Professional Documents
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PROCESSING
TECHNOLOGY
ELSEVIER Fuel Processing Technology 42 (1995) 85-107
Abstract
Tubular reforming and autothermal or secondary reforming of natural gas are the most
important process steps in the production of synthesis gas. The paper reviews the state-of-the-
art of the technologies with emphasis on new developments in equipment design, especially
relating to the tubular reformer furnace and to the burner for the autothermal or secondary
reformer. The chemical reactions are briefly described, and the various steam reforming
processes - tubular, fired reforming, heat exchange reforming, and adiabatic pre-reforming
- are reviewed. The difference between autothermal and secondary reforming and new develop-
ments in these process technologies are highlighted.
1. Introduction
Natural gas is the most important raw material for, production of ammonia,
methanol, hydrogen, carbon monoxide, and many other important products. In
almost all cases it is converted catalytically by reaction with steam and/or oxygen-
containing gases, i.e. air, enriched air, or oxygen. The related technologies, i.e. the
various versions and combinations of steam reforming and autothermal or secondary
reforming, are thus key technologies in the petrochemical and fertilizer industries
today.
The technologies have been known and applied in the industry for more than 50
years and must today be considered quite mature. However, important new develop-
ments are constantly being made, both in equipment design and in the related
catalysts. The purpose of the present paper is to review the state-of-the-art and to
describe recent developments for tubular reforming and autothermal and secondary
reforming with emphasis on process concepts and design of critical items.
2. The reactions
Steam may be replaced by carbon dioxide, which gives a more favourable hydrogen
to carbon monoxide ratio for many syntheses:
80
60
40
Fig. 1. Equilibrium composition (dry gas). Steam reforming of methane. Pressure 30 bar, steam-carbon
ratio = 4.0.
The product gas composition from a reformer can be estimated from thermodyn-
amic calculations because it will in most cases be close to that of the equilibrated gas.
A list of equilibrium constants may be found in [2]. The overall heat of reactions
(l)-(3) may be positive, zero, or negative, depending on the process conditions. At low
steam to carbon ratios and at low catalyst exit temperatures, the overall reaction is
only slightly endothermic or even exothermic, if the feed contains high concentrations
of higher hydrocarbons. This is caused by methanation of carbon monoxide formed
by reaction (3) and reflected by a high content of methane in the product gas. In such
cases, it is possible to carry out the process without external heating, e.g. in an
‘adiabatic pre-reformer’. However, for the production of gases with lower methane
contents such as synthesis gas and hydrogen, a high catalyst outlet temperature is
required, and the overall reaction becomes strongly endothermic. In such cases, heat
must be supplied to the reaction, which then takes place in a tubular reformer.
The conversion of hydrocarbons with oxygen is done in the catalytic autothermal
or secondary reforming processes and also in the non-catalytic partial oxidation
processes. Due to the internal combustion these processes are exothermic and takes
place in adiabatic reactors.
Reactions (1) and (3) may be accompanied by the following reactions forming carbon:
2co = c + coz, AH = - 41 kcal/mol (6)
CH4 = C + 2Hz, AH = + 18 kcal/mol (7)
C,H, -+ nC + m/2Hz (8)
Reaction (6) is normally referred to as the ‘Boudouard reaction’. At high temper-
atures (above about 65o”C), higher hydrocarbons may react in parallel to reaction (3)
by thermal cracking (pyrolysis or “steam cracking”) into olefins which may easily
form coke via reaction (9):
C,H, + olefins + polymers + coke. (9)
Reactions (6) and (7) are reversible, whereas (8) and (9) are irreversible for n > 1.
Carbon formation is discussed in detail in [Z-4].
88 I. DybQzrlFuel Processing Technology 42 (1995) 85-107
A Topsere reformer furnace is shown in Fig. 2 [S]. The tubes, which are filled with
catalyst, are arranged in a single row, and burners are placed in the furnace walls at
four to six levels. With this arrangement, it is possible to adjust and control the heat
input along the length of the tube, thus ensuring an optimum temperature profile at all
operating conditions. Hot flue gas leaves the radiant chamber through a refractory-
lined duct, and the heat is utilized in the flue gas waste heat section. Feed
gas passes from a distribution header through the inlet hairpins to the tubes.
