Synthesis Gas production and

derived chemicals
3.1 Introduction
3.2 Steam reforming process
3.3 Industrial Ammonia Synthesis and
applications
3.4 Industrial Methanol Synthesis and
applications
 3.1 Introduction
• Synthesis gas (or syngas) is a general term used to designate mixtures
of hydrogen and carbon monoxide in various ratios.
• Syngas may be produced from a variety of raw materials ranging from
natural gas to coal by reaction of steam or oxygen.
• The choice for a particular raw material depends on the cost and
availability of the feedstock, and on the downstream use of the
syngas
• Syngas is generally produced by one of three processes, which are
distinguished based on the feedstock used
– steam reforming of natural gas (methane) or light hydrocarbons,
optionally in the presence of oxygen or carbon dioxide
– partial oxidation of (heavy) hydrocarbons with steam and oxygen
– partial oxidation of coal (gasification) with steam and oxygen
 Mixtures Main uses
H2 Refinery hydrotreating and hydrocracking
3 H 2 : 1 N2* Ammonia
2 H2 : 1 CO Substitute natural gas (SNG)
2 H2 : 1 CO Alkenes (Fischer–Tropsch reaction)
2 H2 : 1 CO Methanol, higher alcohols
1 H2 : 1 CO Aldehydes (hydroformylation)
CO Acids (formic and acetic)
*With N2 from air

Table 3.1: Syngas applications in refining, the chemical process industry and fuel
production
• Most syngas today is produced by steam reforming of natural gas or
light hydrocarbons up to naphtha
• The steam reforming feed usually has to be desulfurized
• Sulfur is a poison for metal catalysts because it can block active sites by
the formation of rather stable surface sulfides
• When sulfur is present as hydrogen sulfide (H 2S), sulfur removal might
used adsorption (for instance on activated carbon), reaction with an
oxide (for instance zinc oxide), or scrubbing with a solvent.
• If the feed contains more stable sulfur compounds, hydrotreating may
be required
• Processes for the production of syngas based on coal and heavy
oil fractions require removal of sulfur
• compounds (mainly H2S) from the syngas. Feed purification is not
possible with these raw materials, although attempts have been
made using biotechnological approaches.
 Syngas from natural gas: Reactions and
Thermodynamics
• The formation of syngas is strongly endothermic and requires high
temperatures
• Steam reforming of natural gas proceeds in tubular reactors that
are heated externally
• The process uses nickel catalyst on a special support that is
resistant against the harsh process conditions
• Waste heat from the oven section is used to preheat gases and to
produce steam. Plant that generates syngas with H2/CO ratios in the
range of 3-4, and is suitable for hydrogen production
• The ratio depends on the its feedstocks and the process conditions.
• Feed streams too rich in H2 can be adjusted by using membranes to
selectively strip out the excess H2
• When converting natural gas (methane) in the presence of steam the
most important reactions are the steam reforming reaction and the
water–gas shift reaction.
– CH4 + H2O ⇋ CO + 3H2 (Primary reformer)
– CO + H2O ⇋ CO2 + H2 (Secondary reformer –Water-gas shift)
• The main reactions may be accompanied by coke formation, which
leads to deactivation of the catalyst
• Coke may be formed by decomposition of methane or by
disproportionation of carbon monoxide
– CH4 ⇋ C + 2H2 (Carbon formation – CH4 decomposition)
– 2CO ⇋ C + CO2 (Carbon formation - Disproportionation of CO)
• Side reactions might also occur during the reforming process:
– CH4 + 2O2  CO2 + 2H2O (complete oxidation of CH4)
– CO + ½ O2  CO2 (oxidation of formed CO)
– H2 + ½ O2  H2O (oxidation of formed H2)
 3.2 Steam reforming process
Primary reforming
• The reforming process starts with natural gas which contains
methane molecules and impurities such as sulfur.
• After desulfurization, the methane proceeds and water is added in
the form of steam
• As soon as the steam and methane mixture reaches a high heat flux
reactor (at T = 700 – 1100degC and P = 3 – 25 bar), the catalyst
causes the chemical reaction between them forming hydrogen and
carbon monoxide and relatively small amount of carbon dioxide.
Secondary reforming (Water-gas shift reactor)
• To increase the hydrogen production, a second catalyst (iron-chrome
based) is included. This is where the remaining carbon monoxide
reacts with steam into carbon dioxide and more hydrogen is formed.
• This process is known as the water-gas shift reaction

