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Copyrights
This presentation contains copyrighted
material as indicated in the attributions
on individual slides, or by F. Civan
2003. This material is provided in
support of class presentation and for no
other use. Permission for any other
use, duplication or distribution must be
obtained from the copyright holder.
Copyright 2003 by Faruk Civan
Important Notice
Natural Gas
Hydrates
Copyright 2003 by Faruk Civan
= 3,208 psia
Estimating Water
Content
VaporPressure
For H2O
Temperature
Copyright 2003 by Faruk Civan
Estimating Water
Content
Daltons Law:
PT
i = 1
=
=
Pi
Pi
PT
P
vap
w
PT
Estimating Water
Content
If the laboratory analysis shows the
molar concentration of the species Yi
in the dry gas analysis, then the
corrected analysis for the water vapor
saturated gas can be obtained
from the following equation:
Copyright 2003 by Faruk Civan
Estimating Water
Content
(Y i )C
Mole of i/mole
of saturated
gas
= (Y i
)L
(1 Y w
Mole of i/mole
of dry gas
(from lab)
Copyright 2003 by Faruk Civan
Mole of dry
gas/mole
of saturated gas
9
Estimating Water
Content
Thus the water content of a gas is:
WHC
WHC
WHC
Yw
1 lbmole
lbmole _ W
lbm _ W
=
M
w
380 .9 SCF
(
)
1
_
_
Y
lbmole
gas
lbmole
W
Yw M w
Yw M w 10 6
or
WHC =
=
380 .69 (1 Yw )
380 .69 (1 Yw )
lbm
=
MMscf
10
Estimating Water
Content
Looking back to the previous equation
and substituting the value of Yw
vap
w
P
Yw =
PT
W HC
P M w 10
=
vap
P Pw 380 . 69
vap
w
11
Estimating Water
Content
For high pressure, charts should
be used
VaporPressure
For H2O
P1
P2
P3
P4
P1<P2<P3<P4
Temperature
Copyright 2003 by Faruk Civan
12
),
ps
ia
(Is
ob
ar
s
ss
ur
e
Pr
e
WHC!
WHC2
Temperature, T 13
14
Estimating Water
Content
Hydrogen sulfide and carbon dioxide
are very common contaminants in
natural gas.
15
Estimating Water
Content
General Formula (GPSA):
16
Effective Water
Content, Lb/MMscf
Isobars
Temperature
Source: GPSA Figure-20.9
Copyright 2003 by Faruk Civan
17
Effective Water
Content, Lb/MMscf
Isobars
Temperature
Source: GPSA Figure-20.8
Copyright 2003 by Faruk Civan
18
Hydrate
As defined by GPSA:
Hydrate is a
physical combination of water and
other small molecules to produce a
solid which has an ice-like
appearance but possesses a
different structure.
19
Hydrate
Why hydrate is not desired ?
Pipeline
Equipment
Instrumentation
20
Hydrate
When gas is produced to the surface,
there are two hydrate inducing
factors:
Reduction in temperature
Reduction in pressure
Copyright 2003 by Faruk Civan
21
Hydrate
Hydrate
Formation
Pressure
Specific
Gravity
1.0
Temperature
Copyright 2003 by Faruk Civan
22
Pressure
PT Chart for
Hydrate Formation
ne r.
a
th p.G
e
M 6S
0.
0.7.8
0 Hydrate-Free
Region
Temperature
Source: GPSA Figure-20.15
Copyright 2003 by Faruk Civan
23
T
J =
P H
< 0, then P
Pi and
Ti
and T
Pf and
Tf
24
Initial Pressure
Temperature
Tinitial
o isotherm
Tfinal
o
isotherm
No
hydrates
Hydrate
formation
Pfinal
Final Pressure
Intersection
with the 45o
line gives the
final
temperature
to be reached
after
expansion
Source: GPSA
Figure-20.16
25
Example 2 Expansion /
Hydrate Formation
Given:
Initial P = 3000 psia, T=160 oF; and gas
specific gravity is 0.7
Required:
What is the minimum pressure to
which the gas can be expanded
without forming hydrate and to what
temperature will the gas be cooled ?
Copyright 2003 by Faruk Civan
26
Example 2
Initial Pressure
Temperature
Source:
GPSA
Figure20.17
3,000 psia
160oF
158 psia
59oF
Specific
Gravity = 0.7
Final Pressure
Copyright 2003 by Faruk Civan
27
Example 2
Given:
A 0.7 gravity natural gas is saturated
with water vapor at 150 oF and 3,000
psia. This gas is expanded through a
choke and its pressure is reduced to a
pressure of 1000 psia.
Required:
Will hydrate be formed at the outlet of
the choke?
Copyright 2003 by Faruk Civan
28
Example 2 (Solution)
Enthalpy
Btu/lbmole
Pressure, psia
Isobars
Entropy, Btu/lbmoleoF
Copyright 2003 by Faruk Civan
29
Example 2 (Solution)
Pressure
Region
Temperature
No hydrate will be formed
Copyright 2003 by Faruk Civan
30
Vapor-Solid
Equilibrium
Reference: SPE15306 and SPE 50749
Vapor
Solid
hydrate
31
Vapor-Solid
Equilibrium
Let:
Xi = Mole fraction of component i in
the solid hydrate phase on a waterfree (or dry) basis
Yi = Mole fraction of component i in
the vapor phase on a water-free (dry)
basis
Copyright 2003 by Faruk Civan
32
Vapor-Solid
Equilibrium
The vapor-solid equilibrium ratio for
species i is given by:
Yi
Kvsi = = Kvsi (P,T)
Xi
Similar to dew-point calculation, for
the first hydrate phase formed, it is true
Yi
that
=1
X =1
i =1
K
i =1
vsi
( P, T )
33
Vapor-Solid
Equilibrium
Application:
34
Vapor-Solid
Equilibrium
Iso-bars
Y
K =
X
Increasing
Pressure
Temperature
Note: Each component has its own chart
Copyright 2003 by Faruk Civan
35
Hydrate Prevention
Hydrate formation can be avoided by
using the following methods:
Operating outside the thermodynamic
condition (P&T) of hydrate formation.
