NATURAL GAS PROCESSING

Why Process?

 Removal of components that are harmful during further

processing and at end usage
 Separation of components that are useful as such (LPG
component, e.g. propane & butane and Helium as industrial
gases, sulfur) or can be converted to some useful products
(ethane as feedstock for cracking to make polyethylene)
 Higher molecular weight compounds as liquid fuel and feed
stock for different petrochemicals.
HYDROCARBONS Ethane
CH4 - Methane Propane
C2H6 - Ethane n-butane
C3H8 - Propane SWEETENING iso-butane
Natural gasoline
C4H10 – Butane
C5H12 – Pentane
C6H14 – Hexane
C7H16 – Heptane
C2H4 - Ethene
DEHYDRATION
Methane
C3H6 - Propene
C4H8 – Butene
Non-hydrocarbon
Nitrogen N2 MERCURY REMOVAL
Carbon dioxide CO2 Water
Hydrogen sulfide H2S Helium
Helium He PARTICULATE REMOVAL CO2
Water vapor H2O H2S
Carbonyl sulfide COS Nitrogen
Carbon disulfide CS2
Sulfur S
Mercaptans *RSH
SWEETENING

• Safety and Environmental Protection

• Product Specification
• Corrosion Prevention
• Improved Heating Values
• CO2 Solid formation (cryogenic operations)
• Economics (sometimes)
SWEETENING
 Sour Gas contains either components H2S or CO2.
 H2S is by far the most dangerous but CO2 can cause problems with solids formation in
compression and cooling.
 Both these components are acid gases and are removed by similar “sweetening” processes.
 Quality requirements:
 Shall not contain more than 23 mg of H2S per m3. (16 ppmv)
 Shall not contain more than 115 mg of total Sulphur per m3
 Shall not contain more than 2% by volume of CO2.
Sweetening processes are designed to remove
 H2S -Hydrogen Sulphide
 CO2 -Carbon Dioxide
 COS -Carbonyl Sulphide
 CS2 -Carbon Disulphide
The removal of acid gases (H2S and CO2) can be achieved with a wide range of
different technologies. The chemical absorption of acid gases on amines is the most
common but molecular sieves and non-regenerative adsorbents can also be used for
specific applications. Chemical absorption of acid gases can be improved by use of
activators or by combined use of amines and physical solvents allowing the removal
of additional sulphur compounds (RSH, COS, CS2).
A list of available Gas Sweetening processes is the following:
1. Conventional Amines: MEA, DEA, MDEA (Methyl Diethyl Amine). The most widely
used is the MDEA as it is more selective to H2S with lower regeneration heat while
DEA is used in case total CO2 and H2S removal is required. A higher selectivity of
H2S vs. CO2 can be achieved with use of conventional MDEA by means of a special
design with very low residence times in Amine Absorber reducing CO 2absorption
and allowing a higher H2S/CO2 ratio in acid gas. The same principle is used for
Acid Gas Enrichment upstream the Sulphur Recovery Units
2. Activated Amines: Amine (MDEA or DIPA) is mixed with an activator called
Piperzine to modify absorption and regeneration properties such as improving
the efficiency of CO2 removal, improving the selectivity for H 2S, reducing
regeneration heat and allowing absorption of COS or RSH, etc.
3. Mixed Solvents: Amines are mixed with physical solvents in order to enhance
physical absorption of sulphur compounds
4. Molecular Sieves: Normally used for the removal of Mercaptans and H 2S from
gas phase at a concentration of a maximum of some hundreds of ppmv while
CO2 can be efficiently removed at a max of 0,1 %. Molecular sieves are 5A type
or larger and the typical process scheme is based on open loop regeneration
(spent regeneration gas is not recycled). Molecular sieves can also be used for
the sweetening of NGL or LPGs
5. Non-Regenerative Adsorbents: Used for the removal of H2S at lower
concentrations (typically lower than a hundred ppmv) and based on high activity
metal oxides which by reaction with H2S are converted to stable sulphides.
Inlet Separator
Removal of liquids and/or solids
Separator should be sized to handle surge capacity. Poor separator design can cause
problems in the treating facilities.
Absortion Tower
Sour gas enters the bottom of the tower and moves upward through the trays
H2S and CO2 in the gas react with the liquid amine solution and are removed from the gas
stream.
The reaction is often assisted by placing fresh lean amine on various trays down the tower.
This ensures that the gas will contact lean amine a few times as it moves up the tower.(This
is not shown on the diagram).
As the sweet gas leaves the tower, it is often contacted with water to remove any amine that
has vaporized and is travelling with the gas.
The top 2 or 3 trays may be used for this function. This is considered a “water wash” section
of the tower.
The water wash is often used if the temperature in tower is especially high or if MEA is used
as the amine.
Outlet Separator
The sweetened gas is passed through a
separator to remove any amine solution (or
liquid water) that may be travelling with the
gas flow
The gas is now saturated with water and must
proceed through dehydration facilities to lower
the water dew point before sale.
Flash Drum
From the contactor, the amine may enter a
flash drum to allow any hydrocarbon an
opportunity to leave the amine solution.
Heat Exchanger (HTEX)
The rich amine passes through a heat exchanger
where it picks up heat from the hotter lean
amine on its way to the contactor.
Since this service is clean, plate and frame
exchangers can be used, but often a more
common shell and tube exchanger is put in
service.
Stripper
The rich amine enters the stripper, where hot acid gas and
steam heat the rich amine, removing the H2S and CO2 that is
bound into the product.

