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
 Introduction
Hydrates in Pipelines
• When will it form?
• T drops below dew point AND hydrate formation T
• Typical locations:
– Low points in the lines/pockets of water
– Large pressure drop:
• Orifices, sudden enlargement on pipeline, elbow, etc.
• Problems: block pipeline, cause pipe rupture around the pipe bend,
• pipe rupture due to high P generated by the plug momentum

• Removal is challenging and dangerous:

– Large pressure differential across the plug
– Large release of gas upon melting – especially sour gas
– Refer to company guidelines for hydrate handling
 Introduction
Prevention of Hydrate Formation
• Hydrate formation is prevented by drying the natural gas by heating
the flow-line, or by chemical addition
• Drying the natural gas with triethylene glycol (TEG) or solid
desiccant is the best protection.
• Dehydration is generally carried out at the central facility

• Heating or chemicals prevent hydrate formation until the gas can be

dried economically
• Flow-line heating is used upstream of chokes and in short gathering
lines because initial investment is modest, heaters operates with
minimum of attention, and fuel is readily available
• For long flow-lines (over 1 or 2 miles) the gas approaches ambient
temperature and chemical injection may be preferred.
 Hydrate Prevention

• Reducing the P below that of the hydrate formation (for a given T)

• Adding heat: keeping the operating T above the hydrate formation T

• Dehydration: reducing water content in the gas to keep the system

above water dew point

• Inhibition: reducing the thermodynamic potential for hydrate

formation or modify the rate formation

• Ensure proper design of the system

 Prevention of Hydrate Formation

• Many chemical depress the temperature at which hydrates and/or

ice form (ammonia and brine were used in the past, the current
choice is either glycol or methanol).

• The most popular inhibitors are ethylene glycol (EG), diethylene

glycol (DEG), and methanol (CH3OH).

• Triethylene glycol (TEG) and tetraethylene glycol (TREG) are too

viscous for general use.

• Glycol and methanol injection are compared by considering

temperature effects, injection techniques, potential downstream
problems, and recovery economics.
 Prevention of Hydrate Formation

• Glycol must be sprayed into the wet gas as very small droplets
• Glycol is usually cheaper for continuous injection is required and/or
high gas volumes are being inhibited.
• Methanol injection has a low investment cost (no recovery unit) but a
high operating cost due to the chemical consumption.
• Injection of EG or DEG requires a higher initial cost but relatively low
operating cost
• Glycol units are used when the required methanol injection rate
exceeds 30 gal/h.
• Glycol can prevent hydrates, it will not attack or dissolve hydrates
already present. Methanol can dissolve existing hydrates to some
degree.
• A pipeline plugged with hydrates can be unplugged by reducing the
pressure. Make sure to reduce the pressure on both sides of the plug.
 Design Procedures

• Hydrate inhibition involves the transfer of water from the natural gas
to the liquid inhibitor. In steady state operation the mass flow rates
of all three components gas-water-inhibitor into the system must
equal the corresponding exit flow rates

• The required injection rate of inhibitor solution is calculated using

1 MMscf of dry gas as a basis.
• All other flow rates are expressed in lb/MMscf of dry gas.

• Minimum Liquid phase Inhibitor Concentration may be calculated

using two approaches
• 1. semi-empirical correlation of Hammerschmidt (1939)
• 2. Computer simulations, such as Aqua*Sim or Equi-Phase
•
 Minimum Liquid phase Inhibitor Concentration

• Minimum Liquid phase Inhibitor Concentration may be calculated

using two approaches
• 1. semi-empirical correlation of Hammerschmidt (1939)
• 2. Computer simulations

• Hammerschmidt’s equation estimates the minimum inhibitor

concentration in the exit liquid stream that is required to prevent
hydrate formation

• Inhibitor losses to the hydrocarbon phase:

• For glycol → small
• For methanol → significant
 Minimum Liquid-Phase Inhibitor Concentration

• Hammerschmidt’s equation estimates the minimum inhibitor

concentration in the exit liquid stream that is required to prevent
hydrate formation

