAL GAS

ON SITE MEASUREMENT OF WATER CONTENT

EP 20266_a_A_ppt_04 H2O CONTENT OF MOISTURE-SATURATED GASES

2009 - IFP Training

H2O CONTENT ESTIMATION METHODS Case of SWEET gases

Gordon Wichert chart (extension of


McKetta chart) with corrections for
density, water salinity, H2S and CO2
content
(JM Campbell charts give equivalent
results)

BUKACEK correlation

Thermodynamic simulation programs


(PRO II, HYSYS)

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Constants depending
on P and T
Given by TABLE
or GdF equations
2009 - IFP Training

Example :

H2O CONTENT OF SWEET NATURAL GAS


- JM Campbell charts -

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H2O CONTENT ESTIMATION METHODS Case of SWEET gases


BUKACEK CORRELATION GdF equations for A and B calculation

2009 - IFP Training

EP 20266_a_A_ppt_04 H2O CONTENT OF MOISTURE-SATURATED GASES

H2O CONTENT ESTIMATION METHODS Case of SWEET gases


McKETTA Chart
1 - What is the H2O content of a natural gas at 200F and 3000 psi.a ?
280
.

lb/MMSCF

2 For the same base pressure (3000 psi.a), what will be the H2O content of this natural gas at lower
temperature (100F) ?

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lb/MMSCF

Conclusion: the moisture content of a natural gas increases, when the temperature INCREASES

3 For the same base temperature (200F), what will be the H2O content of this natural gas at lower
pressure (1500 psi.a) ?
lb/MMSCF

Conclusion: the moisture content of a natural gas increases, when the pressure DECREASES

EP 20266_a_A_ppt_04 H2O CONTENT OF MOISTURE-SATURATED GASES

2009 - IFP Training

480
.

H2O CONTENT ESTIMATION METHODS Case of SWEET gases


McKETTA Chart

4 What is the Dew Temperature at 1000 psi.a of this same gas (moisture-saturated at 200F and
3000 psi.a) ?
150

5 What is the Dew Pressure at 100F of this same gas (moisture-saturated at 200F and 3000
psi.a) ?
170
.

psi.a

EP 20266_a_A_ppt_04 H2O CONTENT OF MOISTURE-SATURATED GASES

2009 - IFP Training

Remark: the water contents of gases do not exceed 47,484 lb/MMSCF of wet gas, which
corresponds to pure vapor stream (100% water). This is clearly shown on the McKETTA chart.

H2O CONTENT ESTIMATION METHODS Case of SWEET gases


McKETTA Chart Correction for Specific Gravity

The McKETTA chart is aimed at a gas


Specific Gravity of 0.6 (air = 1.0).
Given that:
Sp.GrGas

M:
Sp.Gr:

MGas
MAir

MGas
kg
29
kmol

Molecular Weight (kg/kmol)


Specific Gravity

..
17.4
EP 20266_a_A_ppt_04 H2O CONTENT OF MOISTURE-SATURATED GASES

kg/kmol

2009 - IFP Training

This is equivalent to a gas molecular weight of :

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H2O CONTENT ESTIMATION METHODS Case of SWEET gases


McKETTA Chart Correction for Specific Gravity

6 What will be the H2O content of the same natural gas (moisture-saturated at 200F and 3000
psi.a) if we take into account the correction factor for Specific Gravity (Molecular Weight 23.2
kg/kmol) ?
Gas Molecular Weight:

23.2

kg/kmol

Gas Specific Gravity:

0.8
..

Correction Factor for Specific Gravity, Cg:

.
0.975

H2O content without correction for Sp.Gr:

..
280

lb/MMSCF

H2O content corrected for Specific Gravity:

..
273

lb/MMSCF

EP 20266_a_A_ppt_04 H2O CONTENT OF MOISTURE-SATURATED GASES

2009 - IFP Training

Conclusion: the H2O content of a natural gas increases when the Specific Gravity DECREASES.

