1. Hydrates and Hydrate Composition
A hydrate is a physical combination of liquid water
and other smaller molecules to produce a solid which has an ice-like or dirty
wet-snow appearance but possesses a different structure than ice.
They are 90% (by weight) water; the other 10% is
composed of one or more of the following compounds: methane, ethane, propane,
iso-butane, n-butane, nitrogen, carbon dioxide and hydrogen sulphide.
The simplified structure of the hydrate crystal is
water molecules with the smaller hydrocarbon molecules occupying spaces between
the water. In a sense, the water molecules trap the hydrocarbons in a crystal
lattice.
Hydrates have specific gravities ranging from 0.96 to
0.98 and therefore float on water and sink in liquid hydrocarbons.
Hydrates are found in most areas of a gas producing
operation:
-
Downhole,
-
Gathering systems
-
Processing systems
Hydrates are a constant challenge in producing natural
gas and must be considered in all designs and production practices.
2. Hydrate Formation
Dangers
and problems created by Hydrates
An obstruction caused by a hydrate formation
can:
a)
reduce or block flow
b)
increase back pressure
c)
increase differential
pressure through a process
The pressure differential across a hydrate “plug” can cause it to
break loose and travel down the pipe at
very high velocities. People have been killed by hydrate plugs dislocating and
smashing through process equipment.
Hydrates can form single or multiple plugs in
lines.
The
formation of hydrate plugs can cause pressure to be trapped between two plugs.
Once formed, hydrates cause a threat to
personnel and equipment if not handled properly during removal. Pressure on both sides of a plug must be
reduced to keep it from dislocating and moving to the low pressure side.
The conditions that affect hydrate
formation are:
®
Pressure
®
Temperature
®
Composition
®
Gas must be at or below its
water dew point or saturation
condition
Note that when the natural gas is in the reservoir, it is assumed to be in
contact with water at equilibrium. The
gas is saturated with water. Therefore, even if free water is not present,
changing the conditions (pressure or temperature) can cause free water to form.
An example of changing the conditions would be passing the gas through a choke.
Pressure
and Temperature
Hydrates tend to form when the pressure
is high and the temperature is low.
All compositions have different points at which hydrates will form. The
most important point to remember is that it does not have to be colder than 0oC in order to have the
conditions necessary for hydrate formation.
When the formation of a hydrate causes a
restriction in a flow line, the restriction causes a pressure drop. The
resulting expansion of gas causes a cooling of the gas (Joule-Thomson effect).
This scenario is referred to as auto-refrigeration and can cause the
further growth of hydrates until the flow is blocked completely.
Hydrates often form at chokes, orifices, thermowells, bends in pipe etc.
3. Composition
The composition of the gas has a large effect on the formation of hydrates.
e.g. A small amount of propane or iso-butane in methane will cause hydrates
to form at warmer temperatures than in pure methane alone.
The presence of H2S will also affect the formation of hydrates.
When H2S is present in a gas composition, it will result in the
formation of hydrates at warmer temperatures at a given pressure.
The presence of CO2 has a much smaller impact and often reduces
the hydrate formation temperature at fixed pressure for a hydrocarbon gas
mixture.
4. Hydrate Inhibition
It is convenient to divide hydrate formation into two categories:
1)
Hydrate formation due to a
decrease in temperature with no sudden pressure drop, such as in the flow
string or surface line, and
2)
Hydrate formation where a sudden
expansion occurs, such as in flow provers, orifices, back-pressure regulators
or chokes.
A review of the conditions that tend to promote
the formation of natural gas hydrates are:
1)
Natural gas at or below
its water dew point with liquid water present.
2)
Temperatures below the
“hydrate formation” temperature for the pressure and gas composition
considered.
3)
High operating pressures
that increase the “hydrate formation” temperature.
4)
High velocity or agitation
through piping or equipment.
5)
Presence of a small “seed”
crystal of hydrate.
6)
Presence of H2S
or CO2 is conducive to hydrate formation since these acid gases are
more soluble in water than hydrocarbons.
4. Dehydration - Overview
Ø removal of water associated with the production of natural gas.
Ø prevents hydrates and reduces corrosion.
Ø Prepares gas for further processing (e.g. cryogenic)
Ø Removal of free water to prevent accumulations and promote single-phase
pipeline flow.
·
Three major methods of gas
dehydration are commonly used:
a) Absorption (wet)
i) triethylene
glycol (TEG)
ii) diethylene
glycol (DEG)
b) Adsorption (dry)
i) molecular
sieves (commonly called zeolites)
ii) silica
gel (essentially SiO2 in bead or powder form)
iii) activated
alumina (in extrudate or pellet form)
c)
Low Temp Processes
i)
Processes that
intentionally form and melt hydrates (LTX)
ii)
Processes that use hydrate
inhibitors
iii)
Processes that use
mechanical refrigeration
4.1. Absorption
·
dehydration by glycol
absorption is one of the most common methods of dehydration used to bring the
water content of a gas stream to pipeline spec.
·
a common dehy unit
consists of a absorption tower (contactor) in which wet gas is contacted with
lean glycol and a stripper in which heat is used to remove water from the rich
glycol.
