PE5623 - Lecture 05 - Natural Gas Hydrates PDF

Natural Gas Processing
Dr. Faruk Civan, Ph. D.

Professor, The University of Oklahoma
Copyright 2003 by Faruk Civan
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on individual slides, or by F. Civan
2003. This material is provided in
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Important Notice
All of Dr. Faruk Civans lecture

notes, course syllabuses, handouts,
homeworks, and exams are
copyright material.
They cannot be reproduced,
recorded and copied in any way or
form without the written permission
from Dr. Faruk Civan. All rights
reserved.
Natural Gas
Hydrates
H2O Vapor Presence

Critical values for water:
Critical Pressure
= 3,208 psia
Critical Temperature = 705 oF
Reservoir pressures are much

higher, therefore, gases are
saturated with H2O vapor
Estimating Water
Content
VaporPressure
For H2O
Temperature
Estimating Water
Content
Daltons Law:
PT
Mole (Vol.) Fraction: Y

H2O partial
Pressure:
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:
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)
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
Industrial Practice of reporting

water content
(Sales Gas Specification is 7 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
12
),
ps
ia
(Is
ob
ar
s
ss
ur
e
Pr
e
Water Content, lb/MMscf
Mcketta and Wehe

Chart
WHC!
WHC2
Temperature, T 13
Mcketta and Wehe

Chart
Most Common chart used in the
processing industry
This chart is for hydrocarbon
gases only
It has been used in design since
1958
Source: GPSA Figure-20.3
14
Estimating Water
Content
Hydrogen sulfide and carbon dioxide
are very common contaminants in
natural gas.
Correction factors are applied to

correct the water content estimation
in natural gas
15
Estimating Water
Content
General Formula (GPSA):
Wtotal = YHC WHC +YCO2 WCO2 +YH2S WH2S

where, Y is the molar volume
concentration and W is the water
content in lbm/MMscf (read from
charts)
16
Effective Water
Content, Lb/MMscf
Correction for CO2

o
Isobars
Temperature
17
Effective Water
Content, Lb/MMscf
Correction for H2S

o
Isobars
Temperature
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 ?
Creates various transmission

problems such as plugging:
Pipeline
Equipment
Instrumentation
and hence restricts the flow

20
Hydrate
When gas is produced to the surface,
there are two hydrate inducing
factors:
Reduction in temperature
Reduction in pressure
21
Hydrate
Hydrate
Formation
Pressure
Specific
Gravity
1.0
Temperature
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
23
Gas Expansion and

Joule-Thomson Effect
The Joule-Thomson coefficient
> 0, then P and T
T
J =
P H
< 0, then P
Pi and
Ti
and T
Pf and
Tf
24
Initial Pressure
Hydrate Formation for

certain gravity gas
Pinitial
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 ?
26
Example 2
Initial Pressure
Temperature
Source:
GPSA
Figure20.17
3,000 psia
160oF
158 psia
59oF
Specific
Gravity = 0.7
Final Pressure
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?
28
Example 2 (Solution)
Enthalpy
Btu/lbmole
Determine first the final temperature

from Mollier-Diagram
Temperature, oF
Isotherms
Pressure, psia
Isobars
Entropy, Btu/lbmoleoF
29
Example 2 (Solution)
Pressure
Second check the hydrate region

ne r.
a
th p.G
e
M 6S
0.
0.7.8
0
Hydrate-Free
Region
Temperature
No hydrate will be formed
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
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:
yi is normally given or measured

Solve for P if T is given, or
Solve for T if P is given.
34
Vapor-Solid
Equilibrium
Iso-bars
Y
K =
X
Increasing
Pressure
Temperature
Note: Each component has its own chart
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
36
Kinetic Hydrate
Inhibitors
A polymeric material that delays the
hydrate crystal growth
N-vinylpyrrolidone
N-vinylcaprolactam
Saccarides
37
Anti-agglomerates for
Hydrate Inhibition
Prevents agglomerations of hydrate
crystals from growing into large
size
Alkyl aromatic sulphonate

Quaternary ammonium salt
Alkyl glycoside surfactant
38
Thermodynamic
Hydrate Inhibitors
Methanol
Ethanol
Iso-propanol
Ethylene glycol
Propylene glycol
Diethylene glycol
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.
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
43
Dehydration
Processes
Remove free water by two means:
Using solid adsorbent

Using liquid absorbent
Detailed evaluation of dehydration
processes will be discussed later.
44
Hydrates
Inhibitors
Salts
Alcohols
Ammonia
Monoethanolamine
45
Salts Inhibitors
Aqueous solutions salts are:
Electrolytes are very effective

inhibitors.
These prevent formation of lattice
around the gas molecules.
Salts also cause corrosion.
46
Salts Inhibitors
Chlorides: Effectiveness sequence
Al+3 >
AlCl3
Mg+2 >
MgCl2
Ca+2 >
CaCl2
Na+ >
NaCl
K+
KCl
Preferred because of low cost

Sulfates: Na2SO4, MgSO4, Al(SO4)3
Phosphates: Na3PO4
47
Alcohols Inhibitors
Types:
Glycol base (Ethylene glycol is the

preferred)
Methanol base
48
Alcohols
Inhibitors
Applications for cryogenic
processes:
Methanol amine is preferred

because the glycol viscosity
makes separation difficult at
cryogenic conditions.
49
Alcohols
Inhibitors
Applications for non-cryogenic
conditions:
Glycol is desired because of low

cost.
Ethylene glycol is also used as a
car antifreeze.
50
Ammonia & MonoEthanol-Amine Inhibitors