Reboiler
The amine at the bottom of the stripper tower is heated to
105oC –140oC (depending on the type of amine being used).
This causes the acid gas/amine reaction to reverse and the
acid gas vaporizes with steam from the amine solution.
The acid gas/steam vapour re-enters the stripper and contacts
new rich amine on its way out the top. Amine carried with the
acid gas/steam vapour tends to reunite with the rich liquid
amine thereby removing it from the vapour flow.
Condenser
After leaving the top of the stripper tower, the acid gas/steam vapour is cooled
to remove heat and condense out the water from the flow.
The water is separated in a reflux drum and returned to the stripper tower as a
liquid.
The acid gas vapour is sent downstream to a Sulphur Recovery Unit (SRU).
If the plant has a gas sulphur inlet rate of less than 1 tonne/day (this is a very
small pollutant amount), the acid gas may be incinerated.
Burning the H2S creates SO2 which is a monitored.
DEHYDRATION

 Purpose of dehydration:
 The term dehydration means removal of water vapor.
 All natural gas downstream from the separators still contains water vapor to
some degree. Water vapor is probably the most common undesirable impurity
found in untreated natural gas.
 The main reason for removing water vapor from natural gas is that water vapor
becomes liquid water under low temperature and/or high-pressure conditions
(causing the formation Hydrates).
Water content can affect
 long distance transmission of natural gas due to the following facts:
o Liquid water and natural gas can form hydrates that may plug the pipeline
and other equipment.
o Natural gas containing CO2, H2S is corrosive when liquid water is present.
o Liquid water in a natural gas pipeline potentially causes slugging flow
conditions resulting in lower flow efficiency of the pipeline.
o Water content decreases the heating value of natural gas being transported.
 Gas dehydration is a fundamental step in gas treatment and is included in
nearly all gas processing units in order to prevent the formation of hydrates in
high pressure natural gases during gas transmission or during cryogenic gas
processing (such as LPG / NGL recovery or in LNGs). Dehydration is also
applied to prevent corrosion from condensed water in sour gas streams.
 Based on most common applications, the typical water dew points are the
following:
 For natural gas transportation, depending on geographic areas, in the range 0
°C to -20 °C, but can be lower for long subsea pipelines
 For Condensate / LPG recovery in the range -20 °C to -50 °C
 For NGL recovery and for LNGs, a residual water content lower than 0.1 ppmv,
corresponding to a water dew point lower than -80 °C, is required.
Methods of Dehydration:

 Absorption dehydration.
 Adsorption dehydration.
 Dehydration by cooling
Absorption Dehydration:

For more stringent dew point values, which is the most common case, dehydration
with glycols (MEG, DEG and mostly TEG) in the range of -10 o C to -40 o C is applied
 Water levels in natural gas can be reduced to the 10 ppm.
 The procedure of absorption is passing another fluid which has high affinity for
water towards the non dehydrated natural gas so it absorbs water then
regenerated in a separated circuit ,while the natural gas is dehydrated
towards 10 ppm.
Properties of absorbent:
 A high affinity for water and a low affinity for hydrocarbons
 A low volatility at the absorption temperature to reduce vaporization losses.
 A low viscosity for ease of pumping and good contact between the gas and
liquid phases.
 A good thermal stability to prevent decomposition during regeneration.
 A low potential for corrosion.

GLYCOLS ARE THE MOST EFFICIENT ABSORTION LIQUID SPECIALLY TEG

TEG dehydration
 Scrubbing of wet gas with glycol (in most cases TEG – tri ethylene glycol) is
one of the most applied dehydration technologies for natural gas.

The wet gas is flowing through the column

while the glycol in a counter flow absorbs the
water.
The loaded glycol is regenerated in a stripper
column heated by a re-boiler.
Regenerated glycol flows in a closed circuit back
to the glycol column.
 Advantages of absorption:
• Low initial cost
• Low pressure drop across absorption towers
• Recharging of towers present no problems
• Materials that would cause fouling of some solid adsorbents can be tolerated in the
contactor
 Disadvantages of absorption:
• Suspended matter, such as dirt, scale, and iron oxide may contaminate glycol
solutions.
• Over heating of solutions may produce both low and high boiling decomposition
products
• The resultant sludge may collect on heating surfaces, causing some loss in efficiency,
or, in severe cases, complete flow stoppage
• When both oxygen and hydrogen sulfide is present, corrosion may become a problem
because of the formation of acid material in the glycol solution.
• Highly mineralized water entering the system with inlet gas may, over long periods
crystallize and fill the re-boiler with solid salts.
Adsorption Dehydration.

