Qatar University

College of Engineering
Department of Chemical Engineering
Fall 2011

Introduction to Gas Engineering

CHME 451

Dr. Abdulreda Ali Alsaygh

ralsaygh@qu.edu.qa
Constituents of Wellhead Natural Gas

Class Component Formula Shorthand

Hydrocarbons Methane CH4 C1
Ethane C2H6 C2
Propane C3H8 C3
i-Butane iC4H10 iC4
n-Butane nC4H10 nC4
i-Pentane iC5H12 iC5
n-Pentane nC5H12 nC5
Cyclo-pentane C5H10
Hexanes and C6+
heavier
Inert Gases Nitrogen N2
Helium He
Argon A
Hydrogen H2
Oxygen O2
Acid Gases Hydrogen Sulfide H2S
Carbon Dioxide CO2
Sulfur Mercaptans R-SH
Compounds Sulfides R-S-R
Disulfides R-S-S-R
Water Vapor H2O

Solids Mill-scale and rust

Reservoir fines
Mercury
 Chapter 4
Water-Hydrocarbon Phase Behavior
• As produced at the wellhead, natural gases are nearly always
saturated with water.

• Liquid water can collect in pipelines and so increase the pressure

drop and/or cause slug flow.

• Free water can freeze into ice and/or form solid hydrates and so
reduce the gas flow or even plug the lines completely.

• Acid gas H2S and/or CO2 dissolve in free water and cause severe
corrosion
 Water Content of Natural Gases

• Methods for predicting the saturated water content of

natural gases may be classified as follows:

1. Charts for sweet gas (McKetta and Wehe, 1958)

Water content depends on pressure, temperature only

2. Charts for acid gas (Robinson, et al., 1958, Campbell, 1976)
– Robinson et al.
– Campbell
water content depends on pressure, temperature, and acid-gas content
3. Equation of state methods
Rigorous multi-component equilibrium calculation performed on the
computer
 Sweet natural Gas Charts and Tables

• Sweet Natural Gas

• Figure 4.6 : McKetta

• See Figure 4-6 page 52 (reliable 5% average error) for gases

containing up to 10% CO2 and/or H2S at pressure below
500 psia.
Figure 4.6 page 52
 Acid Gas Charts

• Robinson et al.
• Convert the carbon dioxide concentration into an equivalent H2S
concentration by multiplying the actual CO2 composition by 0.75
• See Figure 4.7a -4.7c pages 53-55
H 2 S (equivalen t) = Con.H 2 S + 0.75 (Con.CO 2 )

• Water content as ordinate and temperature (°F) as abscissa

• Pressure interpolation should be logarithmic

• Covers pressure range (300-10,000 psia)

• Temperature range (50- 375 °F)

• Based on computer calculations using SRK equation of state

Figure 20.10 and 20.11 (GPSA)
Figure 4.7a and 4.7b page 53-54
 Campbell Chats

• Campbell methods uses the following empirical

combination rules:
W = yhcWhc + yCO2WCO2 + y H 2 SWH 2 S

• Where :
• W = water content of sour gas (lb H2O/MMscf)
• Whc = water content of sweet gas (lb H2O/MMscf) [from Figure 4.6)
• yhc = mole fraction of all components except H2S and CO2
• WCO2 = effective water content of CO2 from Figure 4.8 (lb H2O/MMscf)
• yCO2 = mole fraction of CO2 in natural gas
• WH2S = effective water content of H2S from Figure 4.9 (lb H2O/MMscf)
• yH2S = mole fraction of H2S in natural gas
Figure 4.7a and 4.7b page 53-54
 Comparison

• Example 4.1: Estimate the water content of a sour

natural gas (65% HC, 20% H2S, 15% CO2) at 100 °F and
1500 psia
1. Use McKetta-Wehe plot (Figure 4-6)
2. Robinson et al chart (Figure 4-7)
3. Campbell correlation (Figure 4-6, 4-8)
 Solution

1. Use McKetta-Wehe plot (Figure 4-6) sweet gas

At T= 100 F and P= 1500 psia

Figure 4.6 page 52 (sweet gas)

W = 46 lb H2O/MMscf
 Solution

1. Robinson et al chart (Figure 4-7)

Equivalent H2S concentration = yH2S + (0.75)(yCO2)

