HYDRATEA IN NATURAL

GAS SYSTEMS
 Under normal production conditions, natural gas is saturated
with water . Water as a vapor is not the major problem. However,
when water combines with the gas molecules, e.g. methane,
ethane, propane and forms solid hydrates such as CH4.7H20,
C2H6.8H2O and C3H8.18H2O , then it becomes a problem.
[ Hydrates form ice-like solids when free water combines with
the components of a gas stream ]
Below 200 psia , hydrates form at 32F at higher pressures
temperature increases, these hydrates deposit and build up on
solid surface.

Hydrate formation is undesirable because:

1-Cause plugging of flow lines, equipment and instruments.
2-Result in unnecessary maintenance and lost production.
3-Cause physical damage.
4-Accelerate corrosion.
The conditions which affect hydrate formation are :
1-Primary considerations.
* Gas must be at or below its water dew point.
* Low temperature
* High pressure
* Composition
2-Secondary considerations :

* Mixing
* Kinetics
* Physical site for crystal formation and agglomeration such as pipe elbow,
orifice , or line scale
* Salinity

 In general , hydrate formation will occur as pressure

increases and/or temperature decreases to the formation
condition.
  Methods of preventing hydrates formation

. Adding heat to assure that the temperature is always above the hydrate
formation temperature ( indirect heaters are used to heat gas streams
at the well head and in pipelines)

- Lowering the hydrate formation temperature with chemical inhibition

- Dehydrating the gas so that water vapor will not condense into free
water.

- Design the process so that if hydrates form they can be melted before
plug equipment:
i-Reduce pressure drops by minimizing line lengths and restrictions.
ii-Check the economics of insulating pipe in cold areas.
 Temperature control Methods
The two main pieces of equipment used to control gas stream temperature and
inhibit hydrate formation are :
1-Down hole regulators
2-Indirect heaters

 Down hole regulators

• Down hole : A terms describing tools , equipment , and instruments used
in the well bore.Also describes conditions or techniques applying to the
well bore.
• Down hole regulators inhibit hydrate formation by expanding gas streams
while they are in the well bore.
• Down hole regulates is generally feasible when the gas well has the
following conditions :
1-A high reservoir pressure that is not expected to decline rapidly
2-Excess pressure
3-High capacity
•
• Down hole regulator contain a spring –loaded value and stem set from the
surface by using wire line run through the well bore tubing

• The design of down hole regulators requires using complex calculations that
must account for the following :
1-Down hole pressure and temperatures.
2-well depth.
3-well bore configuration.

 The performance of these involved calculations is not

necessary because production equipment vendors provide
detailed information on the design of down hole regulators
 Down hole regulators have the following
advantages :

1-low initial investment.

2-Do not require routine service.
 Down hole regulators have the following limitations or
disadvantages :
 They may not inhibit hydrate formation during startup. It may be necessary
to inhibit hydrate formation by injecting either methanol or glycol until the
gas flow and temperature stabilize.
 Generally, an outside vendor must change the pressure drop on the
regulator.
 When well output falls below normal production levels, processors must
remove and replace down hole regulators with another hydrate inhibition
method.
 When work is performed inside a well bore, the well may be permanently
damaged.
 Indirect Heaters
Two types of indirect heaters are used to inhibit hydrate formation: wellhead
and flow line.
The expansion of gas streams at or near wellheads often results in the
formation of hydrates. Wellhead heaters keep the temperatures of these gas
streams above their hydrate-formation temperatures.
Flow line heaters inhibit hydrate formation by replacing lost heat and keeping
the temperature of the gas stream above its hydrate-formation temperature.
Flow line heaters also inhibit hydrate formation by heating gas streams
expanded or choked downstream from the wellhead.

 Indirect Heater Sizing

The determination of the size of a heater depends on the following
conditions:
 Amounts of gas, water, oil, or condensate expected in
the heater.
 Inlet temperature and pressure.
 Outlet temperature and pressure (to avoid hydrate-
forming conditions).
 Often, heaters are necessary only while wells are being
started up. Installing preheat coils ahead of chokes is
generally practical for wells operated only intermittently.

 The advantages of using indirect heaters to inhibit the formation

of hydrates include the following:
 Minimal maintenance or attention required.
 Very low chemical requirements.

