Natural Gas as a Chemical

Feedstock
Contents
• Importance of Natural Gas as a Feedstock
• Synthesis Gas - As an Intermediate
• Methods of Synthesis Gas Production
• Technologies -Synthesis gas production
• Technologies - Utilization of Synthesis Gas
• Haber Bosch Process.
• Case Study
Importance of Natural Gas
Natural gas is the preferred feedstock primarily because:
• It is the most hydrogen rich and, therefore, contributes more
hydrogen compared with other feedstocks on a unit weight basis.
• The heavier feedstocks, like coal and oil, are more complex to process;
therefore, the capital costs are higher compared to natural gas
 Synthesis Gas - Intermediate
What is Synthesis Gas ?
• Synthesis gas (syngas) is a mixture of hydrogen and carbon monoxide
which has uses in petrochemical and metallurgical processes
Methods of Synthesis Gas Production
• Synthesis gas (syngas) can be produced from a variety of sources and is
an intermediate for production of chemicals and fuels.
• Gas-to-Liquids (GTL),
• Coal-to-Liquids (CTL),
• Biomass-to-Liquids (BTL)
All rely on the catalytic conversion of syngas.
Value Chain of Petrochemical Products
Value Chain of Petrochemical Industry from
Natural Gas
Application of SynGas
 Technologies - Synthetic Gas Production
• Various synthesis gas production technologies from natural gas are
• Dry reforming of methane,
• Steam reforming of methane,
• Partial oxidation of methane
 Dry Methane Reforming (DMR)
• Methane dry reforming is one of the most important processes used
in the production of syngas (H2 and CO).
• This process is not widely-used in the gas processing industries
because of rapid catalyst deactivation due to carbon deposition.
• Carbon dioxide reformation (also known as dry reforming) is a
method of producing synthesis gas (mixtures of hydrogen and carbon
monoxide) from the reaction of carbon dioxide with hydrocarbons
such as methane.
• The dry reforming reaction may be represented by:
CO2 + CH4 → 2 H2 + 2 CO
 Dry Methane Reforming (DMR)
• A challenge to the commercialization of this process is that the
hydrogen that is produced tends to react with the carbon dioxide.
• For example, the following reaction typically proceeds with a lower
activation energy than the dry reforming reaction itself:
CO2 + H2 → H2O + CO
• Typical catalysts are noble metals, Ni or Ni alloys.
 Steam Methane Reforming (SMR)
• Steam methane reforming is a catalytic process that involves a
reaction between natural gas and steam.
• Steam methane reforming is the benchmark process that has been
employed over a period of several decades for hydrogen production.
• The process involves reforming natural gas in a continuous catalytic
process in which the major reaction is the formation of 
carbon monoxide and hydrogen from methane and steam.
• Approximately 75% of the world's hydrogen production is produced
by using methane and natural gas.
• Hydrogen-rich gas is the output of the SMR process, and the highest
proportion of extracting hydrogen is done by this method.
 Steam Methane Reforming
• First, hydrocarbons must be fed into a
purification system to remove sulfur
and other impurities from the fuel.
• Now, purified hydrocarbons react with
steam at 850°C and 1.5–3 MPa to
produce a syngas including CO, CO2,
and H2O based on the following
reaction:

• So, if we use methane, the equation

will be changed to
 Steam Methane Reforming
• Then the synthesis gas is injected into
the water shift reaction unit. The CO
reacts with the water in this unit to
produce more hydrogen:

• Afterward, the process is continued by

injecting the product into the CO2
removal unit where liquid absorption
system separates CO2 from our
product.
• Finally, to achieve higher purity
hydrogen, the product is fed into a
methanation process.
 Technologies - Utilization of Synthesis Gas
• Some of the emerging technologies in utilization of synthesis gas
(or methane) for the production of petrochemicals
• Fischer-Tropsch synthesis - Fischer-Tropsch synthesis is being studied in great
detail world over and it is promising technology for manufacture of olefins
from synthesis gas.
• Oxidative coupling of methane with chlorine to yield ethane and ethylene
• Methanol to olefin technology (MTO).
• CO that can be separated from synthesis gas either by cryogenic or by
pressure swing adsorption is a promising feedstock for production of a variety
of products.
Partial Oxidation of Methane
Partial Oxidation vs Auto Thermal Reforming
 Tri-Reforming Process
• The tri-reforming of methane
may drastically reduce the
carbon deposition.
• The presence of O2 in the
feed allows the generation of
energy in situ, due to the
exothermal oxidation of
methane, which increases
the energy efficiency of the
process.
Tri-Reforming Process
 Global Demand of Ammonia

Other application industries include textiles, pharmaceuticals, industrial & household cleaning, food
and beverages, metallurgical processes, water and wastewater treatment, rubber, pulp & paper, and
leather.
Ammonia Production from Natural Gas-Integrated Plant
Haber-Bosch Process
 Haber-Bosch Process
• The Haber process, also called the Haber–Bosch process, is a nitrogen fixation
process and is the main industrial procedure for the production of ammonia today.
• The process converts atmospheric nitrogen (N2) to ammonia (NH3) by a reaction
with hydrogen (H2) using a metal catalyst under high temperatures and pressures:

• Conversion is typically conducted at 150–250 atm and between 400–500 °C, as the
gases (nitrogen and hydrogen) are passed over four beds of catalyst, with cooling
between each pass so as to maintain a reasonable equilibrium constant.
• On each pass only about 15% conversion occurs, but any unreacted gases are
recycled, and eventually an overall conversion of 97% is achieved.
• The steam reforming, shift conversion, carbon dioxide removal, and methanation
 Haber-Bosch Process
• The major source of hydrogen is methane from natural gas.
• The steam reforming, is conducted with steam in a high temperature and pressure
tube inside a reformer with a nickel catalyst, separating the carbon and hydrogen
atoms in the natural gas.
• Nitrogen (N2) is very unreactive because the molecules are held together by strong
triple bonds. The Haber process relies on catalysts that accelerate the scission of
this triple bond.
• The most popular catalysts are based on iron promoted with K2O, CaO, SiO2, and
Al2O3.
• The original Haber–Bosch reaction chambers used osmium as the catalyst, but it
was available in extremely small quantities
 Haber-Bosch Process
• Methanation is the reaction by which carbon oxides and hydrogen are converted to
methane and water.  The reaction is catalysed by nickel catalysts.  In industry, there
are two main uses for methanation, to purify synthesis gas (i.e. remove traces of
carbon oxides) and to manufacture methane.
Chemical Reactions