CHE329

Petrochemical , Manufacturing & Application

Module 3
Synthesis Gas production and derived chemicals
: Steam Reforming
Course Outcome
Describe the industrial manufacturing
process of various petrochemical
products and its applications.

Explain the process block diagram and

P&ID of various types of petrochemical
processes including the unit operations
and utility systems involved.
Course Learning Outcome
By the end of the module, students should be able to:

• Describe the steam reforming process in

1 gas production and derived chemicals

• Describe the industrial Ammonia

2 Synthesis and applications

• Describe the industrial Ammonia

3 Synthesis and applications
 1.Introduction

4.Industrial
Methanol 2.Steam
Synthesis OUTLINE reforming
and process
applications

3.Industrial
Ammonia
Synthesis and
applications
 Introduction
• Synthesis gas (or syngas) – refers to mixtures of
hydrogen and carbon monoxide in various ratios.
• Table 5.1 shows some syngas applications.
• Syngas term is universal: the N2/H2 mixture for
ammonia production is also referred as syngas.
• Source of syngas - ranging from natural gas to coal.
• Raw material choice depends on cost, availability of
the feedstock and syngas applications.
• Syngas produced by one of three processes,
distinguished based on the feedstock used:
• steam reforming of natural gas 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.
• Steam reforming - reaction of HCs + steam + catalyst.
• This process should not be confused with the
catalytic reforming process for improving the
gasoline octane number.
• In the gas industry, reforming is used for the
conversion of a HC by reacting it with oxygen-
containing molecules, usually H2O, carbon dioxide,
and/or oxygen.
• Autothermal reforming - a combination of steam
reforming and partial oxidation, in which
endothermic and exothermic reactions are coupled
• Partial oxidation is the non-catalytic reaction of
hydrocarbons with oxygen and steam.
• This process may be carried out in an
autothermal or allothermal way.
• Catalysis is possible and the process is then
referred to as catalytic partial oxidation.
• Gasification is the more common term to
describe partial oxidation of coal or petroleum
coke (petcoke).
The different sources and routes to synthesis gas.
• Syngas - produced by steam reforming of NG or light HCs up to
naphtha.
• Light feedstocks - partial oxidation is not an economic option, because
of the high investment costs due to cryogenic air separation
requirement.
• Partial oxidation - employed where feeds suitable for steam reforming
are not available or where local conditions exist to provide favorable
economics.
• Such conditions - availability of relatively low priced heavy
feedstocks or the need for a syngas with high carbon
monoxide content.
• Coal gasification – an important process for syngas production
in countries with abundant coal resources, such as South
Africa, China, India and the United States. It is also increasingly
used for power generation.
Figure 5.1 General process flow diagrams for the production of syngas.
• Figure 5.1 shows the main processes for syngas production.
• Steam reforming feed 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.
• In steam reforming and downstream uses in many reactors,
transition-metal-based catalysts are used.
• When sulfur is present as hydrogen sulfide (H2S), adsorption
on activated carbon, reaction with an oxide (eg. zinc oxide), or
scrubbing with a solvent may be employed.
• If the feed contains more stable sulfur compounds,
hydrotreating may be required.
• Production of syngas based on coal and heavy oil fractions require
removal of sulfur compounds (mainly H2S).
• Feed purification is not possible with these raw materials, although
attempts have been made using biotechnological approaches.
• Depending on production process and downstream use (Table 5.1),
the raw syngas may be treated in several ways.
• Syngas conditioning includes such processing steps as the water–gas
shift reaction, carbon dioxide removal, methanation and etcetera to
achieve the right composition.
• Partial oxidation of heavy hydrocarbons is very similar to coal
gasification and will not be discussed further.
• This chapter deals with the conversion of natural gas and coal into
syngas.
Steam Reforming Process
• A catalyst is still required to accelerate the reaction even though
steam reforming is carried out at high temperature (>1000 K) due to
the very high stability of methane.
• The catalyst is contained in tubes, placed inside a furnace heated by
combustion fuel.
• The steam reformer (Figure 5.4) consists of two sections.
• In the convection section, heat recovered from hot flue gases is
used for preheating of the gas feed and process steam and
superheated steam generation.
Figure 5.4 Simplified flow scheme of the steam reforming process.
Steam Reforming Process
• In the radiant section the reforming reactions take place.
• After sulfur removal, the NG feed is mixed with steam (and
optionally CO2) and preheated to approximately 780 K before
entering the reformer tubes.
• The heat for the endothermic reforming reaction is supplied by
combustion of fuel in the reformer furnace (allothermal operation).
• The syngas composition leaving the reformer may be further
modified in additional process steps such as secondary reforming
and/or shift reactors that reduce the carbon monoxide content.
• Figure 5.5 shows the general arrangement of a typical steam
reformer.
• The preheated process stream enters the catalyst tubes through
manifolds and pigtails then flows downwards.
• The product gas is collected in an outlet manifold then passed
upwards to the effluent chamber to be further processed.
• The tubes are carefully charged with catalyst particles - evenly
distributed over the tubes and the catalyst bed should be dust free.
• A furnace may contain 500–600 tubes with a length of 7–12 m and
an inside diameter of between 70 and 130 mm.
Figure 5.5 General arrangement of a steam reformer.
(Courtesy of van Uffelen, Technip Benelux B.V)
 a) reformer penthouse structure containing distribution systems for feed, fuel, and combustion
air,including support systems and operator access to burners and catalyst tubes;

