Natural Gas Processing

Dr. Faruk Civan, Ph. D.

Professor, The University of Oklahoma

Copyright 2003 by Faruk Civan 1

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 2

Important Notice
ƒ All of Dr. Faruk Civan’s lecture
notes, course syllabuses, handouts,
homeworks, and exams are
copyright material.
ƒ They cannot be reproduced,
recorded and copied in any way or
form without the written permission
from Dr. Faruk Civan. All rights
reserved.
Copyright 2003 by Faruk Civan 3
Natural Gas
Hydrates
Copyright 2003 by Faruk Civan 4
H2O Vapor Presence
ƒ Critical values for water:
Critical Pressure = 3,208 psia

Critical Temperature = 705 oF

ƒ Reservoir pressures are much

higher, therefore, gases are
saturated with H2O vapor
Copyright 2003 by Faruk Civan 5
Estimating Water
Content
Vapor-
Pressure
o
For H2O

Temperature
Copyright 2003 by Faruk Civan 6
Estimating Water
Content n

Dalton’s Law: PT = ∑
i = 1
Pi

Pi
Mole (Vol.) Fraction: Y i =
PT
vap
H2O partial P
Y w = w
Pressure: PT
Copyright 2003 by Faruk Civan 7
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 8

 Estimating Water
Content…
(Y i )C = (Y i )L × (1 − Y w )
Mole of i/mole Mole of i/mole Mole of dry
of saturated of dry gas gas/mole
gas (from lab) of saturated gas

Copyright 2003 by Faruk Civan 9

Estimating Water
Content
Thus the water content of a gas is:
 Yw lbmole _ W   lbm _ W  1 lbmole
WHC = × M
  w ×
 380 .9 SCF
 (1 − Yw ) lbmole _ gas   lbmole _ W 
Yw M w Yw M w × 10 6
WHC = or WHC =
380 .69 × (1 − Yw ) 380 .69 × (1 − Yw )
lbm Industrial Practice of reporting
WHC =
MMscf water content

(Sales Gas Specification is 7 lbm/MMscf)

Copyright 2003 by Faruk Civan 10
Estimating Water
Content…
Looking back to the previous equation
and substituting the value of Yw
vap
P
Yw = w
PT
P M w × 10vap 6
W HC = w
(
P − Pw × 380 . 69
vap
)
Copyright 2003 by Faruk Civan 11
Estimating Water
Content…
For high pressure, charts should
be used

Vapor- P4
P3
Pressure P2 P1<P2<P3<P4
P1
For H2O

Temperature
Copyright 2003 by Faruk Civan 12
Mcketta and Wehe
Chart

ia
ps
Water Content, lb/MMscf

s ),
ar
ob
(Is
e
ur
ess
Pr

WHC!

WHC2

Copyright 2003 by Faruk Civan Temperature, T 13

Mcketta and Wehe
Chart…
ƒ Most Common chart used in the
processing industry
ƒ This chart is for hydrocarbon
gases only
ƒ It has been used in design since
1958
ƒ Source: GPSA Figure-20.3
Copyright 2003 by Faruk Civan 14
Estimating Water
Content
ƒHydrogen sulfide and carbon dioxide
are very common contaminants in
natural gas.

ƒCorrection factors are applied to

correct the water content estimation
in natural gas
Copyright 2003 by Faruk Civan 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)
Copyright 2003 by Faruk Civan 16
Correction for CO2
Content, Lb/MMscf
Effective Water

o
Isobars

Temperature
Source: GPSA Figure-20.9
Copyright 2003 by Faruk Civan 17
Correction for H2S
Content, Lb/MMscf
Effective Water

o Isobars

Temperature
Source: GPSA Figure-20.8
Copyright 2003 by Faruk Civan 18
Hydrate
ƒ 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.”