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H2O CONTENT ESTIMATION METHODS Case of SWEET gases


McKETTA Chart Correction for Water Salinity

A Correction Factor Cs could be introduced in order to take into account the salinity of
the formation water.
This correction factor is lower than one.

2009 - IFP Training

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H2O CONTENT ESTIMATION METHODS Case of SWEET gases


McKETTA Chart Correction for Water Salinity

7 What will be the H2O content of the same natural gas (moisture-saturated at 200F and 3000
psi.a) if we take also into account the correction factor for formation water salinity (Salt
content : 3% weight of salted water) ?
Salinity of formation water:

Weight %

H2O content corrected to Sp.Gr:

...
273

lb/MMSCF

Correction Factor for Salinity, Cs:

0.93

H2O content corrected for Sp.GR and Salinity:

...
254

lb/MMSCF

EP 20266_a_A_ppt_04 H2O CONTENT OF MOISTURE-SATURATED GASES

2009 - IFP Training

Conclusion: the H2O content of a natural gas increases when the water Salinity DECREASES.
..

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H2O CONTENT ESTIMATION METHODS Case of SWEET gases


BUKACEK Correlation

8 Compare the H2O content obtained by McKETTA to BUKACEK for the same natural gas
(moisture-saturated at 200F = 93.3C; 3000 psi.a = 206.9 bar.a; M = 23.3 kg/kmol and 3 %
weight of water salinity).
McKETTA

BUKACEK
Tables

GdF equations

A coeff. (in the adequate unit system)

547
000

644 556
...

B coeff. (in the adequate unit system)

104
...

1472.4
.

H2O content without corrections, mg/Nm3

4587.7
.

286.3

271.3
.

H2O content without corrections, lb/MMSCF

280
..

0.975
...

Salinity Correction Factor, Cs

0.93

260
.

H2O content with corrections, lb/MMSCF

N.B.

1 lb/MMSCF = 16.9076 mg/Nm3

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254
..

246
..

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Specific Gravity Correction Factor, Cg

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COURSE OUTLINE


INTRODUCTION

H2O CONTENT ESTIMATION METHODS


CASE OF SWEET GASES
CASE OF ACID GASES
USE OF SIMULATION PROGRAMS

WATER DEW CURVE OF A NATURAL GAS

ON SITE MEASUREMENT OF WATER CONTENT

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2009 - IFP Training

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H2O CONTENT ESTIMATION METHODS Case of ACID gases

The McKetta & Bukacek methods are valid for (H2S + CO2) < 10% mol

Otherwise correction factors are required :


CAMPBELL method
GASUNIE method

2009 - IFP Training

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H2O CONTENT ESTIMATION METHODS Case of ACID gases

CAMPBELL method
WSour Gas = YHC WHC + YCO2 WCO2 + YH2S WH2S
WSour Gas

: water content of sour gas

WHC

: water content of sweet gas (HC fraction)

YHC

: mole fraction of all components except H2S and CO2


: effective water content of CO2, given by charts

YCO

: mole fraction of CO2 in natural gas

WH

: effective water content of H2S, given by charts

YH

: mole fraction of H2S

2S

2S

EP 20266_a_A_ppt_04 H2O CONTENT OF MOISTURE-SATURATED GASES

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WCO

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CORRECTION FOR ACID GASES CAMPBELL METHOD


CAMPBELL

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CORRECTION FOR ACID GASES CAMPBELL METHOD


CAMPBELL

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H2O CONTENT ESTIMATION METHODS Case of ACID gases

CAMPBELL method
9 Using the CAMPBELL method, what will be the H2O content of the same natural gas (moisturesaturated at 200F, 3000 psi.a), given a H2S content of 4% mol and a CO2 content of 6 % mol.
For simplification corrections for Specific Gravity and Salinity will not be considered.
H2O content of the sweet gas (without acid components) :

..
280

lb/MMSCF

Effective H2O content of H2S:

..
1 083

lb/MMSCF

Effective H2O content of CO2:

400
..

lb/MMSCF

H2O content of gas with acidity correction:

320

lb/MMSCF

EP 20266_a_A_ppt_04 H2O CONTENT OF MOISTURE-SATURATED GASES

2009 - IFP Training

Conclusion: the H2O content of a natural gas increases when the acidity INCREASES.