 A typical molecular sieve dehydration plant consists of 2 or 3 adsorption towers

filled with solid desiccant. One or two of the adsorption towers is used for the
dehydration of wet inlet gas while the parallel installed tower aims to regenerate
loaded (water saturated) desiccant.
 In general, all liquid and solid impurities are removed from the feed stream of a
molecular sieve plant by an inlet separator or scrubber (upstream). As wet gas
contacts the solid desiccant bed, water vapour is adsorbed until equilibrium is
established between the water content in the gas stream and on the solid
desiccant particles. Dried natural gas leaves the bed, flows through the exit
switching valve, and finally leaves the dehydration unit via the dry gas outlet
header.
 While one or two bed is “on drying”, the other bed has to be regenerated.
Regeneration can be carried out using dry product gas or wet inlet gas.
Regenerator gas has to be heated upstream the regeneration tower. Hot
regeneration gas heats up the bed, drives the water off the desiccant particles,
and carries the resulting water vapour out of the bed. The regeneration stream is
cooled down and the water content is separated in the regeneration separator.
REMOVAL OF MERCURY
 There is an increased awareness on the part of gas processors to better protect
their assets and address environmental concerns by removing mercury at the
most appropriate location from their facilities
 It is important to remove mercury from the source to minimize process
emissions.
 Mercury-induced corrosion of LNG aluminum alloy cryogenic exchangers has led
to many instances of equipment failure, causing serious structural damage,
particularly when liquid mercury comes into contact with air or water.
 Mercury present in a hydrogen, syngas or hydrocarbon gas stream shortens the
useful lives of many precious metal catalysts.
 Product streams such as condensates, LPG, NGL are less valuable when
“distressed” by mercury
 From both worker safety and environmental perspectives, mercury removal may
be necessary. (OSHA) has set exposure regulations for inorganic mercury
compounds.
REMOVAL OF MERCURY (contd.)

o Elemental and organic mercury fall into the

category of being hydrocarbon soluble.
o Ionic mercury species are water soluble and
comprise examples that include both
sulphate and chloride salts of mercury (HgSO4
and HgCl2).
o Suspended mercury is a broadly comprising
particulates including mercury-containing
species such as HgS.
REMOVAL OF MERCURY (contd.)

Region Mercury level

Asia-Pacific 200-2000 μg/Nm3
Australia 50-200 μg/Nm3
Europe 1-500 μg/Nm3
North Africa 1-130 μg/Nm3
The Americas 1-100 μg/Nm3

In recent years, mercury levels have increased from typical

highs of 30 or 40 μg/Nm3 to levels exceeding 1000 μg/Nm3
in the Pacific Rim area.
REMOVAL OF MERCURY (contd.)

 Mercury removal process options

1. Regenerative adsorbents
2. Non-regenerative adsorbents
REMOVAL OF MERCURY (contd.)

Regenerative adsorbents for mercury removal

Molecular sieves are frequently used as adsorbent to remove water traces from
natural gas. Regenerative molecular sieve products that contain silver on the
outside surface of the molecular sieve pellet or bead can easily remove mercury
from the gas stream.
Mercury from the process fluid (either gas or liquid) amalgamates with the silver
and a mercury-free dry process fluid is obtained at the bed outlet. An additional
layer of HgSIV adsorbent, to an existing dryer configuration, results in removal of
design water load and the mercury from feed gas. Mercury and water are both
regenerated from the HgSIV adsorbents using conventional gas dryer techniques
where the mercury-silver amalgam on the molecular sieve is regenerated
thermally. The mercury desorption profile from the HgSIV adsorbent is similar to
a typical water regeneration profile, except that mercury is completely removed
from the HgSIV adsorbent well before the full regeneration temperature is
reached (for water removal). 
REMOVAL OF MERCURY (contd.)

 Non-regenerative adsorbents for mercury removal

There are two types of non-regenerative MRU:

 carbon systems and
 metal sulphide beds.
The common and traditional approach to mercury removal has historically
been through the use of sulphur-impregnated carbon beds. Existing sulphur-
impregnated activated carbon options tend to be less effective at positions
upstream of molecular sieve drying systems or glycol injection due to the risk of
capillary condensation in the micro pores of the carbon sub-structure. The pore
size distribution of carbon products is such that this has been problematic in the
past, particularly where MRU locations have been in the up-front position,
where raw gas is often at or close to its dew point and entrained liquids are
common. This is where fixed-bed, metallic-based MRU products find greatest
success in their ability to treat “wet” gas streams in up-front positions.
REMOVAL OF MERCURY (contd.)

Non-regenerative metal sulphides can successfully remove mercury from raw gas,
upstream of the amine unit and the dehydration vessels. Utilizing larger MRU
vessels, this approach protects the brazed aluminum heat exchanger and ensures
significantly less mercury contamination in and around the process plant. This
option has become increasingly popular, since
1. It minimizes the total mercury present before there is any opportunity for
mercury to migrate to various locations within a gas processing plant and
2. Avoids the risk of subsequent partitioning into processed natural gas and
condensate streams.
3. It also avoids subsequent adsorption onto any pipeline asset or piece of
equipment downstream.