Pressure swing adsorption

• Because many end-users needs very pure hydrogen, the gas mixture
now needs to be purified
• In this final process step called "pressure-swing adsorption," carbon
dioxide and other impurities are removed from the gas stream,
leaving essentially pure hydrogen.
• These leftover gases are used as fuel for the furnace, while the
hydrogen is ready for customers
Carbon formation
• Carbon is formed when; catalyst has a low activity, low steam to
hydrocarbon ratio, or higher hydrocarbons as feed.
• Carbon formation in steam reformers must be prevented for two
main reasons.
– Coke deposition on the active sites of the catalyst leads to
deactivation
– Carbon deposits grow so large that they can cause total
blockage of the reformer tubes, resulting in the development of
“hot spots”
• Carbon forming reactions can be suppressed by adding excess
steam
• A common practice is to operate the reformer at steam-to-carbon
ratios of 2.5−4.5 mol H2O/mol C, the higher limit applying to higher
hydrocarbons such as naphtha
Methane slip (% of unreacted methane)
• Most applications require syngas at elevated pressure. Therefore,
most modern steam reformers operate at pressures far above
atmospheric, despite the fact that this is thermodynamically
unfavorable.
• The advantages of operating at elevated pressure are the lower
syngas compression costs and a smaller reformer size. The down
side is a lower methane conversion.
• To counterbalance the negative effect on the equilibrium, higher
temperatures are applied and more excess steam is used
• It is generally economically advantageous to operate at the highest
possible pressure and, as a consequence, at the highest possible
temperature
• The tube material, however, places constraints on the temperatures
and pressures that can be applied: a maximum limit exists for the
operating temperature at a given pressure because of the creep
limit of the reformer tubes
• At typical reformer temperatures and pressures an appreciable
amount of methane is still present in the syngas produced.
• A low methane slip is often crucial for the economics of the
process.
• There is a trend towards higher operating temperatures (exceeding
1200 K), which is made possible by the increasing strength of the
tube materials
 Syngas as feedstocks

Power
Ammonia
Generation Hydrogen
Chemicals

SYNGAS Syngas
production

Fischer-
Methanol Tropsch Naphtha

Petrol

Acetic Acid DME Ethylene Diesel

 3.3 Industrial Ammonia
Synthesis and applications
 Background
• Ammonia is a major product of the chemical industry
• Industrial Revolution and the related growth of the population
generated a large demand for nitrogen fertilizers
• Natural resources of nitrogen-containing fertilizers were saltpeter
(KNO3), Chile saltpeter (NaNO3), and guano (seabird droppings)
• At the beginning of the twentieth century, ammonia was produced
as by-product in coke ovens and gas works.
• It was recognized as early as the twentieth century that fertilizer
supplies were not sufficient for agricultural needs due to the
development of the explosive industry
• Around 1910 it was well documented that at atmospheric pressure in a
mixture of nitrogen, hydrogen and ammonia hardly any ammonia is
present
• Haber found that at 1290 K the fraction of NH3 in an equilibrium
mixture of N2, H2, and NH3 (N2/H2 = 1/3 mol/mol) was only 0.01%
• These data convinced many experts, that industrial synthesis based on
nitrogen would never be economically feasible
• Haber extrapolated these data to lower temperatures and concluded
that an industrial process was feasible, if suitable catalysts could be
developed.
• Interestingly, Haber also pointed out that an industrial process is
possible even if conversion is not complete by proposing a recycle loop
under pressure and the use of heat exchanger
• In the unbelievably short period of five years (1908–1913), Haber
developed a commercial process in operation (30 t/d) in cooperation
with Bosch and Mittasch at BASF
 Industrial Ammonia Synthesis
• The production of ammonia requires a mixture of hydrogen and
nitrogen in a ratio of 3:1
• The catalyst used is iron promoted with K2O, CaO, SiO2, or Al2O3
• The source of nitrogen is invariably air
• Hydrogen can be produced from a variety of fossil fuels and
biomass.
• Steam reforming of natural gas followed by secondary reforming
with air is most often employed in ammonia plants and accounts for
over 80% of ammonia production
• The reaction: N2 + 3H2 ⇋ 2NH3
• Thermodynamics
– Favorable conditions are low temperature and high pressure.
– However, kinetic limitations exist: at temperature below 670K
the rate of reaction is very low. Therefore, the temperature to
be used is the result of an optimization procedure
– Similarly, regarding pressure, the optimal situation is a
compromise between thermodynamically favorable conditions
and minimal investments
• Typical conditions:
– Temperature: 675 K (inlet); 720-770 K (outlet)
– Pressure: 100 – 250 bar
 The Haber Process
• The Haber Process combines nitrogen from the air with hydrogen
derived mainly from natural gas (methane) into ammonia. The
reaction is reversible and the production of ammonia is exothermic