This is done by adjusting the values of
temperature and pressure
Using dehydrating processes to
remove free water
Adding hydrates inhibitors
Copyright 2003 by Faruk Civan
36
Kinetic Hydrate
Inhibitors
A polymeric material that delays the
hydrate crystal growth
N-vinylpyrrolidone
N-vinylcaprolactam
Saccarides
Copyright 2003 by Faruk Civan
37
Anti-agglomerates for
Hydrate Inhibition
Prevents agglomerations of hydrate
crystals from growing into large
size
38
Thermodynamic
Hydrate Inhibitors
Methanol
Ethanol
Iso-propanol
Ethylene glycol
Propylene glycol
Diethylene glycol
Copyright 2003 by Faruk Civan
39
Controlling Operating
Conditions
a. Controlling hydrate temperature.
b. Controlling of hydrate formation
pressure.
40
Controlling hydrate
formation temperature
Keeping gas above hydrate formation
temperature.
a. Heating the transmission line
continuously by means of electrical
heater. Temperature normally has
limitation to protect pipeline integrity.
Copyright 2003 by Faruk Civan
41
Controlling hydrate
formation temperature
b. Heating can also be accomplished by
an exothermic chemical reaction.
NaNO2 + NH4NO3 N2 + 2H2O
+NaNO3 + Heat
Risk: N2 gas can overpressure the
system Copyright 2003 by Faruk Civan
42
Controlling hydrate
formation pressure
Rapid pressure reduction causes
overcooling and hydrate formation
Lower the pressure gradually at
isothermal conditions
Avoid sudden pressure reduction
Copyright 2003 by Faruk Civan
43
Dehydration
Processes
Remove free water by two means:
44
Hydrates
Inhibitors
Salts
Alcohols
Ammonia
Monoethanolamine
Copyright 2003 by Faruk Civan
45
Salts Inhibitors
Aqueous solutions salts are:
46
Salts Inhibitors
Chlorides: Effectiveness sequence
Al+3 >
AlCl3
Mg+2 >
MgCl2
Ca+2 >
CaCl2
Na+ >
NaCl
K+
KCl
47
Alcohols Inhibitors
Types:
Methanol base
48
Alcohols
Inhibitors
Applications for cryogenic
processes:
49
Alcohols
Inhibitors
Applications for non-cryogenic
conditions:
50
51
CH3OH
EG or TEG
CaCl2
AlCl3
Hydrate
Inhibitors Effect
Wt % in
water 52
K
T =
M
H
w
100 W
53
54
Exercise
Answer the following questions:
1. What are the basic methods used in
hydrate prevention?
2. Describe the various methods
available for prevention of hydrate
formation and their operating
principles.
3. List the primary hydrate inhibitors.
Copyright 2003 by Faruk Civan
55
Exercise
Ethylene glycol (C2H6O2) will be used
as a hydrate inhibitor at a 25 wt. %
concentration in water. Answer the
following questions:
1. What is the molecular weight of ethylene
glycol?
2. How much will the ethylene glycol
solution lower the temperature for
hydrate formation?
Copyright 2003 by Faruk Civan
56
Exercise
A reservoir contains a 0.65 specific
gravity natural gas at 200 oF and
4,000 psia conditions. The wellhead
conditions are 130 oF and 2,000
psia. The wellhead gas is expanded
through a choke to reduce its
pressure to 1,200 psia. Determine:
57
Exercise
1. The amount of free water present
58
Exercise
Development and Demonstration of a
Hydrate Prediction Program.
Carry out the following project based
on Paper SPE 15306, Hydrate
Prediction on a Microcomputer by
B.K. Berge, 1986. However, you can
also use other relevant references.
Copyright 2003 by Faruk Civan
59
Hydrate
Prediction
60
Hydrate
Prediction
Present the equations separately
for:
(a) Compositional gases
(b) Non-compositional gases
61
Hydrate
Prediction
Prepare a step-by-step
computational algorithm required to
carry out calculations for hydrate
prediction for compositional and
non-compositional gases in a
logically sequenced manner.
Copyright 2003 by Faruk Civan
62
Hydrate
Prediction
63
Hydrate
Prediction
64
Hydrate Prediction
65
Hydrate
Prediction
(b) Prepare typical charts for
hydrate prediction for noncompositional gases. You may
present charts in 2- and 3-variables
forms.
Copyright 2003 by Faruk Civan
66
Hydrate
Prediction
(c) Demonstrate several applications of
your program using typical data
similar to those presented in SPE
15306. Decide and present
representative applications, which
best illustrate the capabilities of
your program.
Copyright 2003 by Faruk Civan
67
Hydrate
Prediction
68
References
K. Arnold and M. Stewart, Surface
69
References
Y.E. Makogan and S. A. Holditch, Lab
70