In this case the inlet hairpin is connected to the side of the reformer tube, allowing
higher preheat temperature. The inlet hairpin is flexible, allowing expansion of the
tube.
The tubes are supported at the bottom and expand upwards through the furnace. In
order to reduce the load on the refractory-lined collector and to eliminate any risk of
tube bending, most of the tube weight is supported by a spring arrangement connected
to the top flange of the tube.
Process gas from the outlet of the reformer tubes passes through the transition joint
outside the furnace to the refractory-lined outlet collector. In other applications, an
alternative outlet system with hairpins and hot collector is used. The two outlet
systems are illustrated in Fig. 3 [S].
Lk
Catalyst
TUbe
.I :;
_.;., .:,::.:
Cold Collector
Catalyst Tube -
Pigtail
The gas composition at the outlet of the reformer is strongly influenced by the
process conditions. Therefore it is essential to consider the steam reformer not only as
a furnace but also as a chemical reactor. The most important variables are:
(i) hydrocarbon feed characteristics; (ii) inlet steam to carbon ratio; (iii) outlet tem-
perature; (iv) outlet pressure.
The feed to the reformer can be any hydrocarbon ranging from a hydrogen-rich
off-gas or natural gas to heavy naphtha. In some cases it is also advantageous to add
carbon dioxide at the inlet of the reformer in order to save hydrocarbon feedstock and
decrease the hydrogen to carbon monoxide ratio in the product gas. In such cases the
carbon dioxide from the outlet of the reformer is recycled, and extra carbon dioxide
may be imported when available.
Maximum conversion to carbon monoxide by the reverse shift reaction (2) is
favoured by a low steam to carbon ratio. A low steam to carbon ratio, however, results
in high methane content. In order to compensate for this, the reformer outlet
temperature can be increased. A high outlet temperature also changes the equilibrium
of the shift reaction towards carbon monoxide. In Figs. 4 and 5 [S] the gas composi-
tion at the reformer outlet is shown as a function of steam to carbon ratio and outlet
temperature for a case where the feedstock is naphtha.
Temperature, “C
Fig. 4. Hydrogen to carbon monoxide ratio in reformer exit gas as function of steam-carbon ratio (s/c) and
outlet temperature. Feed: naphtha; pressure 21.6 bar.
I. DybkjmJFuel Processing Technology 42 (1995) 85-107
25
I I I I I I I I I I
Of
760 780 800 820 840 860 880 900 920 940 960 980
Temperature, “C
Fig. 5. Methane content (dry) in reformer exit gas as function of steam-carbon ratio (s/c) and outlet
temperature. Feed: naphtha; pressure 21.6 bar.
Traditionally, the steam to carbon ratio in reformers was relatively high due to the
risk of carbon formation. The development of new highly active steam reforming
catalysts including noble metal based catalysts [6], the use of sulphur passivated
reforming [7], and the installation of adiabatic pre-reformers [8] make it possible to
reduce the steam to carbon ratio to below 1.0.
The outlet pressure strongly affects reaction (1) while reaction (2) is not affected. An
increase in pressure results in high methane content. Normally, the highest acceptable
pressure is chosen so that compression downstream the reformer is avoided or
minimized. In other cases the pressure is dictated by the requirements of downstream
separation or purification processes, e.g. PSA units, membrane units or cryogenic
units.
The heat input required by the reformer, the reformer duty, is the enthalpy
difference between the exit and the inlet gas, and it can easily be calculated from
enthalpy tables. The duty consists of heat of reaction as well as heat required to raise
the temperature to the level of the reformer exit. In a typical tubular reformer furnace,
about 50% of the heat produced by combustion in the burners is transferred through
the reformer tube walls and absorbed by the process gas (in an ammonia plant: 60% for
reaction, 40% for temperature increase). The other half of the fired duty is available in
the hot flue gas and recovered in the waste heat section of the reformer for preheat
92 I. Llybkjar/Fuel Processing Technology 42 (199.5) 85-107
duties and for steam production. In this way, the overall thermal efficiency of the
reformer may approach 95%.