Use Figure 4.7a at 100 °F

W = 0.168 bbl H2O/MMscf at 2000 psia
W = 0.205 bbl H2O/MMscf at 1000 psia

Use logarithmic interpolation

ln W1500 − ln W1000 ln 1500 − ln 1000
=
ln W2000 − ln W1000 ln 2000 − ln 1000
 Solution

ln W1500 − ln W1000 ln 1500 − ln 1000

=
ln W2000 − ln W1000 ln 2000 − ln 1000

ln W1500 − ln(0.205) 7.3132 − 6.9078

=
ln(0.168) − ln(0.205) 7.6009 − 6.9078

ln W1500 − (−1.5847) 0.4054

= = 0.585
− 1.7838 − (−1.5847) 0.6931

ln W1500 = −1.5847 + (0.585)(−0.1991)

ln W1500 = −1.7012

W1500 = 0.1825 bbl/MMscf = 64 lb H 2 O/MMscf

• Water content at 1500 psia
• W = 0.1825 bbl H2O/MMscf

• W = 64 lb/MMscf

• (0.1825bbl)(5.61 ft3)= 1.024 ft3

• (1.025 ft3)(62.4 lb/ft3) = 64.0 lb H2O)
 Campbell Charts

• Campbell methods uses the following empirical

combination rules:
W = yhcWhc + yCO2WCO2 + y H 2 SWH 2 S

• Where :
• W = water content of sour gas (lb H2O/MMscf)
• Whc = water content of sweet gas (lb H2O/MMscf) [from Figure 4.6)
• yhc = mole fraction of all components except H2S and CO2
• WCO2 = effective water content of CO2 from Figure 4.8 (lb H2O/MMscf)
• yCO2 = mole fraction of CO2 in natural gas
• WH2S = effective water content of H2S from Figure 4.9 (lb H2O/MMscf)
• yH2S = mole fraction of H2S in natural gas
 Solution

• Campbell Method (sour Gas)

• At T= 100 F and P= 1500 psia

Given y hc = 0.65, y CO 2 = 0.15, y H 2S = 0.20

W hc = 46 lb H 2 O/MMscf (Figure 4 - 6)
WCO 2 = 56 lb H 2 O/MMscf (Figure 4 - 8)
W H 2S = 142 lb H 2 O/MMscf (Figure 4 - 9)

W = y hc W hc + y CO 2 WCO 2 + y H 2S W H 2S

( 0 .65 )( 46 ) + ( 0 .15 )( 56 ) + ( 0 .20 )(142 ) = 66 .7 lb H 2 O/MMscf

Figure 4.6 page 52
Figure 4.7a and 4.7b page 53-54
 Solution

• Campbell Method (sour Gas)

• At T= 100 F and P= 1500 psia

Given y hc = 0.65, y CO 2 = 0.15, y H 2S = 0.20

W hc = 46 lb H 2 O/MMscf (Figure 4 - 6)
WCO 2 = 56 lb H 2 O/MMscf (Figure 4 - 8)
W H 2S = 142 lb H 2 O/MMscf (Figure 4 - 9)

W = y hc W hc + y CO 2 WCO 2 + y H 2S W H 2S

( 0 .65 )( 46 ) + ( 0 .15 )( 56 ) + ( 0 .20 )(142 ) = 66 .7 lb H 2 O/MMscf

 Water Content Applications

• Measurement of water content of gas is a normal part of the gas

conditioning process

• There are many instrument in the market for this purpose.

• Water content correlations are used primarily for dehydration

calculations to determine how much water (if any) will condense
from the gas. The later involves disposal consideration, corrosion,
and hydrate inhibition.

• Do not underestimate the quantity, be in the safe side.

• Common cause of poor dehydration performance is underpridiction

of the water loading
• Pay more attention to temperature , evaluating gas cooling
 Effect of Nitrogen and heavy ends

• Nitrogen will hold less water than methane

• Including nitrogen as a hydrocarbon is practical and offers a small safety
factor.

• The presence of heavy ends tend to increase the water capacity of the gas

• The nitrogen and heavy end effects tend to cancel out each other in many
production system

• Acid gas components tend to increase the water content by about 10%

• The temperature has profound effect on water content.

• Increase in temperature 2-3 C (4-5 F) increases the water content by 10%

• In many cases temperature is amore important parameter than

compositional effect. (evaluating the gas cooling)
 Measurement of water content

• Measurement of water content of gas is a normal part of

gas conditioning process.

• There are many instrument in the market for this

purpose.