Copyright 2003 by Faruk Civan 19

Hydrate
ƒ Why hydrate is not desired ?
Creates various transmission
problems such as plugging:

• Pipeline
• Equipment
• Instrumentation

and hence restricts the flow

Copyright 2003 by Faruk Civan 20
Hydrate
When gas is produced to the surface,
there are two hydrate inducing
factors:

ƒ Reduction in temperature
ƒ Reduction in pressure

Copyright 2003 by Faruk Civan 21

Hydrate

Hydrate Specific
Formation Gravity
Pressure 1.0

Temperature
Copyright 2003 by Faruk Civan 22
PT Chart for
Hydrate Formation
ane r.
e th p.G
Pressure

M 6S
0.
0.7.8
0 Hydrate-Free
Region

Temperature
Source: GPSA Figure-20.15
Copyright 2003 by Faruk Civan 23
Gas Expansion and
Joule-Thomson Effect
The Joule-Thomson coefficient
> 0, then P and T
 ∂T 
µJ =  
 ∂P  H < 0, then P and T
Pi and Pf and
Ti Tf
Copyright 2003 by Faruk Civan 24
 Hydrate Formation for
certain gravity gas
Temperature Intersection
Initial Pressure

with the 45o

Tinitial line gives the
Pinitial o isotherm final
temperature
Tfinal to be reached
o isotherm
after
No expansion
Hydrate
formation hydrates
Source: GPSA
Pfinal Figure-20.16
Final Pressure
Copyright 2003 by Faruk Civan 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
 Source:
Example 2 GPSA
Figure-
Temperature
20.17
Initial Pressure

160oF 3,000 psia

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)
Determine first the final temperature
from Mollier-Diagram

Temperature, oF
Btu/lbmole

Isotherms
Enthalpy

Pressure, psia
Isobars

Entropy, Btu/lbmoleoF
Copyright 2003 by Faruk Civan 29
Example 2 (Solution)
Second check the hydrate region
ane r.
e th p.G
Pressure

M 6S
0.
0.7.8
0 Hydrate-Free
Region

Temperature
“No hydrate will be formed”
Copyright 2003 by Faruk Civan 30
Vapor-Solid
Equilibrium
Reference: SPE15306 and SPE 50749

Vapor

Solid
hydrate

Copyright 2003 by Faruk Civan 31

Vapor-Solid
Equilibrium
Let:
Xi = Mole fraction of component i in
the solid hydrate phase on a water-
free (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
that Yi
∑ X =1⇒
i =1
i ∑K =1
i =1 ( P, T )
vsi
Copyright 2003 by Faruk Civan 33
Vapor-Solid
Equilibrium
Application:

ƒ yi is normally given or measured

ƒ Solve for P if T is given, or
ƒ Solve for T if P is given.

Copyright 2003 by Faruk Civan 34

Vapor-Solid
Equilibrium
Iso-bars
Y
K = Increasing
X 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:
ƒ Operating outside the thermodynamic
condition (P&T) of hydrate formation.
This is done by adjusting the values of
temperature and pressure
ƒ Using dehydrating processes to
remove free water
ƒ Adding hydrates inhibitors
Copyright 2003 by Faruk Civan 36
Kinetic Hydrate
Inhibitors
A polymeric material that delays the
hydrate crystal growth

ƒ N-vinylpyrrolidone
ƒ N-vinylcaprolactam
ƒ Saccarides
Copyright 2003 by Faruk Civan 37
Anti-agglomerates for
Hydrate Inhibition
Prevents agglomerations of hydrate
crystals from growing into large
size

ƒ Alkyl aromatic sulphonate

ƒ Quaternary ammonium salt
ƒ Alkyl glycoside surfactant
Copyright 2003 by Faruk Civan 38
Thermodynamic
Hydrate Inhibitors
ƒ Methanol
ƒ Ethanol
ƒ Iso-propanol
ƒ Ethylene glycol
ƒ Propylene glycol
ƒ Diethylene glycol
Copyright 2003 by Faruk Civan 39
Controlling Operating
Conditions
a. Controlling hydrate temperature.
b. Controlling of hydrate formation
pressure.

Copyright 2003 by Faruk Civan 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 Æ N2 + 2H2O

+NaNO3 + Heat

Risk: N2 gas can overpressure the

system Copyright 2003 by Faruk Civan 42
Controlling hydrate
formation pressure
ƒ Rapid pressure reduction causes
overcooling and hydrate formation
ƒ Lower the pressure gradually at
isothermal conditions
ƒ Avoid sudden pressure reduction

Copyright 2003 by Faruk Civan 43

Dehydration
Processes
Remove free water by two means:

ƒ Using solid adsorbent

ƒ Using liquid absorbent
Detailed evaluation of dehydration
processes will be discussed later.
Copyright 2003 by Faruk Civan 44
Hydrates
Inhibitors
ƒ Salts
ƒ Alcohols
ƒ Ammonia
ƒ Monoethanolamine
Copyright 2003 by Faruk Civan 45
Salts Inhibitors
Aqueous solutions salts are:

ƒ Electrolytes are very effective

inhibitors.
ƒ These prevent formation of lattice
around the gas molecules.
ƒ Salts also cause corrosion.