 The disadvantages of using indirect heaters to inhibit hydrates

include the following:
 Difficulty of supplying clean and reliable fuel to remote locations.
 Large operating (fuel) costs if cheap fuel is not available.
 Potentially large capital costs.
 Significant plot space required.
 Special safety equipment needed because of fire hazard.
 Comparison of Temperature Control Methods
WELLHEAD HEATERS DOWNHOLE DESIGN FACTORS
REGULATORS
Very high Very low Investment

Low Low Operating Maintenance

Very low None Chemicals

Very high None Plot Area
High High Hazards
  CHEMICAL INJECTION
 Methanol (MeOH) and monoethylene glycol (MEG) are the two
chemicals most commonly injected into gas streams to inhibit
hydrate formation.
Consider the use of chemical injection to inhibit hydrate formation
for the following:
 Situations where hydrate problems are of short duration.
 Gas streams operating a few degrees above their hydrate-formation
temperature.
 Gas-gathering systems in pressure-declining fields.
 Gas pipelines in which hydrates form at localized points.

 Methanol
Methanol works well as a hydrate inhibitor because of the following reasons:
• It can attack or dissolve hydrates already formed.
• It does not react chemically with any natural gas constituents.
• It is not corrosive.
• It is reasonable in cost.
• It is soluble in water at all concentrations.
 Methanol Injection System
The following figure shows a simplified schematic of a typical methanol injection
system. This system inhibits hydrate formation at a choke or pressure-reducing
valve. A gas-driven pump injects the methanol into the gas stream upstream of
the choke or pressure-reducing valve. The temperature controller measures the
temperature in the gas stream and adjusts the power-gas control valve. The
power-gas control valve controls the flow of power gas, which controls the
methanol injection rate.

METHANOL INJECTION SYSTEM

 Calculating Methanol Injection Rates
To determine methanol injection rates, the following conditions
need to be accounted for:
 The amount of free water condensed from the natural gas after chilling or
expanding.
 The concentration of methanol required to depress the hydrate-formation
temperature.
 The flow rate of the gas stream.
 The solubility of methanol in the hydrocarbon vapor.

The total methanol injection rate is calculated in two steps. First, calculate
the methanol injection rate required to achieve the concentration of
methanol in the aqueous solution which inhibits hydrate formation .
Then calculate the methanol injection rate required to compensate for
methanol vapor losses . The sum of the two injection rates is the total
methanol injection rate required to inhibit hydrate formation.
 Glycols
 Glycols are also used to inhibit hydrates. Monoethylene glycol (MEG) is the
form of glycol most commonly used to inhibit hydrate formation.
Glycol does not evaporate as easily as methanol. In some applications, glycol
does not dissolve into liquid hydrocarbons as easily as methanol. Recovering
glycol, therefore, is generally more economical than recovering methanol.
Economical recovery of glycol often compensates for its higher material cost,
lowering its operating cost below that of methanol.

Calculating Glycol Injection Rates

Calculating glycol injection rates is similar to calculating methanol injection
rates, but it is more critical to maintain the glycol solution between 60 wt % and
80 wt %. Also, glycol vapor losses are insignificant: therefore, you do not need
to account for them.
The method used to calculate methanol injection rates can be used for glycol.
However, because dilution is much more critical for glycol, the method must be
altered to account for glycol dilution restrictions.
GLYCOL INJECTION AND RECOVERY SYSTEM
The glycol injection and recovery cycle is as follows:
• The injection nozzle injects the lean glycol into the gas stream.
• The lean glycol absorbs the water and inhibits hydrate formation in the choke
or pressure-reducing valve.
• The three-phase separator separates the water and rich glycol from the
hydrocarbon gas and liquid.
• The separated components are piped to their respective destinations.
• The reboiler boils off excess water from the rich glycol, and thereby prepares
it to be injected again.
Glycol does not evaporate as easily as methanol. In some
applications, glycol does not dissolve into liquid hydrocarbons as
easily as methanol. Glycol solubility in hydrocarbon liquid
increases with:
• Glycol molecular weight
• Temperature increase
• Increase in glycol concentration in water-glycol mixture
  COMPARISON OF CHEMICAL INJECTION
INHIBITORS