Nitrogen Unreacted gas recycled

(from air)
Reactor
1:3 by volume
Separator
T: 700 K (Condenser)
P: 200 bar
Hydrogen Iron cat.
(from
natural gas) Gases are cooled and
ammonia turns to liquid
• To combine the two starting materials of nitrogen and hydrogen to
produce ammonia, the bonds in the diatomic molecules have to be
broken.
• A high pressure of more than 100 bar and temperature above
400°C, nitrogen adsorbed to the catalyst and is splitted up into
atoms.
• Hydrogen can now be adsorbed and ammonia is produced. The
catalyst itself remain unchanged.
• This reaction generate heat and therefore the reacting hot gas in
the ammonia reactor is cooled with the supply of cold steam. This is
achieved with the flow system of synthesized gas based on the heat
exchange principle
• The ammonia is collected as a liquid and stored in tanks. The
remaining synthesis gas returns to the reactor and forms more
ammonia.
 Ammonia synthesis reactor
• Ammonia synthesis reactors are classified by flow type (axial, radial
or cross flow) and cooling method
• Temperature control is crucial in ammonia synthesis: the reaction is
exothermic and the heat produced needs to be removed. Two
methods are applied: (1) direct cooling and (2) indirect cooling
– In the case of direct cooling in so-called quench reactors, cold
feed gas is added at different heights in the reactor
– Indirect cooling is achieved with heat exchangers that are placed
between the catalyst beds
• An example of a reactor with direct cooling is the ICI quench reactor
and Kellogg vertical quench reactor
Ammonia synthesis loop
• Unconverted syngas leaves the reactor together with ammonia due
to incomplete single-pass conversion (20-30% per pass)
• Mixture is passed through a separator, ammonia is condensed and
unconverted syngas is recycled to the reactor
• By continual recycling of the unreacted nitrogen and hydrogen, the
overall conversion is about 98%.
Industrial applications of ammonia
• Agricultural and fertilizer industry
– Accounts for 80% of total ammonia production
– Production of ammonia phosphate, (NH4)3PO4
– Production of ammonia nitrate, NH4NO3
– Production of ammonia sulfate, (NH4)2SO4

• Nitric acid production – Produce explosives such as TNT

• Petroleum industry use ammonia to:
– Neutralize acid constituents of crude oil
– Protect equipment from corrosion
• Rubber industry – prevent premature coagulation by stabilizing
natural rubber
• Pulp and paper industry – For pulping wood
• Ammonia-soda industry – Produce soda ash
• Textile industry – Manufacture synthetic fibers such as nylon and
rayon
• Plastic industry – Manufacture of phenolics and polyurethanes
3.4 Industrial Methanol Synthesis
and application
 3.4 Industrial Methanol Synthesis and
application
• Methanol – Also known as methyl alcohol
• Chemical formula CH3OH (abbr. MeOH)

• Simplest alcohol; light, volatile, colourless, flammable liquid with

distinct odour similar to ethanol
• Unlike ethanol, methanol is highly toxic and unfit for consumption
• Methanol synthesis was the second large-scale process involving
catalysis at high pressure and temperature
• The commercial process for the production of methanol based on
syngas was developed by BASF
 Reactions, Thermodynamics, Catalyst
• Main reactions: Formation of methanol from syngas

