What Is Natural Gas?

 Natural gas is the gas obtained from natural

underground reservoirs either as free gas or gas
associated with crude oil.
 It generally contains large amounts of methane (CH4)
along with decreasing amounts of other hydrocarbons.
 Impurities such as H2S, N2, and CO2 are often found with
the gas.
 Higher molecular weight paraffinic hydrocarbons (C2-C7)
are usually present in smaller amounts with the natural
gas mixture, and their ratios vary considerably from one
gas field to another.
 The non-hydrocarbon constituents in natural gas vary appreciably
from one gas field to another.
 Some of these compounds are weak acids, such as hydrogen sulfide
and carbon dioxide.
 Others are inert, such as nitrogen, helium and argon.
 Some natural gas reservoirs contain enough helium for commercial
production.
 Higher molecular weight hydrocarbons present in natural gases are
important fuels as well as chemical feedstock's and are normally
recovered as natural gas liquids.
 For example, ethane may be separated for use as a feedstock for
steam cracking to produce ethylene.
 Propane and butane are recovered from natural gas and sold as
liquefied petroleum gas (LPG).
 Before natural gas is used it must be processed or treated to remove
the impurities and to recover the heavier hydrocarbons (heavier
than methane).
 Raw natural gases contain variable amounts of carbon
dioxide, hydrogen sulfide, and water vapor.
 The presence of hydrogen sulfide in natural gas for
domestic consumption cannot be tolerated because it is
poisonous.
 It also corrodes metallic equipment.
 Carbon dioxide is undesirable, because it reduces the
heating value of the gas and solidifies under the high
pressure and low temperatures used for transporting
natural gas.
 For obtaining a sweet, dry natural gas, acid gases must be
removed, and water vapor reduced.
LIQUEFIED NATURAL GAS (LNG)

• Many people in need of energy are located far from gas fields,
making pipelines too impractical or costly to build.
• To get around this problem, gas can be cooled to make a liquid,
shrinking its volume for easier, safer storage and shipping
overseas.
• Shell has been a pioneer in liquefied natural gas (LNG) for more
than 50 years.
• In Arzew, Algeria, the first commercial LNG liquefaction plant
was delivered in 1964 with Shell involvement, and shipped the
first commercial cargo from Algeria to the UK in the same year
What is LNG and how can we use it?

• LNG is a clear, colourless and non-toxic liquid which forms when

natural gas is cooled to -162 C (-260 F). The cooling process shrinks
the volume of the gas 600 times, making it easier and safer to store
and ship. In its liquid state, LNG will not ignite.

• When LNG reaches its destination, it is turned back into a gas at

regasification plants. It is then piped to homes, businesses and
industries where it is burnt for heat or to generate electricity. LNG is
now also emerging as a cost-competitive and cleaner transport fuel,
especially for shipping and heavy-duty road transport.
 Sour Gas Treating
 Natural gas usually contains some impurities such as hydrogen sulfide (H2S), carbon
dioxide (CO2), water vapor (H2O), and heavy hydrocarbons such as mercaptans.
 These compounds are known as ‘‘acid gases.’’
 Natural gas with H2S or other sulfur compounds (such as COS, CS2 and mercaptans) is
called ‘‘sour gas,’’ whereas gas with only CO2 is called ‘‘sweet gas.’’
 It is usually desirable to remove both H2S and CO2 to prevent corrosion problems and to
increase heating value of the gas.
 Sweetening of natural gas is one of the most important steps in gas processing for the
following reasons:
 1. Health hazards. At 0.13 ppm, H2S can be sensed by smell. At 4.6 ppm, the smell is
quite noticeable. At 500 ppm, breathing problems are observed and death can be
expected in minutes. At 1000 ppm, death occurs immediately.
2. Sales contracts.
 Most important natural gas pipeline specification are related to
sulfur content.
 Such contracts depend on negotiations, but they are quite strict
about H2S content.
3. Corrosion problems.
 The presence of H2S will cause metal embrittlement due to the
stresses formed around metal sulfides formed.
GAS-SWEETENING PROCESSES
There are more than 30 processes for natural gas sweetening.
The most important of these processes can be classified as follows:
1. Batch solid bed absorption
 For complete removal of H2S at low concentrations, the following materials
can be used: iron sponge, molecular sieve, and zinc oxide.
 This method is suitable for removing a small amount of sulfur when gas flow
rate is low and/or H2S concentration is also low.
2. Reactive solvents.
 MEA (monoethanol amine), DEA (diethanol amine), DGA (diglycol amine),
DIPA (di-isopropanol amine), hot potassium carbonate, and mixed solvents.
 These solutions are used to remove large amounts of H2S and CO2 and the
solvents are regenerated.
3. Physical solvents. Selexol, Recitisol, Purisol, and Fluor solvent. They are mostly
used to remove CO2 and are regenerated.
4. Direct oxidation to sulfur. Stretford, Sulferox LOCAT, and Claus. These
processes eliminate H2S emissions.
5. Membranes. This is used for very high CO2 concentrations. AVIR, Air Products,
Cynara (Dow), DuPont, Grace, International Permeation, and Monsanto are some
of these processes.
SELECTION OF SWEETENING PROCESS
There are many factors to be considered in the selection of a given sweetening
process. These include the following:
1. Type of impurities to be removed (H2S, mercaptans)
2. Inlet and outlet acid gas concentrations
3. Gas flow rate, temperature, and pressure
4. Feasibility of sulfur recovery
5. Acid gas selectivity required
6. Presence of heavy aromatic in the gas
7. Well location
8. Environmental consideration
9. Relative economics

