Chapter 3: 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.

 Most syngas today is produced by steam reforming.

 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 (H2S), adsorption
(for instance on activated carbon), reaction with an oxide (for
instance zinc oxide), or scrubbing with a solvent may be
employed to remove it.

 If the feed contains more stable sulfur compounds,

hydrotreating may be required.
Syngas applications in refining, chemical process industry and fuel
production.

Mixtures Main uses

H2 Refinery hydrotreating and hydrocracking
3 H 2 : 1 N 2* 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
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.
Syngas from Natural Gas: Reactions and
Thermodynamics
 Waste heat from the oven section is used to preheat gases and to
produce steam.

 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)

 Themain 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)
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 – 900degC and P = 10-20 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.
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
 Carbonis 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 Formation
 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
 Mostapplications require syngas at elevated pressure. Therefore,
most modern steam reformers operate at pressures far above
atmospheric, despite the fact that this is thermodynamically
unfavorable.

 Theadvantages of operating at elevated pressure are the lower

syngas compression costs and a smaller reformer size. The
down side is a lower methane conversion.
Methane Slip
 To counterbalance the negative effect on the equilibrium, higher
temperatures are applied and more excess steam is used.

 Itis 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 Plant in Malaysia
 BPC Oxo-Alcohols/Syngas Complex in BASF Petronas
Plant, Gebeng – 170k tpa production rate.
 PETRONAS Ammonia Sdn Bhd (Kertih) – production
of 325k mpta
 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.

 IndustrialRevolution 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 20th century, ammonia was produced as
by-product in coke ovens and gas works.

 Itwas 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.

 Fritz 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.

Fritz Haber was a German chemist

who received the Nobel Prize in
Chemistry in 1918 for his invention
of the Haber-Bosch process.
 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 Carl Bosch and Alwin Mittasch at BASF (Badische Anilin und
Soda Fabrik).
 Industrial Ammonia Synthesis
 Theproduction 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 from surrounding air.

 Industrial Ammonia Synthesis
 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.
 Typicalconditions:
◦ 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.

Unreacted gas recycled

Nitrogen
(from air)

Reactor
1:3 by
Separator
volume 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 split 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).

 Mixtureis 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 can raised up to 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.
Ammonia Plant in Malaysia
 PETRONAS Fertilizer (Kedah) Sdn Bhd – production of 350k
mpta
 PETRONAS Ammonia Sdn Bhd (Kertih) – production of 400k
mpta
 Sabah Ammonia Urea Project (Sipitang) – production of 740k mtpa
3.4 Industrial Methanol Synthesis
and Applications.
 Syngas as Feedstocks

Power
Ammonia
Generation Hydrogen
Chemicals

SYNGAS Syngas
production

Fischer-
Methanol Tropsch Naphtha

Petrol

Acetic Acid DME Ethylene Diesel

Background
 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.

 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 (secondary 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.

 Theideal syngas for methanol production has a H2/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.
 Thecomposition 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.

Atlas Methanol Plant in

Trinidad.
 In practice, either the content of carbon oxides in the syngas is
increased or excess hydrogen is burned as fuel This can be done by
one of two methods:

1. 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.

2. Installing an oxygen-fired secondary reformer downstream of

the steam reformer, or using only autothermal reforming. This
will burned the excess hydrogen in the feed syngas.
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 (>300bar).

 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.
Industrial Applications of Methanol
 Primarily used as feedstocks: formaldehyde, MTBE, acetic acid,
DME, Olefins, etc.
◦ Paints, Resins, adhesives, solvents, pigments and dyes.

 Transportationfuel
◦ It has a high octane rating that allows for superior vehicle
performance compared to gasoline.
Industrial Applications of Methanol
 Waterdinitrification
◦ Removal of nitrogen (nitrate from waste water).

 Transesterificationprocess 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
◦ As fuel to heat up the water and turn it into high-pressurized
steam.
Methanol Plant in Malaysia
 PETRONAS Methanol (Labuan) Sdn Bhd – production
of 2.3Mmtpa