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Raising a new Generation of Leaders

Unit Operations in Natural

Gas Engineering
PET 417

Dr. G. A. Adeyemi
 Hydrates Crystal
Hydrocarbons in Hydrates.  The Water Framework Though Is
 .
Methane  CH4 . 7H2O Ice-like, It Has Void Space and It Is
Weak.
Ethane  C2H6 . 8H2O
 The Hydrocarbon or “Guest”
Propane  C3H8 . 18H2O Molecules Are Held Together by
Weak Bonds Within the Void of the
Crystalline Network or Structure of
Butane  C4H10 . 24H2O
the Water to Stabilize Water
Structure.
CO2  CO2 . 7H2O

 The Water Framework Holds the

H2S H2S .6H2O
Hydrocarbon Molecules in a Void
Space or Network.
The Hydrate Crystal
The Water or “Host” Molecules
Are Linked Together by
Hydrogen Bonds Into Cage-like
Structures Called Clathrates.
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 Hydrate Crystalline Structure
 Two Basic Structures:  Hydrate Crystalline Structures.
.
 Structure II  Diamond

 Structure I  Cubic or Body-Centered

 Smaller Hydrocarbon Molecules (C1,C2,CO2, & H2S) Form More Stable and Cubic Structures.

 Larger Hydrocarbon Molecules (C3 & iC4 ) Form Less-stable and Diamond Structures.

 Molecules Larger Than C4 Cannot Form Hydrates Because They Cannot Fit Into the Cavity in the Water
Molecule Structure.

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 Properties of Hydrates
 They Have Fixed Chemical
 Physical Properties of Hydrate Composition BUT No Chemical
 Structures Bond

 STRUCTURE I STRUCTURE II
 They Behave Like Chemical
 Lattice Shape Body-Centered Diamond Cubic
 Stability More Stable Less Stable
Compounds.
 Water Molecules
 per Unit Cell 46 136  They Are Physically Like Ice or Wet
Snow Crystals but Do Not Have
 Cavities per Unit Cell
Solid Structure of Ice.
 Small 2 16
 Large 6 8
 Typical Gases That  They Have Less Density Than Ice.
 Form in Each Cavity Methane* Propane** (SG  0.96 – 0.98)
 of this Structure Ethane* I-Butane**
 H2 S n-Butane**
 They Sink in Liquid Hydrocarbons
 CO2 neo-Pentane**
and Float in Water.
 * Small
 **Large
 They Contain 90% Water by Weight
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SITP / O & G
 Conditions Necessary for Hydrates Formation
 Presence of Free Water.

 Natural Gas at or Below its Water

 Hydrate Formation Temperature
Dew Point.
 Temperature Below Which Hydrates Will Form at a
Particular Pressure.  Operating Temperature Below
Hydrate Formation Temperature for
That Pressure And Fluid
 They Form at Hydrate Temperature of the Gas and Composition.
NOT That of the Component Gases.
 Operating at Higher Pressure That
Increases the Hydrate Formation
 The Hydrates Formed Are Mixtures of the Hydrates Temperature.

of the Component Gases Rather Than Hydrate of the  Presence of Small Hydrate Crystal.
Natural Gas.

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 Conditions Necessary for Hydrates Formation
 Hydrates Form at Gas-water
 Operating at High Velocity or Agitation Through Equipment Boundary With the Forming
Molecules Coming From the
and Pipe Network. Solution.

 Turbulence Encourages Hydrate Formation; Hence Their  Parameters Such as High

Temperature That Encourages High
Presence Mostly Downstream of Valves, Regulators, Orifice Plates, Solubility Enhances Hydrate
Chokes Sharp Bends, Elbows, etc. and Upstream of these Devices Formation.
if Flow is Turbulent and Temperature is Low.
 Contaminants Such as H2S and CO2
are More Soluble in Water Than
 Crystal Formation Sites  Pipe-Elbows, Orifice Plates, etc. Hydrocarbon and as Such, More
Conducive for Hydrate Formation.
(Where Full Force of Stream Flow Cannot Prevent Hydrate Build-up).

