Hydrates Formation and Inhibition

"OIL AND GAS PROCESSING PLANT DESIGN 2002
AND OPERATION TRAINING COURSE"

DGEP/SCR/ED/ECP
"HYDRATES FORMATION AND INHIBITION" Page 1
"HYDRATES FORMATION
AND INHIBITION"
Excerpt from PRODEM

DGEP/SCR/ED/ECP
RECOMMENDATIONS 5
SCOPE 6
REFERENCES 6
GENERAL 7
PREDICTING METHODS TO EVALUATE THE MAXIMUM OF WATER

VAPOR CONTENT OF NATURAL AND ASSOCIATED GASES 8
1. CHARTS 8
1.1. Wichert charts published in 1993 ( Fig.IV-A1, 2 and 3) 8
1.2. Campbell charts 10
1.3. A.T.G. Chart (Association Technique de l'Industrie du Gaz de France) 11
2. COMPUTER PROGRAMS 12
2.1. General 12
2.2. Thermodynamic computer program use 13
WATER-HYDROCARBON PHASE BEHAVIOUR "WATER DEW POINT"

DEFINITION 14
AMOUNT OF WATER LIQUID PRODUCED IN A WELL AND IN A FLOWLINE

DETERMINATION EXAMPLE 17
COMPARISON OF PREDICTING METHODS TO EVALUATE THE MAXIMUM

OF WATER VAPOR CONTENT OF NATURAL GASES 19
SCOPE 21
REFERENCES 22
GENERAL 23
1. HYDRATES COMPONENTS AND PROPERTIES 23
2. CONDITIONS FOR HYDRATE FORMATION IN A HYDROCARBON MIXTURE 23
3. HYDRATE EQUILIBRIUM CONDITIONS IN MULTIPHASE MIXTURES 24
Excerpt from PRODEM

DGEP/SCR/ED/ECP
PREDICTING OF HYDRATE FORMATION CONDITIONS 25

1. CHARTS 25
2. COMPUTERS PROGRAM 25
PREVENTION OF HYDRATE FORMATION 26

1. GENERAL 26
2. DESIGN CONSIDERATIONS FOR HYDRATE INHIBITION 28
2.1. Economics 28
2.2. Methanol specific problems 28
3. QUANTITY OF INHIBITOR REQUIRED TO PREVENT AN HYDRATE FORMATION 29
3.1. Minimum inhibitor concentration in the free water phase 29
3.2. Inhibitor losses to the hydrocarbon phase 30
4. DESIGN TEMPERATURE TO BE ADOPTED FOR EQUIPMENT DESIGN TO PREVENT
HYDRATE FORMATION IN A HYDROCARBON MIXTURE 31
USE OF GLYCOLS TO INHIBIT SIMULTANEOUSLY HYDRATE FORMATION

AND CO2 CORROSION 32
1. GENERAL 32
2. GLYCOL INJECTION EFFECT 32
2.1. Corrosion inhibition effect 32
2.2. Top-of-the-line corrosion and distribution of glycol in a large wet gas
pipeline 32
2.3. Glycol slug effect 33
3. QUANTITY OF INHIBITOR REQUIRED TO PREVENT CO2 CORROSION 33
GLYCOL – INJECTION SYSTEM INTO PROCESS 34
MEANS USED TO ELIMINATE AN HYDRATE PLUG 35

1. ELIMINATION OF AN HYDRATE PLUG IN A PIPELINE OR A FLOWLINE 35
1.1. General 35
1.2. Procedure to eliminate an hydrate plug 35
2. ELIMINATION OF AN HYDRATE PLUG FROM A SUBSEA FLOWLINE 36
2.1. Localisation of the hydrate plug 36
2.2. Proposed procedure to eliminate the hydrate plug 37
Excerpt from PRODEM

DGEP/SCR/ED/ECP
APPENDIX
Figure IV-A1 - Equilibrium water vapor content of sweet natural gas (Wichert Chart)
Figure IV-A2 - Correction for gas relative density
Figure IV-A3 - Ratio of the water-vapor content of sour gas (Wichert Chart)
Figure IV-A4 - Water content of sweet, lean natural gas (Campbell Chart)
Figure IV-A5 - Water content contribution of CO2 (Campbell Chart)
Figure IV-A6 - Water content contribution of H2S (Campbell Chart)
Figure IV-A7 - Well and flowline simulation scheme
PRO/II – Flash Unit with decantable water
Figure IV-B1 - Gas-gravity chart for natural gas (Katz)
Excerpt from PRODEM

DGEP/SCR/ED/ECP
RECOMMENDATIONS
Maximum water-vapor content of natural and associated gases can be predicted by charts or
computer programs. Wichert or Campbell charts can be used to determine a good estimated value
(their results are very closed).
Only the S.R.K.K.D. option of PRO/II gives in all cases satisfactory results. The S.R.K. with
G.P.S.A. option can be used for sweet gases only (CO2 mol % < 2 ; H2S mol % < 1.5). Results
obtained with the S.R.K. correlation without GPSA option are wrong.
FHYD from Professor Penelous (Marseille University) available at ETP gives very satisfactory
results.
Hysim program gives satisfactory results.
Be aware :
In the practice, the water content of a gas is very often defined by the couple of pressure and
temperature of the "gas water dew point".
If pressure value is not given, temperature value is not sufficient to determine the amount of water
vapor allowable in gas.
"Water dew point" is also used when hydrate or ice are producing at given conditions (pressure
and temperature) instead of water liquid (see page 16).
Due to the difficulty to measure a "water dew-point" with a dewscope it is recommended to specify
the amount of water vapour contained in gas in :
"mass of water unit per one unity of volume of wet gas at standard or normal conditions" not in
"water dewpoint".
Excerpt from PRODEM

DGEP/SCR/ED/ECP
SCOPE
It is very important to know in what conditions liquid water appears in natural and associated gases
and of course the amount of liquid water formed, because :
• pressure favors the combination of liquid water with natural gases to form solid gas
hydrates, even though the temperature is above the freezing point of water.
The formation of gas hydrates, which resembles wet snow, is to be avoided since they
plug pipelines and valves, interrupting the steady flow of gas.
• Liquid water :
♦ forms with the CO2 and the H2S a severe corrosive product for the pipes and fittings :
carbonic acid and sulfhydric acid,
♦ reduce the capacity of transport of the pipelines.
REFERENCES
• Natural gas Engineering - Production and Storage (1990), Donald L. Katz - Robert
L. Lee - Mc. Graw Hill Publishing Company.
• G.P.S.A. SI Engineering Data Book, (1980), Gas Processors Suppliers Association, Tulsa,
Oklahoma. 74103.
• Engineering Data Book, (1994), U.S. Units, Volume II, Gas Processors Suppliers
Association, Tulsa, Oklahoma 74145.
• Gas Conditioning and Processing, (1992).

The basic principles - J.M. CAMPBELL.
Campbell Petroleum Series, 1215 Crossroads Blood, Norman, Oklahoma 73069.
• Chart estimates water content of Sour Natural Gas,

Gordon C. Wichert, Edward Wichert.
Oil and Gas Journal. Mar. 29, 1993, pp. 61 to 64.
• A.S.T.M. - D 1142-63 (1963 and 1980).