W
d M W100
•
d M W  K H 6-1

• W = weight % pure inhibitor in liquid water phase

• d = desired depression of hydrate formation temperature, F
• MW = molecular weight of inhibitor
• KH = hammerschmidt constant for inhibitor
•
EG DEG Methanol
KH 4000 4000 2335
MW 62 106 32
 Inhibitor Required in Liquid Phase

The quantity of inhibitor required may be calculated readily by a

material balance:
lb water in outlet stream lb water in inlet stream
water removed from gas  (lb pure inhibitor) ( )( )
lb inhibitor lb inhibitor

Stated mathematically, the equation becomes:

 100  Wout   100  Win 

w G  I      (6-3)
 W out   Win 

Where:
wG = water removed from gas stream (lb/MMscf)
I = pure inhibitor required (lb/MMscf)
Win = concentration of inhibitor in inlet inhibitor stream (weight percent)
Wout = concentration of inhibitor in outlet inhibitor stream (weight percent)
 Prevention of Hydrate Formation

The water removed from the gas stream is also equal to the increase
in weight of the liquid-phase inhibitor solution; therefore:

 100   100 
w G  I      (6-4)
 out   in 
W W

If the Wout is fixed by the Hammerschmidt equation, combine equation

6-1 and Equation 6-4 to obtain

 (d)(MW)  K H  100
w G  I    (6-5)
 (d)(MW)  Win

If the inhibitor enters pure (i.e., Win is 100 weight percent-then:

(I)(K H )
wG  (6-6)
(d MW)
 Design Example

Example 6-1. (page 92)

Ten MMscf of a 0.7 SG natural gas cools down to 45 °F in a buried

pipeline. Minimum pipeline pressure is 900 psia. Concentration of
commercially available glycol inhibitor is 75% by weight. What
volume of inhibitor solution must be added daily if the gas enters the
line saturated at 90 °F? Solve for EG, TEG, and Methanol

Solution:
A safety margin of 5°F to 10°F is recommended to allow for operation condition
excursions and uncertainty in data and in J-T cooling effects.
• Estimate the hydrate formation temperature.
• Estimate the water content of the gas.
Estimate the hydrate formation temperature
Figure 4.10 (page 58)
Estimate the water content of the gas
Figure 4.6 (page 52)
 Solution

• Estimate the hydrate formation temperature. Figure 4-10 (page 58)

@t P = 900 psia and 0.7 S.G. gas
T = 64 °F

• Estimate the water content of the gas. Figure 4-6 (page 52)
@t P = 900 psia and T = 90 °F
Water content = 48 lb/MMscf [about 45 lb/MMscf]

@t P = 900 psia and T = 40 °F

Water content = 9.6 lb/MMscf [about 9.5 lb/MMscf]

• Free water formed = 48 – 9.6 = 38.4 lb/MMscf

 Solution (EG Injection Rate)

Estimate the minimum EG concentration using Hammerschmidt

equation (Eq. 6-1)

W
d  M W 100
d  M W  K H

W
64  4062100  (24)(62)(100)  148800  27.1 wt%
64  4062  4000 (24)(62)  4000 5488
The EG injection rate is calculated using equation 6-4
 100   100 
w G  I     
 out   in 
W W
 Solution (EG Injection Rate)

The EG injection rate is calculated using equation 6-4

 100   100 
w G  I     
 out   in 
W W

 100   100 
38.4  I     I [1.538  1.333]  0.205 I
 65   75 
38.4
I  187 lb EG/MMscf
0.205

The gas flow rate = 10 MMscf

The pure EG/day required:
= (187)(10) = 1870 lb pure EG/day
 Solution (EG Injection Rate)

If the 75 wt% inlet EG enters at 90 °F

From Figure 6-10 (page 93)

The density of the inlet glycol solution is 1.084 g/ml or 9.03 lb/gal

The EG volume solution/day =

 1870 lb EG  100 lb solution  gal solution  gal solution

     276.1
 day  75 lb EG  9.03 lb solution  day
 Inhibitor injection rate

 XR 
mI  mW  
 XL  XR 
mI = mass flow of inhibitor solution [lb/d]
mW = mass flow of liquid water [lb/d]
XR = rich inhibitor concentration [wt.%]
XL = lean inhibitor concentration [wt.%];
• 60 – 80% for glycol, ~ 95 - 100% for methanol

