Gas Hydrates and Gas Sweetening

PE 5603: Introduction to Natural Gas Engineering and Management

Gas Hydrates

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 Natural Gas Hydrates
• Clathrates or Hydrates have a long history. These
compounds were first discovered in the 1800s
when British chemists Humphrey Davy and
Michael Faraday were experimenting with
Chlorine-water mixtures.
• They noticed when chlorine-water mixtures
cooled during the night, a solid material formed
at temperatures above the normal freezing point
of water.
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 Natural Gas Hydrates
• It was not until 1930s when E.G. Hammerschmidt discovered
that methane hydrate was responsible for plugging some
natural gas pipelines, especially those operating in cold
environments.
• But it was not until 1990s that the global view of clathrate
technology changed dramatically and methane hydrates were
observed as naturally occurring constituents of subsurface
sediments in gas fields in Siberia, north slope of Alaska and
deep offshore wells.
 What are Gas Hydrates?

Gas hydrates are naturally occurring, crystalline, ice-like

substances composed of gas molecules (methane, ethane,
propane, etc.) held in a cage-like ice structure or clathrate.

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 Natural Gas Reserves

• Methane hydrates represent the largest

Natural gas reservoir in the world. According
to some estimates, at present global demand
for natural gas, it may last for almost 700
years.
• However, yet-to-be-developed technologies
remain elusive at present.

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 Natural Gas Hydrates
Gas hydrates are formed by the chemical combination of natural
gas and liquid water under pressure and at temperatures
considerably above the freezing point of water.
The chemical formulas for natural gas hydrates are:
– Methane CH4 • 7H2O
– Ethane C2H6 • 8H2O
– Propane C3H8• 18H2O
– Carbon Dioxide CO2•7H2O

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Water Content of Hydrocarbon Gases

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 Natural Gas Hydrates
• Figure 20-4 can reveal one of the greatest
potential resources of natural gas.
• For example, at the ocean floor at a depth
of 7,000 ft the pressure would be over
3,000 psia. This means if the temperature
is less than 72°F (from Figure 20-4)
hydrates can & will form.

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 Natural Gas Hydrates

• In reality temperature at that depth is far

lower, closer to 32°F. This means that
natural gas hydrates will form if natural
gas is present.
• In fact at 40°F, natural gas hydrates will
form if the pressure is 250 psi, i.e., a
depth of less than 600 ft.

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 Natural Gas Hydrates
• There is ample evidence that the bottom of the oceans
contain massive quantities of natural gas in the form of
hydrates. In some cases, geologists have postulated that
the frozen hydrate may be the only cap-rock to
hydrocarbon reservoirs.
• One ft3 of hydrate contains 170 SCF of gas and
1 ft3 of hydrate weighs about 14.6 lb or
• l.0 lb of hydrate contains 11.6 SCF of methane.
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Conditions for Hydrate Formation
 Conditions for Hydrate Formation
The formation of a hydrate requires three basic conditions:
1. The right combination of temperature and pressure.
Hydrate formation is favored by low temperature and
high pressure.
2. A hydrate former must be present. Hydrate formers
include methane, ethane, and carbon dioxide etc.
3. A sufficient amount of water – not too much, not too
little.
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 Conditions for Hydrate Formation

4. A small ‘seed’ crystal of hydrate or acid gas

(H2S or CO2) is present in the system and the
flow rate is high with agitation, it will promote
the formation of natural gas hydrates.

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Hydrates In Natural Gas Systems

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Hydrate Structures
Hydrates Burn

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Factors Promoting Hydrate Formation
1. Pressure
2. Temperature
3. Composition
4. Gas being at or below its dew point with
free water present.
5. Pressure pulsations
6. Mixing
7. Introduction of small particles (e.g.
pipeline scale)
8. Physical site for crystal formations (e.g.
pipe elbow, orifice, valves, thermo-wells) 20
Natural Gas-Hydrate Equilibrium

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Conditions for Hydrate Formation

Fig. 20-12, based on experimental data,

presents the hydrate pressure-temperature
equilibrium curves for pure methane,
ethane, propane, and for a nominal 70%
ethane 30% propane mix.

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Prediction Of Hydrate Formation

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 Conditions for Hydrate Formation

Fig. 20-13 through 20-15, based on gas gravity,

may be used for first approximations of hydrate
formation conditions and for estimating
permissible expansion of sweet natural gases
without the formation of hydrates.