 Several commercial processes are available, as shown in the schematic

flowsheet of Figure 2.
 This diagram can help in selecting the suitable process.
 If the sulfur recovery is not an option, then indirect processes can be considered.
 These processes can be classified into liquid-phase processes and dry-bed
processes.
 In this case, the total sulfur to be removed should not be large.
 The dry-bed processes can be classified as iron oxide sponge or zinc oxide
process, in this case, because the oxides are not expensive, the
corresponding sulfide might not be regenerated on site but rather by a
contracting company, and this might lower the operational cost and does not
require further processing for sulfur recovery.
 Alternatively, the molecular sieve bed can be used when the bed is
regenerated on site.
 If the operating conditions require the removal of a large amount of H2S
and/or CO2, liquid-phase processes are used.
 If it is required to selectively remove H2S, then physical solvents will be
suitable, they also remove COS and CS2.
 If the feed contain high amount of heavy hydrocarbons (C+3), then the use of
physical solvents may result in a significant loss of these heavy hydrocarbons
because they are released from the solvent with the acid gases and cannot
be recovered economically.
 On the other hand, if the feed contains a high amount of H2S and CO2 and it
is required to remove both of them, then chemical solvents such as amines
or carbonates could be used.
 The amine processes offer good reactivity at low cost and good flexibility in
design and operation.
 However, carbonates can be used if it is required to remove COS and CS2
from the feed.
 The carbonate process also can be run at a lower utility cost.
 If the sulfur recovery is an option, then a direct conversion process can be
used.
 They are only selective for H2S.
 Stretford, Lo Cat, and Sulferox are some of the process used for removal of
H2S from natural gas.
 In the case of the regeneration of solid fixed beds or amine regeneration
units, concentrated streams of H2S are obtained.
 However, final selection should consider environmental, economical, and
any other considerations
BATCH PROCESSES
In this case, H2S is basically removed, and the presence of CO2 does not affect
the processes.
Usually, batch processes are used for low-sulfur-content feeds.
Iron Sponge
 Iron sponge fixed-bed chemical absorption is the most widely used batch
process.
 This process is applied to sour gases with low H2S concentrations (300 ppm)
operating at low to moderate pressures (50–500 psig).
 Carbon dioxide is not removed by this treatment.
 The inlet gas is fed at the top of the fixed-bed reactor filled with hydrated
iron oxide and wood chips.
 The basic reaction is the formation of ferric sulfide when H2S reacts with
ferric oxide:
The reaction requires an alkalinity pH level 8–10 with controlled injection
of water. The bed is regenerated by controlled oxidation as

Some of the sulfur produced might cake in the bed and oxygen should be
introduced slowly to oxide this sulfur:

Repeated cycling of the process will deactivate the iron oxide and the
bed should be changed after 10 cycles.
 The process can be run continuously, in this case, small amounts of air or
oxygen are continuously added to the inlet sour gas so that the produced
sulfur is oxidized as it forms.
 In this case, higher sulfur recovery per pound of iron oxide is obtained also.
 A typical flow diagram of high-pressure continuous operation of the iron oxide
process is shown in Figure 3.
 In this case, one of the towers is on stream removing H2S from the sour gas
while the second tower is in the regeneration cycle by air blowing.
 The last regeneration step should be carried out with caution because reaction
(2) is highly exothermic, and the rate of reaction must be controlled.
 Care must be taken in replacing the exhausted iron sponge beds from the two
towers shown in Figure 3.
 On opening the beds, entering air causes a sharp rise in temperature which
can result in spontaneous combustion of the bed.
 The entire bed should be wetted before recharging.
 In some cases, it is more economical to operate the process with a
single bed and the exhausted bed of iron sulfide is trucked away to
a disposal site.
 The tower is then recharged with a new bed of iron oxide and the
tower is put back to service.
 The spent bed is left to react slowly with oxygen in the air, as
shown in reactions (2) and (3), which can be done by a contracting
company.