/DISADVANTAGES ADVANTAGES INHIBITOR

LIMITATIONS
High initial cost
Possibility of glycol
contamination Limited use
(only noncryogenic
applications)
Cannot dissolve hydrates
already formed
High operating cost
Generally, use glycol
injection if methanol
injection rate is over 30
gph
Large vapor losses (high
volatility)
Usually lower operating cost
than methanol when both
Glycol
systems recover injected
chemical
Low vapor losses (low
volatility)
Relatively low initial cost
Simple system
Methanol
Does not generally need to be
recovered
Low viscosity
When injected, distributes
well into gas streams
Can dissolve hydrates already
formed
  Procedures for Calculating the Saturated Water
Content
of a Sweet Natural Gas Stream.
Step1. Use Figure 1 to determine the uncorrected water content of the
hydrocarbon components, WH.
Step 2. Use Figure 1 to determine the correction factor for gas gravity,
CG.
Step 3. Use Figure 1 to determine the correction factor for salinity, CS.
Step 4. Determine the corrected water content of the hydrocarbon
components
, W. W = WH (CG)
(CS)
Where:

W = Corrected water content of the hydrocarbon components.

WH = Uncorrected water content of the hydrocarbon components.
CG = Factor to correct for gas gravity.
CS = Factor to correct for gas salinity.
Figure 1: Water Content of Hydrocarbon Gas
 Example:
Determine the saturated water content for a sweet gas
Given :
Operating pressure = 1000 psia
Gas temperature =150 F
Molecular weight of gas=26 lb/mole
Gas in equilibrium with a 3% brine
* Solution

 From figure (1 )
W = 220 lb/MMscf
For a 26 molecular weight gas, CG = 0.98
For a gas in equilibrium with a 3% brine , Cs =0.93

 From equation:
W = WH (CG)(CS)
= 220(0.98)(0.93)
= 200.508 lb/MMscf
 Procedures for Calculating the Saturated Water Content of
a Sour Natural Gas Stream
Step1. Use Figure 1 to determine the corrected water content of the hydrocarbon
components, WH.
Step2. Use Figure 3 to determine the effective water content of the CO2
component, WCO2.
Step3. Use Figure 2 to determine the effective water content of the H2S
component, WH2S.
Step4. Use the following equation to calculate the total saturated water content
of the gas stream.W = y (W )+ y (W ) +
H H CO2 CO2
yH2S (WH2S)
Where:

W = Saturated water content of gas stream, lb H2O/MMSCF

Wi= Effective saturated water content of each component, lb H2O/MMSCF

yi = Mole fraction of component in gas stream

Figure-2 Effective Water Content of H2S in Natural Gas
Mixtures vs. Temperature at Various Pressures
Figure-3-Effective Water Content of CO2 in Natural Gas
Mixtures vs. Temperature at Various Pressures
 Example:
Determine the saturated water content for a sour gas
Given :
Operating pressure = 2000 psia
Gas temperature =160 F
 Gas composition:
ComponentMole%C180CO210H2S10
Solution
 From figure (1 )
WH= 167 lb/MMscf
From figure (2 )
WH2S= 280 lb/MMscf
From figure (3)
WCO2= 240 lb/MMscf
Then:
W= yH (WH)+ yCO2 (WCO2) + yH2S (WH2S)
= (0.80) (167) +(0.10) (280) +(0.10) (240)
= 185.6 lb/MMscf
 PROCEDURES FOR DETERMINING THE HYDRATE-FORMATION
TEMPERATURES OF SWEET AND SOUR GAS STREAMS
Step 1. Calculate the weight of component per mole of gas mixture by
multiplying the mole fraction of each component by the molecular
weight of each component.
Step 2.Calculate the total molecular weight of the gas mixture.
Step 3. Use the following equation to calculate the specific gravity (relative to
air) of the gas mixture.
MWgas
Sp.gr. gas  
Where:
MWair
Sp. gr.(gas) = Specific gravity of the gas stream
MWgas = Molecular weight of gas stream, lb/mole
MWair = Molecular weight of air = 29 lb/mole

Step 4 . Use the following equation to determine the hydrate-formation

temperature of the gas stream .
T  13.47 LnP  34.27 LnSG  1.675 LnP  LnSG   20.35
Where
T= hydrate formation temperature, 0F
P= Pressure , psia
SG= gas specific gravity relative to air
Note: accurate over the range of T< 65 0F and P< 1500 psia
 Example:
Determine the Hydrate-Formation Temperatures of Sweet and Sour Gas
Streams , Given :
Operating pressure = 325 psia
 Gas composition:

Mole Fraction Component

0.784 Methane CH4
0.060 Ethane C2H6
0.036 Propane C3H8
0.005 Iso-butane C4H10
0.019 n- butane C4H10
0.094 Nitrogen N2
0.002 Carbon dioxide CO2
  Solution
Lb/Mole of Molecular weight Mole Fraction Component
Mixture
12.544 16 0.784 Methane CH4
1.800 30 0.060 Ethane C2H6
1.584 44 0.036 Propane C3H8
0.290 58 0.005 Iso-butane C4H10
1.102 58 0.019 n- butane C4H10
2.632 28 0.094 Nitrogen N2
0.089 44 0.002 Carbon dioxide CO2
20.041 1.000 Total

1. The right column of table shows the calculation of the weight of each gas
component per mole of gas stream .
2. The weight of each gas component per mole of gas stream is totaled at
the bottom of the right column of the table.
3. The use of the following equation to calculate the specific gravity (relative
to air) of the gas mixture results in the following:

MWgas
Sp.gr. gas  
MWair
20.041
Sp.gr. gas    0.692
28.964

4. The use of the following equation, to calculate the hydrate-formation

temperature of the gas stream

T  13.47 LnP  34.27 LnSG  1.675 LnP  LnSG   20.35

T  13.47 Ln 325  34.27 Ln 0.692 

 1.675 Ln 325  Ln 0.692   20.35
T  48.504 0 F
Procedures for Calculating Methanol Injection Rate Required
to Inhibit Hydrate Formation in a Natural Gas Stream
Step 1
Calculate the amount of water condensed out of gas stream If the saturation
temperature equals the operating temperature:
W  WToperation  WTmin
Where:
W = Amount of free water condensed out of the gas stream, lbH2O/MMSCF
WToperating= Saturated water content of the gas stream at its operating temperature,
lbH2O/MMSCF
WTmin =Saturated water content of the gas stream at the minimum temperature of the gas
stream, lbH2O/MMSCF

* If the saturation temperature is higher than the operating temperature:

W  WTsaturation  WTmin
Where:
WTsaturation =Water content of a gas stream at its saturation temperature lbH2O/MMSCF
Step 2
Determine hydrate formation temperature
TH  13.47 LnP  34.27 LnSG  1.675 LnP  LnSG   20.35

Where:
TH =Hydrate formation temperature of gas stream,0F
P = Pressure, psia
SG = Gas specific gravity

Step 3
Estimate required depression of hydrate-formation temperatures

T  TH  Tmin  S
Where:
DT = Depression of hydrate-formation temperature, °F
TH = Hydrate-formation temperature of gas stream, °F
Tmin= Minimum temperature of system, °F
S = Safety factor to account for uncertainty in T H, °F = (5°F)
Step 4
Determine the weight percent of inhibitor

W 
 T  M 
100 
K H   T  M 
Where:
w I = Weight percent of the chemical inhibitor in the solution.
T = Depression of hydrate-formation temperature, °F
M = Molecular weight of the chemical inhibitor (methanol or glycol).
KH = 2,335 for methanol and 4,000 for glycol.
Step 5
Determine methanol injection rate required to compensate
for
vapor losses
QMeOHVapor=( Vapor-to-liquid composition ratio) (W)

Where:
Q MeOHvapor = Methanol injection rate required to compensate for vapor losses,
lbMeOH/MMSCF/wt % MeOH
W = Weight percent of methanol in the aqueous solution
Vapor –to- liquid composition ratio form chart.
Step 6
Determine methanol injection rate required to achieve aqueous
methanol concentration
QMeOHaq 
 W WMeOH 
Wwater 
Where:
Q MeOHaq = Methanol injection rate required to achieve the concentration of methanol in the
aqueous solution that inhibits hydrate formation, lbH2O/MMSCF
W = Amount of free water condensed out of the gas stream, lbH2O/MMSCF
W MeOH = Weight percent of methanol in the aqueous solution
W water = Weight percent of water in the aqueous solution