The balance between heat input through the reformer tube walls and heat con-
sumption in the endothermic reforming reaction is the central problem in steam
reforming. The stress value in the tubes is strongly influenced by the maximum tube
wall temperature and by the maximum heat flux. Even a slight increase in the
maximum tube wall temperature may result in a serious decline of the expected tube
lifetime.
Recent developments in metallurgy have allowed safe designs with exit gas temper-
atures exceeding 950°C corresponding to tube wall temperatures up to 1050°C. The
new materials which have superior creep rupture characteristics, allow a design with
a considerable reduction in tube wall thickness. The use of a thin tube wall improves
the tube lifetime by increasing the tolerance of the tube to thermal cycling and thermal
shock [9].
The tube geometry has a complex influence on the reformer design. Increasing the
length of the tubes is more economical than increasing the number of tubes, because
more tubes mean more complex inlet and outlet systems. However, the tube length is
limited by the risk of tube bending and by restrictions in pressure drop across the
catalyst.
For a given tube length, feed flow, and reformer duty, the number of tubes is
determined by the selected tube diameter, d,, the average heat flux, qav, and the space
velocity, SV. These parameters are interrelated. It can be shown by a total heat
balance and by assuming constant inlet and outlet conditions that, independent of the
number of tubes:
qay = d, * sv. (10)
This means that only two of these three parameters can be selected freely. If qav is
constant and d, increases, the number of tubes decreases, also decreasing the number
of inlet and outlet hairpins. The pressure drop over the reformer also decreases,
whereas the dimensions of the furnace box remain’roughly constant. The catalyst
volume, however, increases linearly with d, (reduced SV, Eq. (lo)), and the total weight
of the tubes increases more than proportional to d, due to increased tube wall
thickness above a minimum diameter below which the tube wall thickness must be
kept constant for other reasons.
Tubular reformers are designed with a variety of tube and burner arrangements.
Basically there are four types of reformers as illustrated in Fig. 6 [Z].
The bottom fired type has an almost constant heat flux profile along the length of
the tube. The furnace appr0aches.a counter-current design resulting in high metal
temperatures at the outlet. The terrace wall fired reformer is a modification of the
bottom fired type, having slightly lower tube wall temperatures. The top fired
reformer is characterized by a peak in the tube wall temperature in the upper part of
the reformer, and it has the highest heat flux where the metal temperature is at its
1. DybkjmlFuel Processing Technology 42 (1995) 85-107 93
maximum. The side wall fired furnace allows adjustment and control of the tube wall
temperature. The maximum temperature is at the outlet of the tube, whereas the
highest heat flux is at a relatively low temperature. The side wall fired design thus
offers more flexibility in design and operation, and higher average heat flux and more
severe operating conditions are possible. As an added advantage, the short residence
time in the flames in the side wall fired furnace ensure very low NO, levels in the flue
gas, typically below 50 ppm for reformers without combustion air preheat.
Typical tube wall temperature and heat flux profiles for top- and side fired
reformers operating at the same conditions are shown in Fig. 7 for start of run. The
600 -
1 I I
20 40 60 80 100
Tube Length, %
Fig. 7. Tube wall temperature and heat flux profiles. Side and top fired reformers. Start of run.
94 I. DybkjmlFuel Processing Technology 42 (1995) 85-107
temperature profiles are based on measured data from operating reformers. The heat
flux profiles are calculated on the basis of the temperature profiles using computer
models, which take into account both the geometry of the furnace chamber, the heat
transfer from the furnace to and through the tube, and the heat transfer and catalytic
reactions inside the tube.