A.S.T.M. 104.S1 (1971).
Excerpt from PRODEM

DGEP/SCR/ED/ECP
GENERAL
Natural and associated gas always contain water vapor. A dehydration unit lowers the amount of
water vapor contained in a natural or associated gas, but does not eliminate the whole amount of
water vapor. So, a "dry gas" still contains water vapor.
The amount of water vapor contained in a gas is expressed in :
MASS OF WATER UNIT PER ONE UNITY OF VOLUME OF WET GAS AT STANDARD OR
NORMAL CONDITIONS.
The standard cubic foot and the standard cubic meter are a "bastard legacy" of historical contracts
for the metering and custody transfer of natural gas. In engineering calculations, it is necessary to
convert these volume terms to an appropriate mass term.
w Gas volume at standard conditions

=
(actual gas volume) (actual gas density)
gas density at standard conditions
g
w Actual gas volume or actual gas density is at the pressure and temperature of the gas.
w Standard conditions in English units (Std) is : 14.7 psia (1 normal atmosphere ), 60°F (15.6°C).
w Usual standard conditions in metric units (S) is : 101.325 kPa (1 normal atmosphere ), 15°C.
w Normal conditions (n) is : 101.325 kPa (1 atmosphere normal), 0°C.
1 m3 = 35.31467 cuft
1 Std cuft (at 60°F, 14.7 psia) = 0.0282623 Sm³ (at 15°C, 101.325 kPa)
1 Sm³ (at 15°C, 101.325 kPa) = 35.382754 Std cuft (at 60°F, 14.7 psia)
The water-vapor content of a gas is given in :
• milligrams of water per cubic meter of wet gas at standard conditions (mg/Sm³) ;
• kilograms of water per million of cubic meter of wet gas at standard conditions
(kg/106Sm³) ;
1 mg/Sm3 = 1 kg/106 Sm 3
• pound mass of water per million of cubic feet of wet gas at standard conditions (lb/106 std
cuft)
1 lb/106 Std cuft = 16.049348 kg/10 6 Sm³,
1 kg/106 Sm³ = 0.0623078 lb/106 Std cuft.
Excerpt from PRODEM

DGEP/SCR/ED/ECP
A gas is said "water saturated" when it contains the maximum of the amount of water vapor
possible at given conditions. This maximum depends on :
• pressure and temperature values of the gas,

• composition of the gas,
• liquid water composition in equilibrium with the gas phase,
(particularly dissolved salts).
PREDICTING METHODS TO EVALUATE THE MAXIMUM OF WATER VAPOR

CONTENT OF NATURAL AND ASSOCIATED GASES
1. CHARTS
Several charts are given in the technical litterature to predict the maximum water vapor contain of
natural and associated gases. They were prepared from several experimental measurements by
different investigators.
1.1. Wichert charts published in 1993 ( Fig.IV-A1, 2 and 3)
1.1.1. General
The method requires use of the figure IV-A1 for the water-vapor content of sweet natural gas and a
figure IV-A3 showing the ratio of the water-vapor content of sour gas compared with that of sweet
gas.
The following are conditions limiting the method :
• pressure to 70 MPa (700 bar),

• temperature to 175°C,
• equivalent H2S content to 55 mol % (see definition in following page).
Figure IV-A1 is an extension of the famous MacKetta and Wehe chart published in 1958. Also are
included in it other features of the MacKetta-Wehe chart, such as corrections for gas relative
density and salinity, as well as comments, regarding the hydrate line and water-vapor content in
the subzero temperature region.
However, as the amounts of carbon dioxide and hydrogen sulfide increase the accuracy becomes
poorer. It is a good practice to make a correction for these contaminants even though it may be
small when concentrations and pressures are low.
Nitrogen will hold less water than methane. At pressures to about 70 bar the water content of
nitrogen is about 6 to 9 % less than for methane. This deviation increases with pressure (2 % more
at 100 bar, which is small and difficult to measure). Thus, including nitrogen as a hydrocarbon is
practical and offers a small safety factor, and avoid to do further corrections.
Excerpt from PRODEM

DGEP/SCR/ED/ECP
The presence of dissolved solids (salts) in water lowers the water capacity of the gas.
In correction salinity chart, the total solids in brine is defined as follows :
Solids or salts mass in brine

Total solids in brine (mass %) = x 100
Pure water mass in brine
While figure IV-A1 includes corrections for gas gravity and salinity of the produced brine, these
"corrections" for gas gravity and salinity of the produced brine are often ignored as "safety factors".
Figure IV-A3 gives the ratio of the water-vapor content of sour natural gas as compared to the
water-vapor content of sweet natural gas at the same pressure and temperature.
To use this chart, it is necessary to calculate an equivalent H2S content for the sour-gas mixture by
adding 75 % of the CO2 content to the H2S content of the sour natural gas.
% Equivalent H2S = 100 (Y H2S + 0.75 YCO 2 )

with : YH 2 S = mol fraction of H2S,
Y co2 = mol fraction of CO2.
Total water content of sour gas is given by following :
W = r W sw
with : W = water content (kg/10³ Sm³ of wet gas),

Wsw = water content of sweet gas,
r = water concentration ratio, H2O in sour gas/H2O in sweet gas given by
figure IV-A3, versus % H2S equivalent, temperature and pressure.
1.1.2. Example problem
Estimating of the maximum water-vapor content of Saint Faust gas at reservoir conditions.
Composition (dry bases) % mol
NITROGEN 0.54
CO2 9.60
H2S 6.48
METHANE 76.06
ETHANE 3.45
PROPANE 1.11
BUTANES 1.01
C5+ 1.75
Excerpt from PRODEM

DGEP/SCR/ED/ECP
Molecular weight : 22.2 kg/kmol
Reservoir conditions : Pressure : 150 bar abs (15 MPa) Temperature : 150°C
Solution :
1st Step : Determine the equilibrium water-vapor content of sweet gas at the same
conditions using the chart in Fig. IV-A1.
(approximately : 32 kg/10³ Sm³).
2nd Step : Determine the correction for gas relative density using the gas relative density
correction chart in Fig. IV-A2.
(Approximately : CG = 0.98)
(and Csw = 0.98 x 32 = 31.36 kg / 10³ Sm³)
3rd Step : Calculate the equivalent H2S content of the mixture
% equivalent H2S = 6.48 + 0.75 x 9.60 = 13.68 %
4th Step : Enter figure IV-A3 at 150°C and move to the right to the 13.68 % equivalent H2S
line. From this point, move vertically to the absolute pressure of 15 MPa. Move to
the left side of the chart and obtain the corresponding water-vapor content ratio
(approximately 1.05).
5th Step : To obtain the equilibrium water-vapor content of the sour-gas mixture, multiply
the water-vapor content ratio by the equilibrium water-vapor content of sweet gas
obtained in Step 2 :
31.36 x 1.05 = 32.93 kg/10³ Sm³
1.2. Campbell charts
The Campbell method is introduced in :
• G.P.S.A. Engineering Data Book,

• Gas Conditioning and Processing. The Basic Principles (vol.1) by J.M. CAMPBELL.
It uses the following empirical combination rule :
W = YHC WHC + YCO 2 WCO2 + YH2S WH2S
with : W = Water content of sour gas,
W HC = water content of sweet gas,

YHC = mol fraction of all components except H2S and CO2,
W CO2 = effective water content of CO2,
YCO2 = mol fraction of CO2 in natural gas,
Excerpt from PRODEM

DGEP/SCR/ED/ECP
W H2 S = effective water content of H2S,

YH 2S = mol fraction of H2S in natural gas.
for W HC the Campbell chart can be use ( Fig. IV-A4), for W CO2 and W H2 S specific charts are given
in the method (IV-A5 ; IV-A6).
For the St Faust gas conditions introduced in the previous item, the predicted water content is :
W HC = 31.36 kg/10³Sm³,
W CO2 = 35 kg/10³Sm³,
W H2 S = 42 kg/10³Sm³,
W CO2 = 0.096,
W H2 S = 0.0648,
W HC = 1 - 0.096 - 0.0648 = 0.8392.
W = 0.8392 x 31.36 + 0.096 x 35 + 0.0648 x 42 = 32.40 kg/10³Sm³.
This value is very close with the value obtained with the Wichert method.
1.3. A.T.G. Chart (Association Technique de l'Industrie du Gaz de France)
The Institute of Gas Technology of Chicago has extensive tables showing the water content of
natural gas over wide ranges of temperature and pressure. These tables are used to legally define
water contents of sales natural gases in specification sheets. Also, they were used to establish the
BUKACEK CORRELATION :
A
W = + B
P
where : W = amount of water contained in the gas (mg/m³ (n)),

P = absolute pressure (bar abs),
A,B = factors function of the temperature,
t = temperature (°C).
Range of temperature : - 40°C to 40°C
A = 4926.5573 EXP (0.0737433 t - 0.00030673912 t²),

B = 44.8739 EXP (0.053570327 t - 0.00019866041 t²).
Range of temperature : 40°C to 90°C
A = 6156.9611 EXP (0.0620686 t - 0.00013096345 t²),