b) reformer radiant box with the catalyst tubes arranged in multiple rows;

c) process gas boiler for cooling of the reformer effluent in a single step to approximately 620 K, with
associated steam drum in “piggyback” arrangement

d) combustion air preheater to reduce fuel consumption;

e) steam drum to provide boiler water to boilers in the convection section;

f) convection section, for heat recovery from flue gas leaving the radiant section, with preheat coils
for the process and coils for steam generation/superheating and air preheat;

g) combustion air fan with air intake;

h) stack for discharge of flue gases to safe location

 Carbon Formation
• Carbon formation in steam reformers must be prevented for two
main reasons.
• Firstly, coke deposition on the active sites of the catalyst leads to
deactivation.
• Secondly, carbon deposits grow so large causing total blockage of the
reformer tubes, resulting in hot spots.
• Hence, the reforming conditions must be chosen to limit the carbon
formation.
• Carbon forming reactions can be suppressed by adding excess steam.
• Common practice to operate the reformer at steam-to-carbon ratios
of 2.5−4.5 mol H2O per mol C, the higher limit applying to higher
hydrocarbons such as naphtha.
 Carbon Formation
• Compared to methane, higher hydrocarbons exhibit a greater
tendency to form carbonaceous deposits.
• At high temperature (>920 K) steam cracking occur to form alkenes
that easily form carbon through reaction:

CnH2n → carbon + H2 ∆ rH298 < 0 kJ/mol

• An additional advantage of using excess steam is that it enhances

hydrocarbon conversion due to the lower partial pressure of
hydrocarbons.
 Methane Slip
• Most applications require syngas at elevated pressure (e.g.
methanol synthesis: 50−100 bar and ammonia synthesis at even
higher pressure).
• Thus, modern steam reformers operate at pressures far above
atmospheric, although thermodynamically unfavorable.
• Advantages of operating at elevated pressure - lower syngas
compression costs and a smaller reformer size.
• The down side - lower methane conversion.
• To counterbalance the negative effect on the equilibrium,
higher temperatures are applied and excess steam is used.
 Methane Slip
• Figure 5.6 shows the effect of pressure (left) and excess steam (right) on the
methane slip (percentage of unreacted methane).
• It is economically advantageous to operate at the highest possible pressure
and consequently at the highest possible temperature.
• 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.
Figure 5.6 Effect of pressure (left) and steam-to-methane feed ratio (right) on
methane slip as a function of temperature.
Advances in Steam Reforming
• Improvements include better materials for reformer tubes,
better control of carbon limits, better catalysts regarding
sulfur tolerance and carbon deposition, and better process
concepts with high feedstock flexibility.
• Various modifications of the basic steam reforming process
(Figure 5.4) implemented.
• If NG feed is rich in higher HCs or if naphtha is used as the
feedstock, a pre-reformer may be installed upstream the
reformer furnace to convert these compounds.
• Hence, the worst carbon precursors are removed in
advance, which allows operation of the actual reformer at
lower steam-to-carbon ratio.
Advances in Steam Reforming
• Several different process configurations for
reforming of higher hydrocarbons, including
circulating fluidized bed membrane reformers
(CFBMRs) have been reported.
• Syngas plants normally produce high-pressure
steam that is only partly used in the plant.
• Heat exchange between the high temperature of
the reformer effluent with additional feed, allowing
reforming part of the feed in a multi-tubular
reactor without using a furnace.
Advances in Steam Reforming
• For newly built syngas plants this concept is usually
not applied due to the severe corrosion (metal
dusting) inside the reactor, requiring the selection
of expensive materials.
• However, for capacity revamps this concept is
attractive, enabling typically 25% capacity increase
at low investment costs.
Summary
References & Acknowledgement
• Jacob A. Moulijn, Michiel Makkee, Annelies Van Diepen
(2007). Chemical Process Technology. John Wiley & Sons.
 Developer

Zarina Omar
zarin363@tganu.uitm.edu.my
Faculty of Chemical Engineering