It is seen that the tube wall temperature profile for the top fired reformer shows
a flat maximum approximately one third down the tube. In the side fired reformer, the
tube wall temperature increases at a controlled rate to a maximum value at the outlet
of the tube. The heat flux profile of the top fired reformer shows a sharp maximum in
the top of the tube - at a location where the tube wall temperature is relatively high. In
the side fired reformer, the heat flux profile is much flatter, there is no distinct
maximum, and the highest local heat flux is much lower that in the top fired reformer,
although the average heat flux is higher.
Furthermore, the tube temperature at the point where the heat flux is highest is
much lower in the side fired reformer than in the top fired reformer. It is thus evident
that the side fired concept allows a much higher average heat flux than the top fired
concept. Comparisons based on the same average heat flux are, therefore, unrealistic.
They may be relevant for comparison of reformers of the same type, but they are
misleading for different types, e.g. in comparisons of side and top fired reformers.
A more relevant comparison would be based on maximum local heat flux. Even in this
case, the conditions on the tube would be more severe in the top fired reformer
concept because of higher temperature at the peak in the heat flux. This means that
also for the same maximum heat flux, the tubes in the side fired reformer are subject to
lower stresses and thus can be designed with thinner wall (at same diameter) or larger
diameter (at same wall thickness).
A further point of considerable interest is the ‘response’ of the furnace to changes in
catalyst activity. Such changes are inevitable due to ageing of the catalyst and possibly
due to poisoning, e.g. by sulphur. Reformers of all types normally contain ample
catalyst activity - the conversion is determined by the heat transfer. This means that
a significant loss of activity can be accommodated without any loss of conversion and
with only modest increase in the temperatures in the lower end of the tube, provided
the required heat is made available. There is, however, a significant effect on the tube
wall temperatures in the upper part of the tube as shown in Fig. 8. The reduced
activity means that less reaction takes place here, whereby the temperatures increase
as indicated by the dotted lines because less heat is consumed. In the top fired
reformer this means that the maximum tube wall temperature increases correspond-
ingly, since the maximum temperature is in the top of the tube. The tubes must
therefore be designed with a considerable margin above the start-of-run maximum
temperature, or, alternatively, the capacity of the unit must be reduced, since reduc-
tion of the total firing is the only possible way to reduce the heat input in the top of the
tube. Also, there is a risk of carbon formation on the hot tube wall, which will
aggravate the problems and lead to so-called ‘hot banding’, very high tube wall
temperatures in a narrow, well-defined area.
In the side fired reformer the temperature in the top can increase significantly
without approaching the design temperature, which is determined by the conditions
I. LlybkjazrlFuel Processing Technology 42 (1995) M-107 95
lOOO-
- Start of Run
600- ----End df Run
Tube Length, %
I 1 1 I ,
20 40 60 80 100
Fig. 8. Tube wall temperature profiles at start and end of run. Side and top fired reformer.
at the lower part of the tube. Furthermore, the firing can be adjusted if the tube wall
temperatures approach the design temperature, and loss of capacity, tube damage by
hot banding, or premature catalyst change can thus be avoided.
The information obtained from the experiments is in the form of outer tube wall
temperature profiles, axial and radial catalyst bed temperature profiles, axial conver-
sion profiles, and pressure drops. This information is then used for evaluation of the
conditions to which the catalyst and tube have been exposed during the experiment,
and for parameter estimation in reaction kinetic models and in heat transfer and
pressure drop correlations.
The catalyst is examined in the laboratory after a certain operating period. Proper-
ties such as physical strength, pore volume distribution, sulphur capacity, carbon
content, and intrinsic activity give important information about risk of carbon
formation and expected catalyst life and thus about the suitability of the tested
catalyst for a given process.
In heat exchange reforming, part or all of the heat required for the reforming
reaction is supplied by heat exchange with process gas. This is in contrast to the
conventional ‘tubular reforming’ where all heat is supplied by external combustion,
and to secondary or autothermal reforming, where the heat is supplied by internal
combustion.