B = 40.5058 EXP (0.055042799 t - 0.00016553793 t²).
Excerpt from PRODEM

DGEP/SCR/ED/ECP
Range of temperature : 90°C to 130°C.
A = 6156.9611 EXP (0.0620686 t - 0.00013096345 t²),

B = 70.0737 EXP (0.032637894 t).
Amounts of carbon dioxide, hydrogen sulfide, nitrogen, heavy ends are poor in sales natural gas,
so ATG Association has established a chart using the Bukacek correlation published in his : "Aide-
mémoire de l'Industrie du Gaz" for sweet natural gases (CO2 mol % < 2 ; H2S mol % < 1.5 ;
relative density < 0.8).
2. COMPUTER PROGRAMS
2.1. General
The previous methods are unable to predict the distribution of hydrocarbons between the
hydrocarbon liquid, aqueous liquid, and gas phases or the water content of the hydrocarbon-liquid
phase.
The water content of hydrocarbon-rich or organic-rich gas in equilibrium with a water-rich liquid can
be made with equations of state (i.e. Peng-Robinson). This approach assumes that the water-rich
liquid phase is 99 mol percent water. When acid gases, methanol, or glycols are present, the
water-rich liquid can contain much less than 99 mol percent water.
A rigorous three-phase (gas or vapor ; water-rich glycol ; hydrocarbon-rich liquid) computer-based

flash calculation can predict the distribution in all three phases of all the components including acid
gases, C6+ fractions, aromatics, and cycloparaffins.
The water content in the hydrocarbon vapor and hydrocarbon-rich liquid phases and the
hydrocarbon content of the water-rich liquid phase are predicted.
In general, the agreement between experimental and predicted water contents is excellent -
usually within 5 %.
In conclusion, methods that include the gas composition are better than those that do not, however
simple and easy-to-use the latter may be. The equation-of-state approach is inherently superior
since it incorporates partial miscibility (or distribution) of all components in all three phases.
However, below 20 bar abs (2 MPa) the sweet gas charts can be used. Above 20 bar abs the
presence of H2S and/or CO2 can increase the saturated water content of a natural gas. The
influence of the acid gases increases with increasing pressure, as clearly shown in figure IV-A3.
Excerpt from PRODEM

DGEP/SCR/ED/ECP
2.2. Thermodynamic computer program use
The maximum water-vapor contained in a gas of known composition (dry bases) is determined
using the three-phase separation operation at given conditions (pressure and temperature).
THREE PHASE
MIXER
SEPARATOR
WET GAS
GAS (dry composition)
HC LIQUID PHASE
P,T
WATER
WATER LIQUID PHASE
Feed is obtained mixing gas of known composition (dry bases) and pure water.
Be aware that the saturated wet gas composition depends of the amount of pure water added to
saturate it. If this amount is too big the composition of the feed is modified, because some
components of gas (dry composition) dissolve in pure water and remain in liquid phase. So the
method consist in adjusting the flowrate of this one to have the minimum of water liquid phase
flowrate (near zero, but not zero).
When using PRO/II program to calculate a three-phase separation, be careful to choose the right
option (see Appendix "PRO/II Flash Unit with decantable water").
Example problem :
Maximum water-vapor content of Saint-Faust gas at reservoir conditions given by HYSIM with
Peng-Robinson equation of state is : 35,43 kg/10³ Sm³.
Excerpt from PRODEM

DGEP/SCR/ED/ECP
WATER-HYDROCARBON PHASE BEHAVIOUR "WATER DEW POINT" DEFINITION
Water is believed to have been present when the gas or the petroleum accumulated in most
reservoirs. In the accumulation, the oil and gas did not completely replace the water adjacent to the
solid surface. This intersticial water found with gas or petroleum in reservoir rock, called connate
water, explains why :
GENERALLY AT RESERVOIR CONDITIONS (PRESSURE, TEMPERATURE).

NATURAL GAS OR PETROLEUM ARE WATER SATURATED.
From reservoir to first separator wellstream pressure and temperature values decrease. In many
cases water vapor condenses in this section involved and a water-liquid phase appears. These are
demonstrated using the Wichert chart.
This chart can be used also to predict in what operation cases water vapor contained in a gas
condenses or not.
If at initial conditions (pressure and temperature) the gas is water saturated its water vapor content
is given by the Wichert chart.
At final conditions (pressure and temperature), the same chart gives its maximum of water-vapor
content. If this last value (at final conditions) is lower than previous (at initial conditions) water-
vapor condense.
The difference of the two water-vapor content values is equal to the amount of liquid water which
appears in the involved section.
If the last value (at final conditions) is higher than previous (at initial conditions) water-vapor does
not condense. The water-vapor content of the gas remains constant.
In this case, the gas is said "undersaturated" at final conditions. That means the gas can accept
more water-vapor at final conditions.
Excerpt from PRODEM

DGEP/SCR/ED/ECP
Different operations cases represented on the Wichert chart
Point (1) : initial conditions (gas is water saturated).

Point (2) : final conditions.
Case 1 : Water vapor condense with the pressure-temperature values variation.

Liquid water appears in the involved section
P ;T P ; T P ;T
W (kg/106 Sm3) W (kg/106 Sm3) W (kg/106 Sm3)

s
s
line
line
line
ure
ure
ure
ess
ess
ess
t pr
t pr
t pr
an
an
an
nst
nst
nst
Co
Co
Co
(1) (1) (1)
(2) (2)
(2)
Temperature Temperature Temperature
Case 2 : Water vapor does not condense with the pressure-temperature values variation.
Liquid water does not appear in the involved section.
P
;
T P T
P ; T P ; T
; ;
W (kg/106 Sm3) W (kg/106 Sm3) W (kg/106 Sm3) W (kg/106 Sm3)
s
s
line
line
line
line
ure
ure
ure
ure
ess
ess
ess
ess
t pr
t pr
t pr
t pr
(2)
an
an
an
an
(2)
nst
nst
nst
nst
Co
Co
Co
Co
(1)
(2) (1) (1) (1) (2)
Temperature Temperature Temperature Temperature
Excerpt from PRODEM

DGEP/SCR/ED/ECP
A water-saturated gas at given conditions (pressure and temperature) is said at its "water
dew point".That means water-vapor begins to condense when gas is slightly cooled at
constant pressure.
In the practice, the water content of a gas is very often defined by the couple of pressure
and temperature values of the "gas water dew point".
If for the same water content of a gas there are an infinite number of "water dew-point", for one
water dew point defined by a couple of pressure and temperature values, there is only one value of
the water-vapor content of the gas.
Be aware "water dew point" is also used when hydrates or ice are produced at given
conditions (pressure and temperature) instead of water liquid.
Fig. IV-A1. is based on the asumption that the condensed water phase is a liquid. However, at
temperatures below the hydrate temperature of the gas, the "condensed" phase will be a solid
(hydrate). The water content of a gas in equilibrium with a hydrate will be lower than equilibrium
with a metastable liquid. This is acknowledged in the "Warning" in figure IV-A1.
Hydrate formation is a time dependent process. The rate at which hydrate crystals form depends
upon several factors including gas composition, presence of crystal nucleation sites in the liquid
phase, degree of agitation, etc.
During this transient "hydrate formation period" the liquid water is termed "metastable liquid".
Metastable water is liquid water which, at equilibrium, will exist as a hydrate. Water content of
gases in the hydrate region is a strong function of composition.
When designing dehydration system (particularly TEG Systems) to meet extremely low water
dewpoint specifications, it is necessary to determine the water content of the gas in equilibrium
with a hydrate using a correlation. If a metastable correlation is used, one will overestimate the
saturated water content of the gas at the dewpoint specification. Where experimental data is
unavailable, utilization of a sound thermodynamic - based correlation can provide an estimate of
water content in equilibrium with hydrates.
Excerpt from PRODEM

DGEP/SCR/ED/ECP
AMOUNT OF WATER LIQUID PRODUCED IN A WELL AND IN A FLOWLINE

DETERMINATION EXAMPLE
Problem : what is the amount of water liquid produced in a well and in a flowline in the
Saint Faust case ?
Stream flowrate : 360 000 Sm³/day (wet basis).
Conditions Pressure Temperature