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CORRECTION FOR ACID GASES GASUNIE METHOD


GASUNIE

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H2O CONTENT ESTIMATION METHODS Case of ACID gases

GASUNIE method
Using the GASUNIE method, what will be the H2O content of a natural gas saturated with
moisture at 30C and 80 bar.a), given a H2S content of 4% mol and a CO2 content of 6 % mol.
For simplification corrections for Specific Gravity and Salinity will not be considered.
Equivalent H2S content:

8.5

% mol

GASUNIE correction factor

40

mg/Nm3

Water content of the sweet gas:

581

mg/Nm3

(Bukacek)
H2O content of gas with acidity correction:

.
621

EP 20266_a_A_ppt_04 H2O CONTENT OF MOISTURE-SATURATED GASES

...
INCREASES

2009 - IFP Training

Conclusion: the H2O content of a natural gas increases when the acidity

mg/Nm3

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COURSE OUTLINE


INTRODUCTION

H2O CONTENT ESTIMATION METHODS


CASE OF SWEET GASES
CASE OF ACID GASES
USE OF SIMULATION PROGRAMS

WATER DEW CURVE OF A NATURAL GAS

ON SITE MEASUREMENT OF WATER CONTENT

EP 20266_a_A_ppt_04 H2O CONTENT OF MOISTURE-SATURATED GASES

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WATER CONTENT COMPUTER SIMULATION PROGRAMS

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COURSE OUTLINE


INTRODUCTION

H2O CONTENT ESTIMATION METHODS


CASE OF SWEET GASES
CASE OF ACID GASES
USE OF SIMULATION PROGRAMS

WATER DEW CURVE OF A NATURAL GAS

ON SITE MEASUREMENT OF WATER CONTENT

EP 20266_a_A_ppt_04 H2O CONTENT OF MOISTURE-SATURATED GASES

2009 - IFP Training

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WATER DEW POINT (DP) / WATER DEW CURVE DEFINITION

Definition:

A water saturated gas at given conditions (P


& T) is said to be at its water dew point
when water vapour starts to condense when
the gas is slightly cooled at constant P.

GAS WATER DEW POINT CURVE


160
140

Water content could be defined by P &


T values of the gas water at dew-point.
For one water content, there is an
infinite number of water dew-points,
defining the water Dew Curve

120
Pressure (bar a)

100
80
60
40
20

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0
0

50

100

Temperatue (C)

150

2009 - IFP Training

For one water dew-point defined by


one (P & T) couple, there is only one
water content

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WATER DEW POINT (DP) / WATER DEW CURVE APPLICATION


Lets consider a natural gas saturated with moisture at 1000 psi.a and 100F.
Fill-in the following table with the water dew points (No corrections for Sp.Gr. nor Salinity)
60.40
..

Water Content (lb/MMSCF)


Dew Temperature (F)
Dew Pressure (psi.a)

20

40

60

80

100

120

130

140

150

17.7
..

43.7
..

101.3
..

223.3
..

474.1
..

1,000

2,191
..

3,387
..

5,524
..

10,291
..