Ammonia:
Very effective but has undesirable
properties also.
May cause corrosion problems
Toxic
Forms carbonates with CO2
Monoethanolamine:
Very effective
51
CH3OH
EG or TEG
CaCl2
AlCl3
Hydrate
Inhibitors Effect
Wt % in
water 52
Hydrate Inhibitor Effect

on Hydrate Formation
Temperature Depression
Hammerschmidt (1939) equation:
K
T =
M
H
w
100 W
53
Hydrate Inhibitor Effect

on Hydrate Formation
Temperature Depression
T = oF
Mw = Inhibitor molecular weight
lbm/lb-mole
W = weight percent of inhibitor
KH = Empirical factor 1,297 for
methanol and 2,222 for ethylene
glycol
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.
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?
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
in the fluid system entering the

choke.
2. The amount of additional water
that will be separated at the outlet
of the choke.
3. Will hydrate be formed at the
outlet conditions of the choke?
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.
59
Hydrate
Prediction
Determine the mathematical

equations leading to the model for
hydrate prediction for
compositional and noncompositional gases in SPE 15306.
Summarize the equations in a
consistent unit system, such as SI
or FPS.
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.
62
Hydrate
Prediction
Prepare an information flow chart to

implement the above algorithm.
Prepare a spreadsheet program to
implement the above algorithm.
63
Hydrate
Prediction
Describe the capabilities of your

program by presenting a list of
tasks that it can perform.
64
Hydrate Prediction
Carry out the following

applications:
(a) Prepare typical charts for
vapor-solid ratios of various light
hydrocarbon components, similar
to typical vapor-liquid equilibrium
ratio charts for compositional
gases. You may present charts in 2and 3-variables forms.
65
Hydrate
Prediction
(b) Prepare typical charts for
hydrate prediction for noncompositional gases. You may
present charts in 2- and 3-variables
forms.
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.
67
Hydrate
Prediction
Submit a written report in the

form of a technical paper by
December 3, 2002 prepared
according to the SPE paper
submission guidelines (see SPE
web page for instructions).
Present the details of calculations
and results in an appendix.
68
References
K. Arnold and M. Stewart, Surface
Production Operations- Design of

Gas-handling Systems and Facilities,
Second Ed., Volume 2, Gulf
Publishing Company, 1999.
Y.E. Makogan and S. A. Holditch,
Experiments Illustrats Hydrate,
Oil&Gas Journal, Feb. 12, 2001, pp.
45-50.
69
References
Y.E. Makogan and S. A. Holditch, Lab
Work Clarifies Gas Hydrate, Oil&Gas

Journal, Feb. 5, 2001, pp. 47-52.
Berge, B.K., Hydrate Predictions on a
Microcomputer, SPE Paper 15306, SPE
Sym. On Petroleum Industry Applications
of Microcomputers held in Silver Creek,
CO, June 18-20, 1986.
SPE Paper 50749
70

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Natural Gas Processing

Dr. Faruk Civan, Ph. D.

Copyright 2003 by Faruk Civan

All of Dr. Faruk Civans lecture

H2O Vapor Presence

Critical Temperature = 705 oF

Reservoir pressures are much

Mole (Vol.) Fraction: Y

Copyright 2003 by Faruk Civan

Industrial Practice of reporting

(Sales Gas Specification is 7 lbm/MMscf)

Copyright 2003 by Faruk Civan

Water Content, lb/MMscf

Mcketta and Wehe

Copyright 2003 by Faruk Civan

Mcketta and Wehe

Correction factors are applied to

Wtotal = YHC WHC +YCO2 WCO2 +YH2S WH2S

Correction for CO2

Correction for H2S

Copyright 2003 by Faruk Civan

Creates various transmission

and hence restricts the flow

Gas Expansion and

Copyright 2003 by Faruk Civan

Hydrate Formation for

Copyright 2003 by Faruk Civan

Determine first the final temperature

Second check the hydrate region

Copyright 2003 by Faruk Civan

Copyright 2003 by Faruk Civan

yi is normally given or measured

Alkyl aromatic sulphonate

Copyright 2003 by Faruk Civan

Using solid adsorbent

Electrolytes are very effective

Copyright 2003 by Faruk Civan

Preferred because of low cost

Glycol base (Ethylene glycol is the

Copyright 2003 by Faruk Civan

Methanol amine is preferred

Glycol is desired because of low

Ammonia & MonoEthanol-Amine Inhibitors

Copyright 2003 by Faruk Civan

Hydrate Inhibitor Effect

Copyright 2003 by Faruk Civan

Hydrate Inhibitor Effect

Copyright 2003 by Faruk Civan

in the fluid system entering the

Determine the mathematical

Copyright 2003 by Faruk Civan

Prepare an information flow chart to

Copyright 2003 by Faruk Civan

Describe the capabilities of your

Copyright 2003 by Faruk Civan

Carry out the following

Submit a written report in the

Production Operations- Design of

Work Clarifies Gas Hydrate, Oil&Gas

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