Step 7
Calculate total methanol injection rate

Q MeOH total = Q MeOHvapor + Q MeOHaq

Where:
Q MeOHaq = Total methanol injection rate required to inhibit hydrate formation, lbH2O/MMSCF
Q MeOHvapor =Methanol injection rate required to compensate for vapor losses, lbH2O/MMSCF
Q MeOHaq = Methanol injection rate required to achieve the concentration of methanol in the
aqueous solution that inhibits hydrate formation, lbH2O/MMSCF
CASE STUDY
Calculating Methanol Injection Rates
Calculate the methanol injection rate required to inhibit the formation of
hydrates in a saturated gas stream being cooled in a chiller.
• Given:
Gas specific gravity = 0.67
Inlet temperature = 60°F
Chiller temperature = 40°F
Operating pressure = 800 psia
• Solution:
1-Determine the water content of the gas at 70°F and 40°F(from Figure 1-
water content of natural gas)
Winlet = 20 lb H2O/MMSCF (at 60°F and 800 psia)
Wchiller = 11 lb H2O/MMSCF (at 40°F and 800 psia)
2-calculate that the amount of free water condensed out of the gas stream.
W = Winlet - Wchiller
= 20 - 11
= 9 lb H2O/MMSCF
3-Determine the hydrate formation temperature of the gas stream

TH=13.47*Ln800 + 34.27*Ln0.67 – 1.675[Ln800*Ln0.67]-20.35

TH = 60 0F

4-Calculate the required depressed of hydrate-formation temperature

T = TH - Tmin + S
= 60 - 40 + 5
= 25°F

5-Determine wt % concentration of methanol in the aqueous solution

W 
 T  M  100 
K H   T  M 

W 
 25 32  100 
2335   25 32 
W  25.5 wt % MeOH
Figure 4- Ratio of Methanol Vapor Composition to
Methanol Liquid Composition
6-Determine the vapor-to-liquid composition ratio from Figure 4
( Ratio of methanol vapor composition to methanol liquid composition)
The vapor-to-liquid composition ratio ( at 400F and 800 psia)
lbMeOH / MMSCF
 1.15
wt % MeOH
7-The injection rate required to compensate for methanol vapor losses.
QMeOHvapor = (vapor-to-liquid composition ratio)(W MeOH)
Q MeOHvapor =1.15* 25.5 = 29.3 lb MeOH/MMSCF

8- Calculate the methanol injection rate required to achieve the

concentration of methanol in the aqueous solution
QMeOHaq =( W * WMeOH) /Wwater
9- The total
= 9methanol injection
* 25.5 / (100- 25.5 )
= 3.1 lb MeOH/MMSCF
Q MeOHtotal = Q MeOHvapor + Q MeOHaq
= 29.3 + 3.1
= 32.4 lb
/MMSCF
10- Convert the total rate to gal
/MMSCF
= 32.4/6.5
 CASE STUDY
Calculating Glycol Injection Rates
Given:

Operating pressure = 1000psia

Minimum operating temperature = 40°F
Saturation temperature of gas stream = 90°F
Gas stream flow rate = 10 MMSCFD
Specific gravity = 0.7

Solution:
1-Determine the water content of the gas at 90°F and 40°F(from Figure 1
-water content of natural gas)
WSaturation = 45 lb H2O/MMSCF (at 90°F and 1000 psia)
Wmin = 9 lb H2O/MMSCF (at 40°F and 1000 psia)

2-calculate that the amount of free water condensed out of the gas stream.
W = WSat – Wmin
= 45 - 9
= 36 lb H2O/MMSCF
The water content is multiplied by the gas stream flow rate
Qwater = W x QGAS
= 36 X 10
= 360 lb H2O/day
3-Determine the hydrate formation temperature of the gas stream
TH  13.47 LnP  34.27 LnSG  1.675 LnP  LnSG   20.35

TH=13.47*Ln1000 + 34.27*Ln0.7 – 1.675[Ln1000*Ln0. 7]-20.35

TH = 64 0F
4-Calculate the required depressed of hydrate-formation temperature
T = TH - Tmin + S
5 + 40 - 64 =
5-Determine wt % concentration of glycol in the aqueous solution

W 
 T  M  100 
K H   T  M 

W 
 29  62  100 
4000   29  62 
W  31 wt % MEG
6. the concentration of the rich glycol Let us suppose that the vendor
recommends a lean glycol concentration of 70 wt % MEG.[usually greater

than 60 wt% glycol ]

If there is an allowable dilution of 10%, the concentration of the rich glycol
W rich = W lean - (allowable dilution)
= 70 wt % MEG - 10%
= 60 wt % MEG

7.Calculating Inhibitor Injection Rate:

1
QMEG  W   QGAS
 100 100 
  
 Wrich Wlean 
1
QMEG  36   10
 100 100 
  
 60 70 
QMEG  1512 lbMEG day