·
glycols are used for
dehydration as water and glycol are mutually soluble in the liquid phase. Water
boils at a lower temp than glycol, so “rich” glycol is heated to a temperature
above the boiling point of water but below the boiling point of the glycol.
This creates “lean” glycol.
·
Commonly used in the field
at a wellsite for hydrate and free water protection, or in a plant handling
greater volumes of gas for final pipeline spec drying.
·
The advantages of a glycol
unit over a solid desiccant unit are:
a.
Lower installed costs
b.
Lower pressure drop in the
contacting tower
c.
Continuous process rather
than batch
d.
Glycol make-up is simple
vs. recharging dry beds
e.
Glycol units require less
make-up heat to regenerate
f.
Glycol systems operate in
the presence of contaminants that would foul a solid desiccant.
g.
Glycol systems are
adequate at water removal for most spec’s (except cryogenic processing).
·
The disadvantages of a
glycol unit are:
a.
Very low water dew-points
cannot be achieved
b.
Glycol is susceptible to
contamination
c.
Glycol is corrosive when
contaminated or decomposed.
4.2. Process Description
Gas Stream:
a.
Gas enters inlet separator
and liquids are removed.
b.
Gas enters contacting tower
and starts upward through a chimney tray.
c.
The gas passes through the
trays or packing, contacting glycol as it travels. The water in the gas has an
affinity for the glycol and attaches to it.
d.
The gas exits the tower
through a mist eliminator to the next process or to the flowline.
Glycol Stream:
a.
Lean glycol in the
accumulator is pumped to the top of the contactor tower.
b.
The glycol picks up water
from the gas as it travels down from tray to tray (or through the packing).
c.
The glycol exits as rich
glycol, is warmed through the accumulator and is dumped into the stripping
column of the reboiler.
d.
The rich glycol is heated
in the reboiler by a natural gas flame in a burner tube. The temperature causes
the water to vaporize and exit the stripping tower (where it contacts more
incoming rich glycol).
e.
The lean glycol spills
over into the accumulator ready for its next pass through the contacting tower.
4.3. Dehydrator Components
Inlet Scrubber
- simple two phase separator used to remove
water and liquid hydrocarbons from the wet gas stream.
Glycol - Gas
Contactor
-
vessel in which wet gas is
contacted with lean glycol.
-
utilizes counter-current
flow: gas upward and lean glycol downward.
-
trays exist in the
contactor (valve or bubble cap) to increase the contact time between the wet
gas and lean glycol.
-
mist extractor is located
at the top of the vessel to remove any glycol entrained in the gas.
-
lean glycol is pre-cooled
by a double pipe heat exchanger prior to entering the vessel (glycol can absorb
more water at cooler temps).
-
Glycol should enter the
dehy at about 10o hotter than the gas temperature. If it is too hot,
it can lead to foaming and inefficient dehydration, and if it is too cold,
hydrocarbons can condense in the glycol.
Filter and Pump
-
rich glycol exits the bottom of the contactor and is
filtered prior to entering a pump.
-
filter removes solid
components from glycol in order to protect the pump and decrease operational
problems with fouling of the dehy. unit.
-
the hydraulic pump
utilizes rich glycol from the contactor as the power fluid to pump lean glycol
from the surge tank to the contactor.
Stripping Still
-
the warm rich glycol enters the stripping still
after being preheated in a heating coil (tube side) in the surge tank.
-
The stripping still is usually filled with ceramic
packing or structured packing to improve the surface area contact of the water
vapour with the rich glycol.
-
allows any glycol vapors
to be condensed to eliminate losses.
-
water vapor exits the top
of the stripping still.
-
Fins on the stripping
still condenser section cool the vapor to help drop out any glycol which may be
entrained or vaporized in the water vapor. A temperature just above the boiling
point of water is optimal for the condensing section.
Reboiler
-
vessel in which rich glycol is heated to 175 – 200oC
to vaporize water.
-
heat source is a natural
gas flame in a fire tube.
-
glycol is regenerated to
99% glycol.
-
Glycol regeneration
efficiency can be improved with a “Stahl column”
-
Dry stripping gas (usually
fuel gas) is injected into a column between the reboiler and accumulator
-
The dry gas mixes with the
lean glycol (99%) and strips out more water. Glycol concentrations of 99.9% can
be achieved.
-
The gas enters the
reboiler and exits with the water vapour.
-
The cost to operate a
Stahl column must be weighed against the benefits. The costs are fuel gas (and
hydrocarbon to the environment).
Heat
Exchange/Surge Tank
-
regenerated glycol leaves the reboiler through an
overflow pipe and enters the shell side of the Surge Tank.
-
the lean glycol is cooled
by the rich glycol on the tube side of the exchanger.
-
the surge tank is a liquid
accumulator for the glycol pump to ensure the pump receives a uninterrupted
supply of glycol.
-
A sweet gas blanket is
often maintained in the vapour space above the glycol in the accumulator. A
slight pressure is held which prevents oxygen from the atmosphere and water
vapour from the reboiler from entering.