• Inhibitor losses to the hydrocarbon phase:

• For glycol → small
• For methanol → significant
Densities of aqueous EG solution
Densities of aqueous DEG solution
Vapor-Phase Methanol Loss
 Solution (DEG Injection Rate)

Estimate the minimum DEG concentration using Hammerschmidt

equation (Eq. 6-1)

W
d  M W 100
d  M W  K H

W
64  40106100  (24)(106)(100)  254400  38.9 wt%
64  40106  4000 (24)(106)  4000 6544
The DEG injection rate is calculated using equation 6-4
 100   100 
w G  I     
 out   in 
W W
 Solution (DEG Injection Rate)

The DEG injection rate is calculated using equation 6-4

 100   100 
w G  I     
 out   in 
W W

 100   100 
38.4  I     I [1.538  1.333]  0.205 I
 65   75 
38.4
I  187 lb DEG/MMscf
0.205

The gas flow rate = 10 MMscf

The pure DEG/day required:
= (187)(10) = 1870 lb pure DEG/day
 Solution (DEG Injection Rate)

If the 75 wt% inlet DEG enters at 90 °F

From Figure 6-11 (page 94)

The density of the inlet glycol solution is 1.093 g/ml or 9.10 lb/gal

The DEG volume solution/day =

 1870 lb DEG  100 lb solution  gal solution  gal solution

     274.0
 day  75 lb DEG  9.10 lb solution  day
 Solution (Methanol Injection Rate)

Estimate the minimum Methanol concentration using

Hammerschmidt equation (Eq. 6-1)

W
d  M W 100
d  M W  K H

W
64  4032100  (24)(32)(100)  76800  24.80 wt%
64  4032  2335 (24)(32)  2335 3103
The Methanol injection rate is calculated using equation 6-4
 100   100 
w G  I     
 out   in 
W W
 Solution (Methanol Injection Rate)

The Methanol injection rate is calculated using equation 6-4

If the methanol enters pure, Win = 100% then equation 6-4 yields:

 100   100 
w G  I      (6-4)
 out   in 
W W

(I)(K H )
wG 
(d)(MW)

(I)2335
38.4   3.04 I
(24)(32)
38.4
I  12.6 lb pure liquid Methanol/MMscf
3.04
Vapor-Phase Methanol Loss
 Solution (Methanol Injection Rate)

Methanol usage in the gas phase is obtained from Figure 6-3

At 40 °F and 900 psia

(lb vapor CH 3 OH/MMscf)

 1.05
(weight percent CH 3OH in solution)

Methanol used = (1.05)(24.8) = 26.0 lb CH3OH/MMscf

Total Methanol required = 12.6 + 26.0 = 38.6 lb pure methanol/MMscf

= 386 lb pure methanol/day
= 386/6.64 = 58.1 gal methanol/day
(density of methanol at 60 °F and 1 atm = 6.6385 lb/US gal)
 Operation
Prevention of Hydrate Formation
Glycol injection
The glycol should be injected into the gas stream just ahead of
cooling vessels (HXER, choke, expander, or chiller), thus providing
sufficient time for good glycol-gas contact.

Glycol-Water-Oil Separation
All vessels for separating glycol-water-oil mixtures (below 30-40 °F)
should be designed for a residence time of about 30 minutes
• Residence time is found by dividing the vessel volume by the
volumetric flow rate of the inlet mixture.
• It is recommended that separation be carried out at 80-100 °F,
which lower viscosity and promote settling
 Glycol Losses

Glycol is lost in three ways:

1. Solution in liquid hydrocarbon
2. Vaporization and entrainment in the exit gas
3. Decomposition in and carry-over from the regenerator.

Glycol solubility in hydrocarbon liquids increases with:

1. Increase in molecular weight of the glycol
2. Increase in temperature
3. Increase in weight percent glycol in the water-glycol mixture
4. The type of hydrocarbon liquid present
 HW

• Solve problem 1 (Chapter 6) in your Textbook