MPa °C
Reservoir 15 150
Wellhead 5.8 105
First Separator 4.5 60
Solution by Wichert chart method.
1st Step : Using Wichert charts determine at given conditions the maximum water-vapor content
of the gas :
Maximum Water Content (kg/10³Sm³)
Conditions Chart 1 CG Sweet Gas r Sour Gas
Reservoir 32 0.98 31.36 1.05 32.93

Wellhead 17.5 0.985 17.24 1.02 17.58
First Separator 3.8 1 3.8 1.02 3.88
Excerpt from PRODEM

DGEP/SCR/ED/ECP
2nd Step : Determine the amount of water liquid produced at the wellhead :
32.93 - 17.58 = 15.35 kg/10³Sm³
For a stream flowrate of 360 000 Sm³/day

360 000 x 15.35 x 10-3 = 5526 kg/day
or 5.526 m³ of water per day
3rd Step : Determine the amount of water liquid produced at the first separator, when a F.W.K.O.
drum (free water knock-out) is installed at the wellhead.
(17.58 - 3.88) x 360 000 x 10-3 = 4932 kg/d
4th Step : Determine the amount of water liquid produced at the first separator, without F.W.K.O.
drum installed at the wellhead :
5526 + 4932 = 10 458 kg/day
Solution by computer program (Hysim with Peng-Robinson equation of state).
Figure IV-A7 shows the simulation scheme.

Amount of water liquid produced at the wellhead : 6294 kg/day or 6.3 m³/day.
Amount of water liquid produced at the first separator without F.W.K.O. drum installed at the
wellhead : 12049 kg/day or 12.0 m³/day.
Excerpt from PRODEM

DGEP/SCR/ED/ECP
COMPARISON OF PREDICTING METHODS TO EVALUATE THE MAXIMUM OF

WATER VAPOR CONTENT OF NATURAL GASES
Problem : At 101 bar abs the water dewpoint temperature of the Bongkot field gas is 49° C.
Determine, with several methods, the maximum amount of water-vapor of gas at these
conditions.
Data : gas % Mol

composition
CO2 22.81
N2 0.88
C1 65.79
C2 5.47 C7+ CHARACTERISTICS :
C3 2.88
i - C4 0.71 (Molecular weight : 123.548 kg/kmol
n - C4 0.69 (Specific gravity : 771 kg/m³
i - C5 0.27 (Normal Boiling Point : 146.83°C
n - C5 0.18
C6 0.21
C7+ 0.11
Maximum of water-vapor content of gas at 101 bar abs and 49°C
Solution by charts methods Sweet gas Sour gas

kg/106 Sm 3 kg/106 Sm 3
• CAMPBELL 1250 1444

• WICHERT 1300 1430
• G.P.S.A. (Engineering Data Book) 1200 ----
• Raoult Law (Ideal Gas) 889 ----
Excerpt from PRODEM

DGEP/SCR/ED/ECP
Solution by thermodynamic computer programs (with gas composition)
kg/106 Sm 3
• HYSIM (P.R. none option) 1670

• PRO/II (3 options)
♦ S.R.K. 880 (1)
♦ S.R.K. (G.P.S.A. option) 1256 (2)
♦ S.R.K.K.D. (VLLE) 1398 (3)
• FHYD (PENELOUX MARSEILLE) 1528
Remarks : compare the PRO/II result with charts methods results

(1) with Raoult Law ; (2) with G.P.S.A. data ;
(3) with Campbell or Wichert method.
Excerpt from PRODEM

DGEP/SCR/ED/ECP
SCOPE
Resembling dirty ice (solid crystals resembling wet snow), hydrates consist of a water lattice in
which light hydrocarbons molecules are embedded. They are a loosely-linked crystalline chemical
compound of hydrocarbon and water called clathrates, a term denoting compounds that may exist
in stable form but do not result from true chemical combination of all the molecules involved.
Hydrates normally form when a hydrocarbon stream containing free water, dispersed or not, is
cooled below its hydrate formation temperature. At high-pressure these solids form at temperature
above 0°C (15°C at 50 bar abs, 20°C at 100 bar abs). In some cases, hydrates will form in
hydrocarbon gases containing water vapor, without free water condensation.
Hydrate formation causes many operating problems, such as partial or complete blocking of
flowlines, chokes, valves and instrumentation, fouling and plugging of heat exchangers, erosion of
expanders, etc... This is especially true in chokes and control valves where there are large
pressure drops and small orifices. The pressure drops cause the temperature to decrease, and the
small orifices are susceptible to plug if hydrates form.
Heat loss from the flowline causes additional gas cooling.
When hydrate problems occur, consequences can be formidable. Depressurising of pipelines in

deep water to remove plugs frequently require days of flow interruption.
For long gas and multiphase pipelines in cold, high-pressure conditions, insulation alone will not be
always sufficient to maintain a hydrate free channel. To lower the hydrate formation temperature,
an inhibitor has to be injected into the flowlines. The inhibitor in most common use is methanol
because of its relatively low cost, effectiveness and low viscosity when compared to other
inhibitors.
As exploration and production operations move to regions of deeper water or lower temperature,
much more methanol will be required and the issue of economics and technicals problems due to
methanol use will receive more attention.
Typical costs to prevent hydrates in a North Sea processing plant are 5 % to 8 % of the total
operating plant cost. As a result of such economics, work is under way to find alternative and more
economical means of prevention or inhibition.
For all these reasons, it is very important to know in what conditions hydrates appears, the means
to prevent their formation, the means to eliminate a hydrate plug in a pipeline.
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DGEP/SCR/ED/ECP
REFERENCES
• Natural gas Engineering - Production and storage (1990).

Donald L. Katz - Robert L. Lee - Mc. Graw Hill Publishing Company.
• G.P.S.A. - S.I. Engineering Data Book, (1998).

Gas Processors Suppliers Association, Tulsa, Oklahoma, 74103.
• Engineering Data Book, (1994), G.P.S.A., Tulsa, Oklahoma, 74103.
• Gas Conditioning and Processing, (1992).

The basic principles (vol.1) J.M. Campbell.
Campbell Petroleum Series, 1215 Crossroads Blvd, Norman, Oklahoma, 73079.
• Prof. A.C. Todd, Department of Petroleum Engineering, Heriot - Watt University,

Riccarton, Edinburg EH 14 4 AS - Tel.: 44 (0) 131 451 3124.
• K.D. ROBIRDS – J.C. MARTIN – How to design a glycol-injection system

The Oil and Gas Journal – April 30, 1962, p. 85 to 89.
• J.N.J.J. LAMMERS – Phase behaviour of glycol in gas pipeline calculated,

Oil and Gas Journal, Apr. 15, 1991, p. 50-55
• E. GULBRANSEN and J. Hervé MORARD. Why does Glycol inhibit CO2 corrosion
Corrosion 98 – NACE International. Paper N° 221
• J.L. CROLET and J.P. SAMARAN

The use of the anti-hydrate treatment for the prevention of CO2 corrosion in long crude gas
pipelines
Corrosion 93 NACE Annual conference and corrosion show. Paper N° 102
• R. NYBORG - A. DUGSTAD and L. LUNDE