• The choice is not routine

– Some difficult, or inconvenient to calibrate
– Some will not stand the physical treatment
– Others are not suitable for hazardous atmospheres
•
 Measurement of water content

• Water content of the natural gas can be measured by

• Different techniques
– Bureau of Mines Dew point Tester
– Electrolysis Method
– Aluminum oxide Humidity Sensor
– Titration method
– Conductivity cell
– Dew-point tubes
•
 Gas Hydrates

• Natural gas molecules smaller than n-butane can react with liquid or
free water to form crystalline, snow like solid solution called hydrates

• In solid hydrates the water or “host” molecules are linked together

by hydrogen bounding into cage-like structures called clathrate

• Hydrate have specific gravity ranging from 0.96 to 0.98 and

therefore float on water and sink in liquid hydrocarbons

• They are about 90% weight water

• Molecular size and solubility are important factors

• Guest molecules dictates which type of structure will be formed, and

its solubility governs the rate of formation
 Gas Hydrates

• The thermodynamic condition promoting hydrate formation are:

– Presence of “free” or liquid water
– Low temperature
– High pressure

• Hydrate formation is accelerated by agitation such as high velocities

or 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
 Prediction of Hydrate Formation Conditions

• The temperature and pressure at which hydrates form may be

estimated by:
– Gas gravity method
– Equilibrium Constant Method (Vapor-Liquid Equilibrium Constant)
– Baillie and Wichert Method
– Equation of State Methods

• The gravity method should be considered a first order estimate, the

Katz et al. equilibrium constant method represents a considerable
improvement, and the equation of state (or computer ) methods are
superior in accuracy and ease of extrapolation.
 Example

• Example 4-2 page 63

• Estimate the hydrate formation temperature at 1000 psia
for the following natural gas

component Mole %

N2 10.1
C1 77.7
C2 6.1
C3 3.5
iC4 0.7
nC4 1.1
C5+ 0.8
Σ 100
 Example 4-2 page 63

• Gas-Gravity Method
• Estimate the hydrate formation temperature at 1000 psia for the
following natural gas component z iMW (z)(MW)
component Mole %
N2 0.101 28 2.83
N2 10.1
C1 0.777 16 12.43
C1 77.7
C2 0.061 30 1.83
C2 6.1
C3 0.035 44 1.54
C3 3.5
iC4 0.007 58 0.41
iC4 0.7
nC4 0.011 58 0.64
nC4 1.1
C5+ 0.8 C5+ 0.008 86 0.69
Σ 100 Σ 1.000 20.38

• SG = 20.38/28.96 = 0.70
• Read hydrate formation temperature from Figure 4-10 at 1000 and 0.7
• Hydrate formation temperature = 65 °F
Figure 4.10
 Example 4-2 page 63

• Equilibrium- Constant Method (Katz et al.)

1. Estimate the hydrate temperature
2. Look up Kv-s from Figure 4-11 through 5-15

zi
3. Compute K v − s

zi
4. Repeat 1-3 until ∑ K v−s
=1

• Hydrate formation temperature = 63 °F

 Equilibrium- Constant Method (Katz et al.)

• Obtain kv-s at T and P for each component

• Calculate zi/Kv-s
• Check if sum of zi/Kv-s
component zi K65v-s Zi/K65v-s K63v-s Zi/K63v-s
N2 0.101 ∞ 0.0 ∞ 0.0

C1 0.777 1.24 0.627 1.22 0.636

C2 0.061 0.90 0.068 0.77 0.079

C3 0.035 0.26 0.135 0.18 0.194

iC4 0.007 0.108 0.065 0.08 0.087

nC4 0.011 ∞ 0.0 ∞ 0.0

C5+ 0.008 ∞ 0.0 ∞ 0.0

Σ 1.000 0.895 0.996

• Hydrate formation temperature = 63 °F

Figures 4-11 and 4-12
Figure 4-13 page 60
Figures 4-14-4-17 (page 61)
 Baillie and Wichert Method

• Step 1. Compute gas gravity. As in gas gravity method

• Step 2. Enter Figure 4-18 page 62 at 1000 psia;

move horizontally to 0%;
drop vertically to the horizontal SG;
follow sloping lines to the horizontal bottom temperature scale;
read the temperature (62 °F)

• Step 3. Add correction: interpolate for 3.5% C3;

drop vertically to 1 x 10-3 line and
read horizontally a correction of +3 °F

• Step 4. Add correction

• Hydrate formation temperature = 62 + 3 = 65 °F

Hydrate-SG Method (Figure 4.10)
Figure 4.18
 Equation of State Method

• A series of computer solutions have been developed

• In general they are as good as , and may be better than
the methods discussed above

• Other graphical methods

– Trekell-Campbell Method
– McLeod-Campbell Method
 Application of Hydrate Calculations

• Hydrate can only form when the gas is saturated with water

• Assumed that no liquid hydrocarbon or ice is present in the system

• (small amounts of liquid hydrocarbon have little effect on the hydrate formation)

• Hydrate are problem only if they allowed to agglomerate to a degree where they
restrict or stop flow.

• Hydrate calculations yield theoretical numbers for planning purposes.

• If they are used as proper guideline with proper design, hydrate should not present a
problem.

• Unusual gas, outside of normal composition, laboratory determination of hydrating

conditions is recommended.

• The positive manner is to keep lines and equipment “dry” of liquid water