 Very High Solution GOR

 Presence of Scales and Solid Corrosion Products . Encourages Hydrates Formation Due
to High Gas Molecules Presence
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Effect of GOR on Hydrates Formation

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 Hydrates Formation Prediction
 Less Accurate for Natural Gas With
 Parameters Predicted SG Between 0.9&1.0 Useless for
 Temperature
Streams With Sulfur Compounds
and/or Larger Molecules.
 OR
 Pressure
 Procedure
 at Which Hydrates Will Form.
 Given Gas Gravity and
Temperature or Pressure
 Katz’ Gas Gravity Method.
 Uses Gas Gravity, Pressure and Temperature.
 Hydrate Formation Pressure or
Temperature is Got From Katz
 It is Simple but Only an Approximation. Graph

 Values Excellent for Methane and 0.7 or Less SG Natural Gas.  If Gas Composition Fractions
are Given, Gas SG is then
 Not Good for Pipeline Gases. Calculated B4 Going to Graph

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Katz Pressure-Temperature Curves for Hydrates
Formation Prediction

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 Katz Hydrate Formation Condition Estimation
Method  Step 1
 Compute the Specific Gravity
 Example 4-3
 Component Mole % MW Z.MW
 Estimate Hydrate Formation Temperature of Natural  N 10.1 28 2.83
Gas With the Composition Shown Below at 1000 Psia.  C1 77.7 16 12.43
 Component  C2 6.1 30 1.83
Mole %
 C3 3.5 44 1.54
 N 10.1  i-C4 0.7 58 0.41
 C1 77.7  n-C4 1.1 58 0.64
 C5+ 0.8 86 0.69
 C2 6.1  100.0 20.38

 C3 3.5
 SG = 20.38/28.9625 = 0.7 .
 i-C4 0.7  Step 2
 n-C4 1.1  Read Hydrate Formation
Temperature From Katz Curve
 C5 + 0.8 (Assume C6)
 Hydrate Formation Temperature = 65 0F

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 Equilibrium Constant(K-Value)
Hydrate Formation Estimation Method
 Estimation Procedure
 Parameters Employed  Given Gas Composition,
 Vapor-Solid Equilibrium Constant (K-Values) Estimate Hydrate Formation
 Pressure Temperature.
 Temperature.
 Employs Calculations Similar to Vapor-Liquid Dew-Point
 Determine K-values for
Calculations with K-Values. Components at Estimated
Hydrate Formation Temperature.
 Has Vapor-Solid K-Values for
 Methane C1,
 Compute  Zi/kv
 Ethane C2,
 Propane C3,
 Iso-Butane I-C4  Repeat Above Steps Until
 Neo-Butane n-C4,   Zi/kv = 1
 Carbon Dioxide CO2 and
 Hydrogen Sulfide H2S
 Temperature at Which 
Zi/kv = 1 is Hydrate SLIDE 11
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 Equilibrium Constant(K-Value) Curves
Vapor-Solid K-Value for
 Vapor-Solid K-Value for Methane Ethane

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 Equilibrium Constant(K-Value)
Method Calculation  .

 Example 4-4
 Determine the Hydrate Temperature of Example 4-3 Using Equilibrium-Constant
Method.

 Component. Mole % KV (650F) Z/ KV. KV(630F) Z/ KV.

 N 10.1  0.0  0.0
 C1 77.7 1.24 0.627 1.22 0.636
 C2 6.1 0.90 0.068 0.77 0.079
 C3 3.5 0.26 0.135 0.18 0.194
 i-C4 0.7 0.007 0.065 0.08 0.087
 n-C41.1  0.0  0.0
 C5+ 0.8 (Assume C ) 
6 0.0  0.0
 100.0 0.895 0.996