• Water-gas shift reaction

• From Table 6.6, the optimum conditions is at a higher pressure and
lower temperature
• The original catalysts (based on Zinc) were only active at high
temperature. Therefore, the pressure had to be very high (250−350
bar) to reach acceptable conversions.
• More active catalysts (based on copper) were known, which led to a
new generation of plants, the “low-pressure plants”
• Industrial catalysts used:
– ZnO-Cr2O3
– CuO-ZnO-Al2O3 (used by BASF)
 Synthesis Gas for Methanol Production
• Syngas for methanol production is produced by steam reforming of
natural gas
• The ideal syngas for methanol production has a H 2/CO ratio of about 2
mol/mol. A small amount of carbon dioxide (about 5%) increases the
catalyst activity
– H2/CO ratio lower than 2 mol/mol leads to increased by-product
formation (higher alcohols, etc.)
– Higher ratio results in a less efficient plant due to the excess
hydrogen present in the syngas
• The composition of syngas depends on the feedstock used. When
naphtha is the raw material, the stoichiometry is approximately right.
When methane is used, however, hydrogen is in excess, which has to
be purged.
• In practice, either the excess hydrogen is burned as fuel or the
content of carbon oxides in the syngas is increased. This can be
done by one of two methods:
– When available, carbon dioxide addition to the process is a
simple and effective way to balance the hydrogen and carbon
oxides content of the syngas. Carbon dioxide addition can be
implemented by injecting it either in the reformer feed stream
or in the raw syngas. In both cases the stoichiometric ratio for
methanol synthesis is achieved, although the compositions will
be somewhat different.
– Installing an oxygen-fired secondary reformer downstream of
the steam reformer, or using only autothermal reforming. In the
latter case, the syngas is too rich in carbon oxides (H2/CO ≈ 1.7–
1.8 mol/mol), so adjustment of the gas is required. This can be
done by removing carbon dioxide or by recovering hydrogen
from the synthesis loop purge gas and recycling it to the reactor
feed
 Classical Methanol Synthesis
• The first industrial plants were based on a catalyst that was fairly
resistant to impurities but not very active nor selective
• To achieve a reasonable conversion to methanol, these plants were
operated at high pressure
• The heart of the process is the reactor with a recirculation loop
according to the same principle as in ammonia synthesis
• The crude methanol is distilled to separate the methanol from
water and impurities
• A bed of activated carbon is used to filter and remove contaminants
and impurities from the feedstock, using chemical absorption
• The high operating pressure (~300 bar) of this classical methanol
process results in high investment costs and high syngas
compression costs
• In addition, large amounts of by-products are formed due to the
low selectivity of the catalyst
• These by-products include ethers, hydrocarbons, and higher
alcohols
• A major breakthrough came in the late 1960s with the development
of low-pressure processes using the more active and selective
copper-based catalysts
• All modern processes are low-pressure processes with plant
capacities ranging from 150 to 6000 t/d, although plants using
remote natural gas may have a capacity as large as 10 000 t/d
 Modern Low Pressure Methanol Process
Plants
ICI process
• In the ICI process, an adiabatic reactor is used with a single catalyst
bed
• The reaction is quenched by adding cold reactant gas at different
heights in the catalyst bed
Lurgi Process
• The Lurgi process is very similar to the ICI process. The most
important difference is the reactor. In the Lurgi process, a cooled
tubular reactor is used
• The catalyst particles are located in the tubes and cooling takes
place by boiler feed water (BFW).
• The Lurgi reactor is nearly isothermal.
• The heat of reaction is directly used for the generation of high-
pressure steam (circa 40 bar), which is used to drive the
compressors and, subsequently, as distillation steam.
Haldor Topsoe Process
• In the Haldor Topsøe process, several adiabatic reactors are used,
arranged in series
• Intermediate coolers remove the heat of reaction.
• The syngas flows radially through the catalyst beds, which results in
reduced pressure drop compared to axial flow.
• Crude methanol purification is the same as in the other processes.
 Industrial applications of methanol
• Primarily used as feedstocks: formaldehyde, MTBE, acetic acid,
DME, Olefins, etc…
– Paints, Resins, adhesives, solvents, pigments and dyes
• Transportation fuel
– has a high octane rating that allows for superior vehicle
performance compared to gasoline
• Water dinitrification
– removal of nitrogen (nitrate from waste water)
• Transesterification process for producing biodiesel fuel
– This process reacts methanol with the triglyceride oils
contained in vegetable oils, animal fats, or recycled greases,
forming fatty acid alkyl esters (biodiesel)
• Electricity generation
End of Chapter 3

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