Top-of-the-line corrosion and distribution of glycol in a large wet gas pipeline
Corrosion 93 – NACE Annual conference and corrosion show. Paper N° 77
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DGEP/SCR/ED/ECP
GENERAL
1. HYDRATES COMPONENTS AND PROPERTIES
Hydrates are crystalline compounds that occur when water forms cage-like structures around
smaller guest molecules present in free water.
In general, nitrogen, CO2, H2S and methane, ethane, propane, iso-butane and normal butane are
guests of the host to form hydrate water structure. N-butane only exists in hydrates when other
smaller hydrates forming (i.e. methane) are present.
Pentane and heavier hydrocarbons are too large to fit into the larger cavities to form hydrates.
Hydrate formation is possible in any place where water exists in sufficient quantity to form
aggregates and cage-like structures. The guest molecules provide stability to the lattice structure in
the same manner that liquid in the pores of subsurface sand prevents subsidence. All cages
doesn't have to be full. Therefore, there is no specific formula for hydrates.
Hydrates have specific gravities ranging from 0.96 to 0.98 and therefore float on water and sink in
liquid hydrocarbons. They are 90 weight percent water; the other 10 weight percent is composed of
guest molecules (N2, CO2, H2S, light hydrocarbons).
2. CONDITIONS FOR HYDRATE FORMATION IN A HYDROCARBON MIXTURE
Very often the individual hydrate crystals form in the liquid-water phase. They are very small but
they can grow to form bigger crystals and plugs. Once seed crystals are formed, hydration occurs
readily. Take care, dust and rust particles may act like seed crystals in initiation hydrate formation.
The conditions promoting hydrate formation are:
• hydrocarbon gas or hydrocarbon liquid at or below its water dew point or saturation
condition,
• low temperature,
• high pressure,
• composition.
Hydrate formation is accelerated by agitation (such as high velocities or other turbulence),

pressure pulsations, "seed" hydrate crystals and a suitable site for crystal formation, such as pipe
elbows, orifice plates, thermowells, scale, and solid corrosion products.
Measurements made in Joule-Thomson cooling streams (restricted flow, chokes, …) shows that:
• hydrate formation is rapid in such streams where temperature changes appear to be

highly inhomogeneous,
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• solids forming are hydrate or ice even when the final equilibrium conditions would be
outside the ice region.
These conditions are always present in the process-piping stream.
3. HYDRATE EQUILIBRIUM CONDITIONS IN MULTIPHASE MIXTURES
Hydrates occur in the liquid-water phase in equilibrium with a hydrocarbon phase. This means that
hydrocarbon phase components are in solution in liquid-water phase.
Experiments with different gas phases and "free" water phase, without liquid hydrocarbons show
that a natural gas mixture forms hydrates more readily than any pure components: a mixture of
different molecular sizes is conducive to hydrate formation.
At same pressure, measured hydrate formation temperatures in laboratory cells can be typically 3
to 6°C lower than the values given by the hydrate equilibrium curve (thermodynamic envelope).
The hydrate equilibrium curve corresponds to the hydrate dissociation curve. It is the curve
predicted by most hydrate modelling packages and corresponds to the observed conditions where
melting hydrate disappears. Above these conditions (defined by the couple of pressure and
temperature values) hydrates cannot exist.
The presence of liquid hydrocarbons in addition to gas mixtures and "free" water leads to a
constant hydrate equilibrium temperature depression (inhibition effect). It is obviously caused by
selective solubility of the preferred hydrate former (e.g. propane) in the hydrocarbon liquid phase.
The order of magnitude of the average hydrate equilibrium temperature depression caused by the
presence of liquid hydrocarbons is 1.5 to 2.5°C. The same results were obtained with crude oils as
for light hydrocarbons condensates.
Furthermore, it was observed that water and crude oil with dissolved gas may form hydrates at
room temperature.
Experiments (such as EUCHARIS project conducted by BP and INFOCHEM) have demonstrated

that presence of dissolved salts in production water leads equally to a hydrate equilibrium
temperature depression. The order of magnitude caused by the presence of dissolved salts is
depending of the pressure in the range of 0.7 to 1.2°C for 20 grams of salt (equivalent NaCl basis)
per liter of production water. This behaviour has been observed with different concentrations until
250 grams of dissolved salts per liter of water. For design purpose a mean value of 1°C by 20g/l of
equivalent NaCl could be used to take into account the hydrate inhibition effect of dissolved salts in
production water.
Be aware: presence of "free" or liquid water is not necessary to promote hydrate formation. In
some cases, when the water - content in gas is low, hydrates can form without
presence of "free" or liquid water. This phenomenon appears when the
representative point of the water-content of the gas versus temperature is on the left
of the position of hydrate formation line represented on the Wichert chart (Fig. IV-
A1)
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PREDICTING OF HYDRATE FORMATION CONDITIONS
The temperature and pressure at which hydrates form may be estimated by chart methods and by
computer programs
1. CHARTS
The following method suppose the presence of "free" or liquid water.
Gas-gravity for natural gas (Katz 1945) (Fig. IV-B1)
In Katz's gas-gravity chart, the temperature and/or pressure at which hydrates form is read directly
from one graph. The natural gas is characterised by a single parameter: the relative density of the
gas.
While this method is very simple, description of a natural gas by a single parameter is approximate.
When Katz's method is compared with an equation of state like P.R., excellent agreement is found
for methane and natural gas with relative density up to 0.7. Significant differences are observed for
natural gases with relative density in the range of 0.9 to 1.0.
Example problem:
Determine the hydrate temperature of Saint Faust gas (relative density = 0.7) at 52 bar abs.
Fig. IV-B1 gives: 16.7°C.
2. COMPUTERS PROGRAM
These methods are based on the fundamentals equations of phase equilibrium: namely that when
hydrates form the temperature, pressure, and chemical potential of H2O have the same values in
the natural gas, liquid-water, and solid-hydrate phases.
These methods are superior both in accuracy and ease of extrapolation.
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PREVENTION OF HYDRATE FORMATION
1. GENERAL
Natural gas or H.C. liquid at water saturation condition
HYDRATES
FORMATION
High Low temperature

pressure (order of magnitude < 25°C)
(> 7 bar)
Hydrate formation is promoted by the meeting of the three factors: gas or liquid at water saturation
condition, high pressure, low temperature. On the opposite, the cancellation of one of this factors
prevents the hydrate formation or favours their dissociation when they are yet formed.
The positive manner to prevent hydrates (and corrosion) is to keep the lines and equipment with a
low amount of water.
This condition is achieved when the amount of water required is removed from natural gas or
hydrocarbon liquid in a drying unit at a central facility.
For economics, it is impossible to dry the stream at the wellhead or at the flowline entry. The
decision is therefore to operate a line containing liquid water at high pressure value. In that case,
hydrate formation is prevented by chemical addition or by coating the flowline with a thermal
insulation or by heating the flowline to maintain the stream temperature at a value upper the
hydrate formation temperature.
Flowline heating is used upstream of chokes and in short gathering lines because initial investment
is modest, heaters operate with minimum of attention, and fuel is readily available, often at low
cost. For long flowlines (over 2 or 3 kilometres), the gas approaches ambient temperature and
chemical injection or coating with a thermal insulation may be preferred.
Many chemicals, like alcohols and salts depress the temperature at which hydrates and/or ice
form. This effect is called "hydrate inhibition". The current choice is either a glycol or methanol.
Triethylene glycol (TEG) and tetraethylene glycol (TREG) are too soluble in liquid hydrocarbons
and too viscous for general use ; therefore, the most popular inhibitors are monoethylene glycol
(MEG), diethylene glycol (DEG) and methanol (MeOH). Methanol may be used effectively at any
temperature. DEG is not recommended generally below - 10°C because of its viscosity and the
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difficulty of separation if oil is present. Above - 10°C, it might be preferred as there is less
vaporisation on loss than MEG or MeOH. All may be recovered and recirculated, but the
economics of methanol recovery will not be favourable in most cases.
On the other hand, these inhibitors can cause problems in downstream process units (see
PRODEM Section VI. Products specifications. Undesirable constituents contained in wellhead
stream. § 4.3. Organic compounds in LPG and natural gasolines or condensates). In these cases
efficient inhibitor separation should be provided when possible.
In a multi-phase pipeline, the liquid can literally keep the hydrates from attaching them selves and
growing. So, research and development to prevent the hydrate plugging of the line consist in the
injection in the stream of dispersing additives, which avoid crystal growth and/or agglomeration.
But today, this remains research way.
Hydrates in oil
The studies on hydrate formation and prevention have been mostly focussed on gaseous systems.
Although the formation of hydrates in oil systems is basically the same as that in gas mixtures and
can be described similarly by numerical models, there are major practical differences between the
two systems, which warrant special considerations for oil transfer lines. The main points are:
• Oil systems contain a large concentration of intermediate hydrocarbon compounds, which