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Hydrate Inhibition
Natural Gas Expansion Without Hydrate Formation

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Natural Gas Expansion Without Hydrate Formation

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 Hydrate Inhibition

Hydrate inhibition utilizes injection of Ethylene glycol (EG),

Di-ethylene glycol (DEG), Tri-ethylene glycol (TEG), inorganic
salts (NaCl, CaCl2 or KCl) or methanol into a process stream
where it can combine with the condensed aqueous phase to
lower the hydrate formation temperature at a given
pressure.
Both glycols and methanol can be recovered with the
aqueous phase, regenerated and re-injected.

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Physical Properties of Glycols And Methanol

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 Estimate of Inhibitor
The minimum inhibitor concentration in the free water
phase may be approximated by Hammerschmidt’s equation.

(d)(M) (K)(X)
X= (100) d=
K + (d)(M) M(100 - X)
Where,
d = depression of hydrate point (F)
X = weight percent inhibitor in the liquid water
phase
M = molecular weight of inhibitor
K = 2335 (Methanol)
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Gas Sweetening

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 Gas/Oil Production System
FLARE
GAS
PIPELINE
SCRUBBER

SWEETENING DEHYDRATION
PLANT

LNG

PRODUCTION
SEPARATOR

WELL-
HEAD

TEST
SEPARATOR
STORAGE TANK
OIL
TREATING DESALTING

PIPELINE
WATER
TREATMENT DISPOSAL
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 Gas Sweetening

There are many methods that may be employed

to remove acidic components (primarily H2S and
CO2) and other impurities from hydrocarbon
streams. The available methods may be broadly
categorized as those depending on chemical
reaction, absorption, adsorption or permeation.
 Properties of Hydrogen Sulfide

Hydrogen sulfide (H2S) is a highly toxic gas. At

concentrations as low as 10 ppmv irritation of
the eyes, nose, and throat is possible.
The human nose can detect Hydrogen sulfide
in concentrations as low as 0.02 ppmv.

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 Properties of Hydrogen Sulfide

However, the human sense of smell

cannot be relied on to detect hazardous
concentrations of Hydrogen sulfide.
Higher concentrations and extended
exposure to hydrogen sulfide will
desensitize the sense of smell.

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 Properties of Hydrogen Sulfide

The concentrations required for different reactions by the human

body are:
1. Threshold limit value (TLV) for prolonged exposure: 10 ppmv
2. Slight symptoms after several hours exposure: 10-100 ppmv
3. Maximum concentration that can be inhaled for one hour
without serious effects such as significant eye and respiratory
irritation: 200-300 ppmv
4. Dangerous after exposure of 30 minutes to one hour: 500-
700 ppmv
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 Properties of Hydrogen Sulfide
5. Fatal in less than 30 minutes: 700-900 ppmv and
above.
6. Death in minutes: greater than 1000 ppmv
7. Hydrogen sulfide is highly flammable and will
combust in air at concentrations from 4.3 to 46.0
volume percent. Hydrogen sulfide vapors are
heavier than air and may migrate considerable
distances to a source of ignition.
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 Properties of Carbon Dioxide

• Carbon dioxide (CO2) is a naturally occurring gas

that is 50% heavier than air and is colorless and
odorless.
• It is also a principal by-product of combustion.
CO2 is inactive and therefore non-flammable.

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 Properties of Carbon Dioxide

• CO2 displaces oxygen and can create an oxygen-

deficient atmosphere resulting in suffocation.
The principal hazard of CO2 is exposure to
elevated concentrations.
• The atmospheric concentration immediately
hazardous to life is 10% (volume) and higher.

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 Types of Contaminants

• Ammonia (NH3) • Nitrogen (N2)

• Hydrogen sulfide (H2S) • Water (H2O)
• Carbon dioxide (CO2) • Sulfur dioxide (SO2)
• Carbonyl sulfide (COS) • Elemental sulfur
• Carbon disulfide (CS2) • Mercury and Arsenic
• Mercaptans (RSH) • Oxygen

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 Gas Sweetening

Removal of these contaminants from hydrocarbon

streams is required for reasons of safety, corrosion
control, gas specifications, to prevent freeze-out at
low temperatures, to decrease compression costs,
to prevent poisoning of catalysts in downstream
facilities and to meet environmental requirements.
 Gas Pretreatment

All gas sweetening units should have well-

designed pretreatment facilities.
Carryover of brine or liquid hydrocarbon (as
slugs or aerosol) from upstream production
operations can cause problems for gas treating
and downstream processing equipment.
 Gas Treating – Process Options
The gas treating process can affect the design of
the entire gas processing facility including
methods chosen for acid gas disposal and sulfur
recovery, dehydration, liquids recovery, liquids
fractionation and liquid product treating.