Copyright 2003 by Faruk Civan 46

Salts Inhibitors
Chlorides: Effectiveness sequence

Al+3 > Mg+2 > Ca+2 > Na+ > K+

AlCl3 MgCl2 CaCl2 NaCl KCl

Preferred because of low cost

Sulfates: Na2SO4, MgSO4, Al(SO4)3

Phosphates: Na3PO4
Copyright 2003 by Faruk Civan 47
Alcohols Inhibitors
Types:

ƒ Glycol base (Ethylene glycol is the

preferred)

ƒ Methanol base

Copyright 2003 by Faruk Civan 48

Alcohols
Inhibitors
Applications for cryogenic
processes:

ƒMethanol amine is preferred

because the glycol viscosity
makes separation difficult at
cryogenic conditions.
Copyright 2003 by Faruk Civan 49
Alcohols
Inhibitors
Applications for non-cryogenic
conditions:

ƒ Glycol is desired because of low

cost.
ƒ Ethylene glycol is also used as a
car antifreeze.
Copyright 2003 by Faruk Civan 50
Ammonia & Mono-
Ethanol-Amine Inhibitors
Ammonia:
ƒ Very effective but has undesirable
properties also.
ƒ May cause corrosion problems
ƒ Toxic
ƒ Forms carbonates with CO2
Monoethanolamine:
ƒ Very effective
Copyright 2003 by Faruk Civan 51
Hydrate
Inhibitors Effect

EG or TEG
CaCl2
AlCl3

CH3OH
∆T o

Wt % in
Copyright 2003 by Faruk Civan water 52
Hydrate Inhibitor Effect
on Hydrate Formation
Temperature Depression
Hammerschmidt (1939) equation:

K W
∆T = H
×
M w 100 − W
Copyright 2003 by Faruk Civan 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
Copyright 2003 by Faruk Civan 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:

Copyright 2003 by Faruk Civan 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?

Copyright 2003 by Faruk Civan 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
ƒ Determine the mathematical
equations leading to the model for
hydrate prediction for
compositional and non-
compositional gases in SPE 15306.
Summarize the equations in a
consistent unit system, such as SI
or FPS.
Copyright 2003 by Faruk Civan 60
Hydrate
Prediction
Present the equations separately
for:
(a) Compositional gases
(b) Non-compositional gases

Copyright 2003 by Faruk Civan 61

Hydrate
Prediction
ƒ 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
ƒ Prepare an information flow chart to
implement the above algorithm.
ƒ Prepare a spreadsheet program to
implement the above algorithm.

Copyright 2003 by Faruk Civan 63

Hydrate
Prediction
ƒ Describe the capabilities of your
program by presenting a list of
tasks that it can perform.

Copyright 2003 by Faruk Civan 64

Hydrate Prediction
ƒ 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 2-
and 3-variables forms.
Copyright 2003 by Faruk Civan 65
Hydrate
Prediction
(b) Prepare typical charts for
hydrate prediction for non-
compositional 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
ƒ 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.
Copyright 2003 by Faruk Civan 68
References
ƒ K. Arnold and M. Stewart, Surface
Production Operations- Design of
Gas-handling Systems and Facilities,
Second Ed., Volume 2, Gulf
Publishing Company, 1999.
ƒ Y.E. Makogan and S. A. Holditch,
Experiments Illustrats Hydrate,
Oil&Gas Journal, Feb. 12, 2001, pp.
45-50.
Copyright 2003 by Faruk Civan 69
References
ƒ Y.E. Makogan and S. A. Holditch, Lab
Work Clarifies Gas Hydrate, Oil&Gas
Journal, Feb. 5, 2001, pp. 47-52.
ƒ 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.
ƒ SPE Paper 50749

Copyright 2003 by Faruk Civan 70