are strongly hydrate formers like propane and isobutane. The presence of these
compounds increases the hydrate formation temperature, however oil is mainly composed
on non-hydrate former compounds like C5+, which interfere with the growth of hydrate
crystals. The growth can also be significantly affected by the presence of surface-active
materials in oil. Hydrates formed in an oil transfer line may not therefore block the pipe
and can be generally transferred as slurry.
• Oil wellstreams contain larger amounts of heavy hydrocarbon cuts and water than gas
systems. These components absorb big quantities of conventional chemical inhibitors
prohibiting therefore their economical use.
• Interstitial or injected water produced from oil wells contains salts, whereas the water
accompanying a gas is generally condensed fresh water. Electrolytes inhibit substantially
the formation of hydrates (1°C by 20 g/l of equivalent NaCl).
Thermal capacity of oil is higher than gas. This is why, for the same thermal losses, in flowlines oil
temperature is higher than gas temperature. Consequently hydrates problems occurs usually in
gas flowlines, not in oil flowlines. But that is not necessary true for cold areas such as ultra-deep
offshore production.
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2. DESIGN CONSIDERATIONS FOR HYDRATE INHIBITION
2.1. Economics
For continuous inhibition one of the glycols usually offers an economic advantage; for temporary
inhibition methanol is preferred.
Diluted glycols are separated from the liquid water, reconcentrated and reused. Methanol recovery
may be marginally economical due to its low cost and high vaporisation losses. However, if the gas
stream is dried downstream in a TEG unit, methanol can be recovered easily and economically
from the TEG regenerator overhead. Glycol is usually cheaper where continuous injection is
required and/or high gas volumes are being inhibited. Because of its lower capital investment (no
recovery units), methanol is frequently used for low gas volumes, temporary installations, or where
hydrate problems are mild, infrequent or seasonal.
In conclusion, methanol injection has a low investment cost but a high operating cost due to the
chemical consumption. Injection of MEG or DEG requires a higher initial cost but a relatively low
operating cost.
One rule of thumb is that glycol units are used when the required methanol injection on permanent
inhibition exceeds 120 l/hr.
2.2. Methanol specific problems
Methanol injection can cause the following three problems if the gas is subsequently passed
through a glycol dehydration plant:
• Methanol is co-absorbed with water vapor by the glycol and so increases the glycol
regeneration heat load (any methanol vented to the atmosphere with the water vapor from
the regeneration still is hazardous).
• Aqueous methanol can corrode carbon steel in the glycol still and reboiler vapor space.
• Methanol also can reduce the capacity of solid desiccant pellets (i.e. molecular sieves),
because methanol is readily co-adsorbed and competes with water for desiccant surface.
Handling methanol requires care: methanol can permeate through thermoplastic

umbilical hoses and can degrade certain hose materials.
Proper safety precautions have to be observed. Methanol is toxic, therefore, inhaling

vapors and/or prolonged contact with skin, have to be avoided.
Swallowing is very dangerous: death can quickly follows.
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3. QUANTITY OF INHIBITOR REQUIRED TO PREVENT AN HYDRATE FORMATION
3.1. Minimum inhibitor concentration in the free water phase
The minimum inhibitor concentration in the free water phase may be calculated, using two
approaches:
• the semi-empirical correlations Hammerschmidt is the most famous (1939),

• the computer simulations.
Hammerschmidt correlation matches very well with laboratory equilibrium data for hydrate
inhibition with methanol solutions up to about 25 weight % and glycols to about 60 to 70 weight
percent.
For methanol concentrations up to about 50 %, the Nielsen-Buckling correlation provides better

accuracy.
Be aware: in truth, no method applies to all systems, because it is affected by system dynamics,
configuration, location and method of injection, etc... Most experienced operators will
adjust the injection rate by trial-and-error following initial start-up.
Here is one of many process calculations that provide little more than a "safe" estimate to guide
operations. An "approximate number" is better than "no number".
The following Hammerschmidt correlation estimates the minimum inhibitor concentration required
in the exit water phase resulting from the original water and that added with the inhibitor to prevent
hydrate formation:
100 M ∆t
W =
M ∆t + Ki
Where:
W: weight percent pure inhibitor, in liquid water phase,

∆t: desired depression of hydrate formation temperature (°C),
M: molecular weight of inhibitor (kg/kmol),
Ki: Hammerschmidt constant (°C.kg/kmol)
Inhibitor MeOH MEG DEG
M (kg/kmol) 32 62 106
Ki (°C.kg/kmol) 1 297 2 220 2 220
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The following Nielsen-Bucklin correlation estimates the minimum methanol concentration required
in the exit water phase resulting from the original water and that added with the methanol to
prevent hydrate formation:
100
W =
0.5625 EXP (- ∆t / 72 )
1 +
1 - EXP (- ∆t / 72 )
Where:
W: weight percent pure methanol, in liquid water phase,

∆t: desired depression of hydrate formation temperature (°C).
3.2. Inhibitor losses to the hydrocarbon phase
The amount of inhibitor to be injected not only must be sufficient to prevent the inhibitor water
phase freezing, but also must be sufficient to provide for the loss in the vapor phase and for the
inhibitor solubility in any liquid hydrocarbon.
3.2.1. Vapor-phase inhibitor losses
Glycols have very low vapor pressures and accordingly vapor-phase losses should be very small
(4 kg/106 Sm³).
Methanol, on the other hand, is quite volatile and vapor-phase losses must be included.
Jacoby (1955) correlated the vaporisation losses in terms of the lowest temperature in the hydrate
inhibition system and the corresponding pressure. Figure IV-B17 presents the ratio of the gas-
phase methanol concentration (kg MeOH/106 (n)m³) to that in the liquid (weight percent MeOH) at
the previously-cited minimum temperature and corresponding pressure.
Be aware: at pressures greater than about 6.9 MPa (69 bar), vapor losses may be several times
higher than those indicated in Figure IV-B17, particularly at high methanol
concentrations.
3.2.2. Hydrocarbon liquid-phase inhibitor losses
Methanol solubility in the hydrocarbon liquid phase is composition dependent. For paraffins,
solubility is low, for aromatics, it is high. So, total liquid phase losses can be significant.
At typical pipeline inhibition conditions, Campbell recommends to adopt a solubility of about
0.4 kg/m³ for planning purposes. This assumes a paraffinic hydrocarbon liquid only, but Campbell
points out that methanol solubility in aromatic hydrocarbons can be 4-5 times higher than this. Ken
Arnold gives methanol solubility in liquid hydrocarbons of about 3 % by weight…
GPSA Engineering Data Book (1998 ed.) presents experimental data showing that solubility of
methanol in a paraffinic hydrocarbon liquid is a function of temperature and methanol
concentration. The order of magnitude of methanol dissolved in condensates is 2kg/m 3. It is
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DGEP/SCR/ED/ECP
indicated that methanol solubility in naphtenic hydrocarbons is slightly less than paraffinic, but
solubility in aromatic hydrocarbons may be four to six times higher than in paraffinic.
For design purpose a loss of 6 kg/m 3 of hydrocarbon liquid could be considered.
All these facts are disturbing. They reveal a lack of knowledge.
Glycol solubility in hydrocarbon liquids increases with:
• an increase in molecular weight of the glycol (TEG is more soluble than DEG, and DEG
than MEG),
• an increase in temperature,
• an increase in weight percent glycol in the water-glycol mixture.
Glycol solubility also depends on the type of hydrocarbon liquid present. Glycols are more soluble
in aromatics and naphtenes than in paraffin hydrocarbons.
True glycol solubility in the hydrocarbon liquids normally occurring at 15°C and for 50-70 weight
percent glycol concentrations, range from 10 to 50 ppm for MEG and 20 to 100 ppm for DEG.
These losses are approximately 0.008 to 0.08 kg/m³ hydrocarbon liquid. Glycol solubility losses
would be lower at lower separation temperatures. For design purpose a total losses of 0.2 kg/m³
hydrocarbon liquid are not uncommon.
3.2.3. Inhibitor losses in regeneration system
Methanol is often not recovered and reconcentrated so no regeneration equipment is needed.
MEG and DEG are lost in regeneration equipment:
• by decomposition in and carry-over from the regenerator,

• by carry-over from the separation of oil from the glycol water-phase.
Carry-over losses from the separator and regenerator vary widely with equipment design and
operation but are usually less than 25 kg/106 Sm³ gas flowrate
Regeneration losses should be small in a well-designed unit unless salt contamination tends to
plug the still column. Salt is a problem in its own right for the water is distilled off and leaves the
salt behind. Salt can be removed from glycol only by vacuum distillation reclaiming.
4. DESIGN TEMPERATURE TO BE ADOPTED FOR EQUIPMENT DESIGN TO PREVENT