Some of the factors to be considered in making a

gas treating process selection are:
 Gas Treating – Process Option
1. Air pollution regulations regarding
sulfur compound disposal and/or Tail
Gas Clean Up (TGCU) requirements.
2. Type and concentration of impurities
in the sour gas.
3. Specifications for the residue gas.
4. Specifications for the acid gas.
5. Temperature and pressure at which
the sour gas is available and at which
the sweet gas must be delivered.
6. Volume of gas to be processed.
7. Hydrocarbon composition of the gas.
8. Selectivity required for acid gas
removal.
9. Capital cost and operating cost.
10. Royalty cost for using the process.
11. Liquid product specifications.
12. Disposal of byproducts considered
hazardous chemicals.
Gas Sweetening Process

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Gas Sweetening Process

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Gas Sweetening Flowsheet

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Guidelines and Calculations
Physical Properties of Gas Treating Chemicals

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Approximate Guidelines For Amine Process

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 Simplified Design Calculations
The simplified procedure for designing sweetening plant involves
estimating the amine circulation rate and using it as the principal variable
in estimating other parameters. For estimating amine circulation rate, the
following equations are suggested:
For MEA:
• GPM = 41 • (Qy/x) Eq 21-6
• (0.33 mol acid gas pick-up per mole MEA assumed)
• For DEA (conventional):
• GPM = 45 • (Qy/x) Eq 21-7
• (0.5 mol acid gas pick-up per mole DEA assumed)
• For DEA (high loading):
• GPM = 32 • (Qy/x) Eq 21-8
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• (0.7 mol acid gas pick-up per mole DEA assumed)
 Simplified Design Calculations
For DGA:
• GPM = 55.8 ∗ (Qy/x) Eq 21-9
• (0.39 mol acid gas pick-up per mole DGA assumed)
• (DGA concentrations are normally 50-60% by weight)
Where:
• Q = Sour gas to be processed, MMscfd
• y = Acid gas concentration in sour gas, mole%
• x = Amine concentration in liquid solution, wt%
• After the amine circulation rate has been estimated, heat and heat
exchanger requirements can be estimated from the information in Fig. 21-
9. Pump power requirements can be estimated from Fig. 21-10.
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Simplified Design Calculations
 Simplified Design Calculations
Similarly, the diameter of the regenerator below the
feed point can be estimated using the following
equation:
D = 3.0 • √GPM
r Eq 21-11
Where:
GPM = Amine circulation rate in gallons per minute
D = Regenerator bottom diameter in inches
r

The diameter of the section of the still above the

feed point can be estimated at 0.67 times the
bottom diameter.
Heat Exchanger Duty

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Power Requirements

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 Example Problem
Example 21-2 — 30.0 MMscfd of gas available at
850 psig and containing 0.6% H2S and 2.8% CO2 is
to be sweetened using 20%, by weight, DEA
solution. If a conventional DEA system is to be
used, what amine circulation rate is required, and
what will be the principal parameters for the DEA
treating system?
 Example Problem
Solution:
Using Equation 21-7, the required solution circulation is:
GPM = 45(Qy/x) = 45(30 x 3.4/20) = 230 gallons of 20%
DEA solution per minute.
Heat exchange requirements (from Fig. 21-9)
Reboiler:
H = 72,000 • 230 = 16.6 x 106 Btu/hr
A = 11.3 • 230 = 2600 ft2 ............
 Example Problem
Contactor diameter:
Dc = 44 • √30 / √ 8 6 5 = 44.4 inches or 48 inches rounded up.
Regenerator diameter below feed point:
Dr = 3.0 • √230 = 45.5 inches or 48 inches (bottom) rounded
up to nearest 6 inches.
Regenerator diameter above feed point:
Dra = 0.67 • 45.5 = 30.5 inches or 36 inches (top) rounded
up to nearest 6 inches.