2009 - IFP Training

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COURSE OUTLINE


INTRODUCTION

H2O CONTENT ESTIMATION METHODS


CASE OF SWEET GASES
CASE OF ACID GASES
USE OF SIMULATION PROGRAMS

WATER DEW CURVE OF A NATURAL GAS

ON SITE MEASUREMENT OF WATER CONTENT

EP 20266_a_A_ppt_04 H2O CONTENT OF MOISTURE-SATURATED GASES

2009 - IFP Training

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ON SITE MEASUREMENT MEASUREMENT OF WATER DEW POINT

PORTABLE MEASUREMENT INSTRUMENTS (Bureau of Mines DP tester)

Consists into detecting condensation over a scope or a glass

Allows to measure either Water or HC DP, whatever the first to meet (the highest temperature)
The detection could be automatic

Could be used up to pressures of 170 bar.a


Temperature drop must be very gradual
0.1C for temperatures higher than 0C
0.3C for temperatures lower than 0C

IN-LINE MEASUREMENT INSTRUMENTS


most are based on the Bureau of Mines tester
the mirror is cooled by elements based on PELTIER effect (an electric current flowing through a loop
composed of two different metals generates a temperature difference between the two weld
junctions)

The measurement thus obtained is processed by the DCS in the control room
Remark: the PANAMETRIX is an instrument used on site for dew point measurement is composed of
GOLD sensors, which can not tolerate any presence of MERCYRY in the gas (formation of amalgam)

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ON SITE MEASUREMENT QUANTITATIVE MEASUREMENT WATER


CONTENT


USE OF SOLID CHEMICAL ABSORBENTS (DRGER TUBE TYPE)

USE OF LIQUID CHEMICAL ABSORBENTS

Typically Magnesium Perchlorate, which has a specific feature to retain moisture


The water content is obtained by measuring the increase in mass of the absorbent (Gravimetry)
More adapted to LOW PRESSURE measurements (relatively high H2O content)
Remark: the absorbent must be pre-saturated with the HC of the gas itself

Chemical solutions that absorb moisture


The most common is Karl-Fisher method (solution of Methanol, containing iodine, pyridine and SO2)
the water content is obtained by Titrimetry
Remark: the Karl-Fisher solution is very unstable (degraded under light effect). More stable reagents
are now available.

OTHER TYPES OF ANALYZERS


Other types are available. All of them are sensitive to liquids (water, methanol, glycols, HC)
Electrolytic Sensors, based on the use of Phosphorous Pentoxide P2O5: slow process
Piezoelectric Sorption: complex and not always precise due to H2S
Dielectric Layers (metal oxide, silicon-optic): good precision initially
Absorption Spectroscopy: danger of overlap by the gaseous compounds
Idem + Tunable Diode Laser (TDL): very good precision

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KEY POINTS TO REMEMBER

Natural gases are almost always saturated with moisture because they are often in
contact with an aqueous phase (except of course after a dehydration and/or
reheating step in contact with water).

The lower the pressure and the higher the temperature, the higher the water
saturation of a natural gas.

The water saturation of a natural gas decreases if the Molecular Weight increases.

The water saturation of a natural gas decreases if the salinity of the reservoir water
(which saturated the gas) increases.

The acidity of a natural gas results in a higher water saturation content (corrections
needed for H2S + CO2 contents in the natural gas greater than 5 % mol)

Some water dew point in-line measuring instruments have gold sensors and
therefore cannot be used for gases containing mercury.

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UNITS CONVERSION
 Normal Conditions:
mmHg

1 atm.a = 1.013 bar.a = 760


0C (Universal!!!)

 Standard Conditions:
mmHg
1 bar = 14.5 psi
1 atm = 14.7 psi

1 atm.a = 1.013 bar.a = 760


US: 60F? (=15.6C); UE: 15C?;

Water content of a gas:

1 lb/MMSCF =

16.9076 mg/Nm3

1 lb = 0.4536 kg

16.0187 mg/Sm3

1 m3 = 35.31467 CF

379.495/18.02 21.06 ppm

23.645/18.02 1.31 ppm volume

1 bbl = 0.159 m3

volume
1 mg/Sm3

0.0282623 Sm3 (at 15C and 101.325

1 Sm3 (at 15C and 101.325 kPa) = 35.382754 SCF (at 60F and 14.7
psi.a)
EP 20266_a_A_ppt_04 H2O CONTENT OF MOISTURE-SATURATED GASES

2009 - IFP Training

1 SCF (at 60F and 14.7 psi.a) =


kPa)

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