 Hydrate Formation Temperature = 630F

 Note That K-values for n-Butane Above 55 0F and Non-hydrate Formers = 

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 Baillie and Wichert Method.
 Estimation Procedure
 Used Mostly to Predict Hydrate Formation Temperature  For the Above Gas at 1000 psia
of Acid Gases  Compute SG As in Example 4-3
Above.(SG = 0.7)

 Range of Application
 Total Acid Gas Content: 1–70%
 Enter Fig. 4-35 at 1000 psia

 H2S Content  1 – 50%  Move Horizontally to 0% H2S

 H2S/CO2 Ratio  1:3 – 10:1  Descend Vertically to the

Horizontal (SG = 0.7)
 Correction Has to Be Made for C3 Content.
 Follow Sloping Lines to the
Horizontal Bottom Temperature
 Chart Good for C3 Content Up to 10%
Scale.
 Read off the Hydrate SLIDE 14
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Temperature = 62 0F 14
 Baillie and Wichert Method.
• .

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 Baillie and Wichert Method.
 Determine Correction for C3.  Other Methods of Hydrates
Formation Temperature Estimation
 Interpolate For C3 = 3.5 Position on C3 Adjustment Chart.

 Pressure -Temperature Curves

 Enter Chart at H2S = 0%  by Gas Processors Suppliers Ass.

 Hydrates Formation Curves for

 Descend Vertically to 1 X 103 psia Line
Gases Undergoing Expansion
 by Gas Processors Suppliers Ass.
 Move Horizontally to Read the Correction. = +3 0F

 Add Correction.
 Hydrate Temperature = 62 + 3
 = 65 0F

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 Hydrates Control and Prevention
 Inhibitors .
 High Stream Flow Rate.  Materials Added to Water to
Depress its Freezing and
 Reduction of H2S and CO2 Content. Hydrate Forming Temperature.

 Keep Lines and Equipment Dry of Liquid Water.  Inhibitor Temperature Range
 Methanol Any
 If Water Must Be Present, Stream Must Flow at Above
Hydrate Formation Temperature.
 Di-Ethylene Glycol (DEG).  -10 0F
 Application of Heat.
 Ethylene Glycol (EG)  -10 0F
 Dehydration

 Tri-ethylene Glycol (TEG)  -10 0F

 If Stream Must Have Water and Must Flow at Low Temperatures, 
Then Inhibitors Must Be Injected.

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  .

 Problems Caused by Hydrates

 Inhibitor Concentration in Water Phase
 Hydrates in Flow Line Reduces
Well Head Pressure.
 W = D. M 100
 Ki + D . M

 Hydrates Can Block Flow Line

 W = Weight % Inhibitor in the Water
and Equipment.
 Base
 M = Mol. Weight of Inhibitor

 D = 0 C (0F) Depression of Hydrate  Hydrates Can Constrict

 Point. Equipment Surface Lines and
 Ki = Constant Flow Strings.
 Inhibitor Ki
 Methanol, 1297 (0C) or 2335 (0F)
 Fouling of Heat Exchangers.
 Glycols 2220 (0C) or 4000(0F)

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 Effect of DEG on Hydrate Formation

 Freezing Point of DEG Glycol

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SITP / O & G
 Natural Gas Water Content
 Dew Point
 NG Contains Some Degree of Water at ALL Conditions  Temperature at Which Natural Gas is
Saturated with Water Vapour at a
 Water Content of Oil and Gas Expressed in Given Pressure
 STB(water)/STO(oil) for Oil
 Water Vapour is in Equilibrium at
Dew Point.
 lb(water)/MM SCF(NG) for Gas

 Reduction of Temperature OR
 McKetta and Wehe Correlation Chart Increase of Pressure Will Result
Water Condensation

 Solubility of Water in Gas  Dew Point Depression

 Increases with Increasing Temperature  Difference in Dew Point Temperature
of Water Saturated Natural Gas
 Decreases with Increasing Pressure Before Dehydration and After
 Dissolved Salt in Water Reduces Solubility of Water in Gas Dehydration
 DPD = DP(Before) - DP(After)
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SITP / O & G
 McKetta and Wehe Correlation Chart

 .

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