HYDRATE FORMATION IN A HYDROCARBON MIXTURE
In some cases hydrate formation is prevented by coating the flowline with a thermal insulation or
by heating the flowline to maintain the stream temperature at a value upper the hydrate formation
temperature.
In other cases for process reasons the stream is cooled till the possible lowest temperature, which
can be the hydrate formation temperature.
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DGEP/SCR/ED/ECP
In such cases the design temperature to prevent hydrates formation is equal to the computed
hydrate formation temperature plus a safety margin of 3°C.
USE OF GLYCOLS TO INHIBIT SIMULTANEOUSLY HYDRATE FORMATION AND

CO2 CORROSION
1. GENERAL
Transportation of wet CO2-containing gases in pipelines requires special measures to prevent

corrosion of the pipe wall. A relatively new option uses injection of monoethylene glycol (MEG) or
diethylene glycol (DEG) to inhibit simultaneously hydrate formation and CO2 corrosion in a number
of wet gas pipelines such as the Troll pipeline.
Troll pipeline is a twin, 66 kilometres, 36 inches pipeline system for the transportation of natural
gas from the offshore Troll field to the mainland. Water-saturated gas is allowed in the pipeline,
and drying of the gas is carried out onshore. To transport the wet, CO2 – containing natural gases
in pipelines without unacceptable corrosion of the steel pipewall, glycol, among others, is injected
at the upstream end of the pipeline, on the platform. Installation of the glycol-treating unit onshore
instead of on the platform represents, apart from capital savings, improved operational flexibility.
Note: As MEG or DEG, methanol inhibits simultaneously hydrate formation and CO2 corrosion in
wet-gas transport lines.
From an environmental point of view, glycol presents a low toxicity, it is not surface active, it is not
bioaccumulable, it is degradable and it is recyclable in the process. With respect to occupational
health, it is not significantly irritating to the eyes and skin, is not readily absorbed through the skin
and its vapor pressure is sufficiently low so that toxic concentrations cannot occur in the air at room
temperatures.
2. GLYCOL INJECTION EFFECT
2.1. Corrosion inhibition effect
CO2 corrosion of carbon steel and its inhibition in mixtures of water and monoethylene glycol or
diethylene glycol has been studied. Experimental results shows that the corrosion inhibition effect
of MEG and DEG is due to changes in water solution properties. With the increase of MEG or DEG
concentration, CO2 solubility, CO2 diffusivity, water activity and solution polarity decrease, but
solution viscosity increase. Furthermore the addition of a pH controlling agent such as amines
(MDEA for instance) or MBTNa enables the stratified aqueous phase to be rendered completely
non-corrosive.
2.2. Top-of-the-line corrosion and distribution of glycol in a large wet gas

pipeline
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As the gas in the pipeline is gradually cooled, water and hydrocarbon condense out and form
separate liquid phases in the bottom of the line. Water is corrosive and can attack both the top of
the line when water in gas condense and the bottom of the line when liquid water settle. By adding
an adequate amount of glycol an acceptable life time of the bottom of the pipeline can be obtained,
but corrosion might still be a problem in the top of the line in stratified flow.
When the pipeline is cooled, the condensing water will wash the glycol out of the gas phase, and
for a stratified flow the water/glycol mixture can be trapped under the hydrocarbon condensate in
the bottom of the line. Further along the pipeline the gas phase and the condensing water can then
be almost free from glycol. This phenomenon will occur only under stratified flow conditions. In slug
flow regimes, no “top-of-the-line” condensation will occur. Moreover, in the slug-flow case, gas and
liquid will resume equilibrium because of intense contact.
In stratified flow regime the amount of glycol in droplets in the gas is much higher than the amount
of glycol as vapor and make a significant contribution to the glycol content of the water condensing
at the top, even when a hydrocarbon layer covers the glycol in the bottom. The presence of a
hydrocarbon layer strongly reduces the glycol droplet content in the gas for flow conditions typical
for large wet gas pipelines. The glycol content in the gas is low for 1.2 and 4.2 m/s gas velocity
when a liquid hydrocarbon layer is present, but increases markedly from 4.2 to 6.4 m/s.
One solution to limit the top-of-the-line corrosion in a wet gas pipeline operated at low flow regime
or at stratified flow regime would be to send periodic glycol slugs a the upstream end of the
pipeline.
For more information and solutions contact DGEP/DO/TEC.
2.3. Glycol slug effect
On an other way, experience shows when a batch of glycol is transported through the pipeline,
accumulated water is swept out and transported as slug through the pipeline.
For a period of time after the slug has passed through the pipeline, the water remains mobile, and
the accumulation in the pipeline is reduced. The presence of inhibitors, should therefore be taken
into account when modelling multiphase flow. The observed influence of glycols on water mobility
is assumed to be a result of altered wettability of the pipeline walls.
3. QUANTITY OF INHIBITOR REQUIRED TO PREVENT CO2 CORROSION
The level of corrosion reduction depends on, among other factors, the composition of the liquid
glycol-water mixture, but to obtain significant reductions in the corrosion rates high concentrations
of glycol are needed (corrosion rate decreases with increasing glycol concentration). Experience
shows that the solubility of CO2 in the aqueous phase decreases with increasing mass percentage
of glycol in the aqueous phase to about 60 %. Above this concentration the solubility again
increases.
To transport wet CO2 containing natural gases in pipelines, minimising the corrosion rates,
DGEP/DO/TEC recommend to adopt a minimum of 50 % as mass percentage of glycol in the
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DGEP/SCR/ED/ECP
aqueous phase. For more details and for new studies of wet natural gas transport in pipelines
contact DGEP/DO/TEC.
In many cases, where hydrate formation and CO2 corrosion must simultaneously be inhibited the
maximum amount of mass percentage of glycol in the aqueous phase is governed by CO2
corrosion inhibition. However in each case computation to determine the quantity of inhibitor
required to prevent an hydrate formation must be done.
GLYCOL – INJECTION SYSTEM INTO PROCESS
To be effective, glycols may be sprayed into the wet gas as very small droplets. If intimate mixing
of the fine liquid glycol spray and the natural gas is not achieved, then glycol injection may not
prevent hydrate formation. The inhibitor must be present at the very point where the wet gas is
cooled to its hydrate temperature: for instance, before a chiller. Therefore, the inhibitor is sprayed
upon the face of the feed gas chiller tube sheet where free gas is present. Injection must be in a
manner to allow good distribution to every tube in chillers and heat exchangers operating below the
gas hydrate temperature.
When expansion lowers gas temperatures below the hydrate point, glycol must be injected into the
line immediately upstream of the expansion. If refrigeration of the gas will take place through a
series of heat exchangers, glycol must be injected at the inlet of each exchanger in which hydrates
conditions will be reached. Glycol flow to each heat exchanger must be proportioned to the
quantity of water condensed there, as compared to the total water load.
If a cooler is used before refrigeration, and glycol is determined to be unnecessary there because
hydrate conditions will not be reached even though water will be condensed, a water-separator pot
should be provided immediately downstream. If hydrate conditions are reached in this cooler,
sufficient glycol to absorb the condensed water will have to be injected upstream this cooler.
Piping layout, or type of heat exchanger involved, will be important.
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DGEP/SCR/ED/ECP
MEANS USED TO ELIMINATE AN HYDRATE PLUG
1. ELIMINATION OF AN HYDRATE PLUG IN A PIPELINE OR A FLOWLINE

(depressurisation from both ends of the pipeline is possible)
1.1. General
Increasing the temperature to remove a hydrate blockage is not usually practical since
the blockage has to be first located and then heating equipment applied to the blockage
area. Nevertheless, this method can be applied in particular cases.
A pipeline plugged with hydrates can be unplugged by reducing the pipeline pressure
on both sides of the plug.
Reducing the pressure on only one side is EXTREMELY DANGEROUS, the solid hydrate
plug can break loose. Then the pipeline pressure drives the ice-hard hydrate plug
towards the lowered pressure side at very high velocity. When the hydrate hits a bend or
restriction, it can break the pipe and even unearth a buried pipeline. Such accidents
have resulted in loss of lives and extensive equipment damage.
1.2. Procedure to eliminate an hydrate plug
1st step: Reduce slowly by steps the pipeline pressure on both sides of the plug, one side
down a pressure near atmospheric pressure, other side down a pressure of few bars
(< 6 bar).
Quick gas depressurisation could generate a gas cooling to negative temperature
values which favour ice formation and prolong in such case melting period of the
hydrate plug. To prevent this event it is a good practice to control the gas temperature
during depressurisation. On the other hand quick depressurisation favours the loosing
of hydrate plugs when several hydrate plugs are formed in the pipeline.
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DGEP/SCR/ED/ECP
4-5 bar Atmosphere
Hydrate Plug
2nd step: Inject methanol to the upper pressure pipeline side when the pressure value starts to
decrease.
In that case, the small flow brings the methanol towards the hydrate plug and favors
by contact his dissociation.
Methanol can dissolve existing hydrates to some degree.

It is not true with glycol: glycol can prevent hydrates, but cannot attack or
dissolve hydrates already present.
2. ELIMINATION OF AN HYDRATE PLUG FROM A SUBSEA FLOWLINE

(depressurisation from one side (platform side) is only possible)
2.1. Localisation of the hydrate plug
Hydrate plugs are porous, thus there is a certain throughflow of gas when there is a differential
pressure over the plug. This fact is used to estimate the location of an hydrate plug in a subsea
gas flowline with the procedure as follows:
1st step: Note the pressure value P1 of the gas in the flowline at the wellhead side and
decrease the gas pressure in the flowline at the platform side to a value P2.
2nd step: Close the flowline at both ends for several hours and wait to observe a sufficient
pressure variation at both flowline sides (two days may be necessary in some cases,
because gas leakage rate through the plug is slow).
3rd step: Note the new pressure value P1' of the gas in the flowline at the wellhead side and the
new pressure value P2' of the gas in the flowline at the platform side.
4th step: Assuming gas temperature is the same along the flowline during all this
experimentation, location of one hydrate plug is given by equation as follows:
Excerpt from PRODEM

DGEP/SCR/ED/ECP
L2 = L
(P − P ) '
(P − P ) − (P − P )
1 1
' '
1 2 1 2
where:
L2 = distance length between the hydrate plug and the platform end
of the flowline,
L = total length of the flowline between the wellhead end and the
platform end,
P1, P1' = gas pressure values at wellhead side at beginning and end of
the observation period of gas pressure variation,
P2, P2' = gas pressure values at platform side at beginning and end of
the observation period of gas pressure variation.
2.2. Proposed procedure to eliminate the hydrate plug

(several days can be required)
1st step: Close the flowline at both ends and decrease the gas pressure downstream the plug
in steps until 10 bar to control that the plug do not loosen from the wall with severe
safety risk. After each pressure reduction step close in again the flowline at the
platform side.
Note: gas flowrate through the plug does not seem to be very dependent on
variations of the differential pressure over the plug.
During gas throughflow of the hydrate plug the temperature at the plug downstream
end might be significantly reduced due to the Joule-Thomson effect. When a
differential pressure between upstream and downstream of the hydrate plug is too
high a value below 0°C can be reached.
In such case the released water during hydrate melting form ice. This prolongs the
melting period extensively and also creates a dangerous situation since an ice plug
melts from the pipewall and inwards. The plug hence looses the adhering forces to
the pipe wall and moves in the flowline at very high velocity with the risk of breaking
the pipe at a bend or restriction location.
To prevent this occurrence gas pressure downstream the hydrate plug must be
maintained at a value 30 per cent lower than the upstream gas pressure.
2nd step: When the gas pressure at the platform side reach 10 bars, keep this value all the time
of melting of hydrates to avoid ice formation.
The platform side closed the gas pressure downstream the hydrate plug increase due
to the low flow of gas through the plug. Take down this gas pressure to 10 bars
several times.
3rd step: When a breakthrough take place in the plug there is a quasi-egalisation of gas
pressure upstream and downstream the hydrate plug. Continue to keep the gas
pressure in the flowline to 10 bars for some hours to melt the rest of the hydrates and
prevent ice formation. After that depressurise the flowline to atmospheric pressure to
reduce the amount of hydrate forming components present.
Excerpt from PRODEM

DGEP/SCR/ED/ECP
4th step: Inject methanol plug topside and pressurise flowline with diesel. Volume pumped
must correspond to the flowline volume.
Flowline can be put into production.
Excerpt from PRODEM

Hydrates Formation and Inhibition

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"OIL AND GAS PROCESSING PLANT DESIGN 2002

AND OPERATION TRAINING COURSE"

Excerpt from PRODEM

PREDICTING METHODS TO EVALUATE THE MAXIMUM OF WATER

WATER-HYDROCARBON PHASE BEHAVIOUR "WATER DEW POINT"

AMOUNT OF WATER LIQUID PRODUCED IN A WELL AND IN A FLOWLINE

COMPARISON OF PREDICTING METHODS TO EVALUATE THE MAXIMUM

Excerpt from PRODEM

PREDICTING OF HYDRATE FORMATION CONDITIONS 25

PREVENTION OF HYDRATE FORMATION 26

USE OF GLYCOLS TO INHIBIT SIMULTANEOUSLY HYDRATE FORMATION

GLYCOL – INJECTION SYSTEM INTO PROCESS 34

MEANS USED TO ELIMINATE AN HYDRATE PLUG 35

Excerpt from PRODEM

PRO/II – Flash Unit with decantable water

Figure IV-B1 - Gas-gravity chart for natural gas (Katz)

Excerpt from PRODEM

Hysim program gives satisfactory results.

Excerpt from PRODEM

♦ reduce the capacity of transport of the pipelines.

• Gas Conditioning and Processing, (1992).

• Chart estimates water content of Sour Natural Gas,

• A.S.T.M. - D 1142-63 (1963 and 1980).

Excerpt from PRODEM

The amount of water vapor contained in a gas is expressed in :

w Gas volume at standard conditions

w Normal conditions (n) is : 101.325 kPa (1 atmosphere normal), 0°C.

The water-vapor content of a gas is given in :

Excerpt from PRODEM

• pressure and temperature values of the gas,

PREDICTING METHODS TO EVALUATE THE MAXIMUM OF WATER VAPOR

1.1. Wichert charts published in 1993 ( Fig.IV-A1, 2 and 3)

• pressure to 70 MPa (700 bar),

Excerpt from PRODEM

In correction salinity chart, the total solids in brine is defined as follows :

Solids or salts mass in brine

% Equivalent H2S = 100 (Y H2S + 0.75 YCO 2 )

Total water content of sour gas is given by following :

with : W = water content (kg/10³ Sm³ of wet gas),

1.1.2. Example problem

Composition (dry bases) % mol

Excerpt from PRODEM

Molecular weight : 22.2 kg/kmol

3rd Step : Calculate the equivalent H2S content of the mixture

% equivalent H2S = 6.48 + 0.75 x 9.60 = 13.68 %

31.36 x 1.05 = 32.93 kg/10³ Sm³

1.2. Campbell charts

The Campbell method is introduced in :

• G.P.S.A. Engineering Data Book,

It uses the following empirical combination rule :

W = YHC WHC + YCO 2 WCO2 + YH2S WH2S

with : W = Water content of sour gas,

W HC = water content of sweet gas,

Excerpt from PRODEM

W H2 S = effective water content of H2S,

W = 0.8392 x 31.36 + 0.096 x 35 + 0.0648 x 42 = 32.40 kg/10³Sm³.

1.3. A.T.G. Chart (Association Technique de l'Industrie du Gaz de France)

where : W = amount of water contained in the gas (mg/m³ (n)),

Range of temperature : - 40°C to 40°C

A = 4926.5573 EXP (0.0737433 t - 0.00030673912 t²),

Range of temperature : 40°C to 90°C

A = 6156.9611 EXP (0.0620686 t - 0.00013096345 t²),

Excerpt from PRODEM

Range of temperature : 90°C to 130°C.