A number of heat exchange reformers have been designed for hydrogen production
in fuel cell plants, where the requirements with respect to compactness, high efficiency,
and good load following characteristics are essential. One mechanical concept of these
units is known as the heat exchange reformer (HER) [18]. The capacity range for the
HER is 504000 N m3/h of hydrogen for fuel cell operating conditions (low pressure).
An alternative design better suited for high pressure applications and for larger
capacities is the convection reformer. A full-scale process demonstration unit with
a capacity of 840 Nm3/h hydrogen has been operated at Topsoe’s Houston pilot
facilities for more than 2000 h.
The convection reformer is designed with a number of bayonet reformer tubes. It is
heated mainly by the flue gas flowing upwards on the outside of the reformer tubes,
but also by the reformer gas flowing upwards through the bayonet. With the purpose
of optimizing the heat transfer, a sleeve has been installed around the cold end of the
reformer tube. At the hot end, the reformer tube is inherently protected against
overheating by means of a patented convection control device. This ensures that the
98 I. Dybkja?rlFuel Processing Technology 42 (1995) 85-107
Tube Length
Fig. 10. Topsee convection reformer. Temperature profiles from the process demonstration unit.
metal surfaces. It is thus important that a gas with a high Boudouard temperature
does not come into contact with a metal surface with a temperature below, but close
to Boudouard temperature. In an operating reformer, the catalyst outlet temperature
will always be above Boudouard temperature (because carbon would otherwise be
formed on the catalyst). A temperature drop in the reformer outlet system or in the
cooling channels of the heat exchange reformer could, however, bring the product gas
below the Boudouard temperature, i.e. into an area where carbon may be formed on
the metal surface.
At most conditions, Fe-Ni-Cr alloys are protected against carburization by an
oxide layer. However, if this film is destroyed, a catastrophic corrosion can occur
[26,27]. The corrosion starts by pointwise attack, probably by carburization at
defects in the oxide layer. The corrosion products can easily be eroded and holes are
formed in the material similar to pitting.
5. Adiabatic pre-reforming
Tubular Reformer
Steam
Hvdrocarbon Feed
Fuel
I .
To Heat Recovery
- All higher hydrocarbons are completely converted to carbon oxides and meth-
ane. Even in plants based on naphtha, natural gas reforming catalyst may be used in
the tubular reformer.
- All traces of sulphur from the desulphurization unit are removed, increasing the
lifetime of the tubular steam reforming catalyst and low temperature shift catalysts.
- Since there is no sulphur poisoning of the top layer of catalyst in the tubular
reformer, the risk of hot banding or hot spots is reduced.
- The production capacity of the plant can be increased. By installing an extra
preheat coil or heater between the pre-reformer and the tubular steam reformer, the
load on the reformer is decreased. This can be utilized either as a capacity increase or
as a decrease in firing with unchanged capacity.
_ The sensitivity of the tubular steam reformer to variations in steam to carbon
ratio and feedstock composition is practically eliminated.
- The benefits can be achieved in all plants having a tubular steam reformer, i.e.
ammonia plants, methanol plants, hydrogen plants, oxogas/carbon monoxide plants,
town’s gas plants, and reducing gas plants. Use of pre-reforming is discussed in
[&lo-12, 29).
6. I. Process concepts
Carbon Dioxide
Fig. 12. Typical process flow diagram for autothermal reforming. Production of synthesis gas with
hydrogen-carbon monoxide ratio 2.0.
102 I. DybkjcerlFuel Processing Technology 42 (1995) 85-307
<
Process Steam <
Natural Gas Feed
11:”
t Stack
Recycle Gas
Combustion Air
J
To Waste Heat
Fuel Gas Recovery and Shih
Fig. 13. ‘State-of-the-art’ reforming section for production of ammonia synthesis gas.
Make-up Gas
Natural Gas
_ I Heat Recovey
(mm Methanol
Synthesis
I I
The autothermal reformer reactor and the secondary reformer are very similar.
Both consist of a compact refractory-lined pressure vessel with a burner, a combustion
chamber and a catalyst bed. The chemical reactions taking place are combinations of
combustion and steam reforming reactions dividing the reactor space into three
reaction zones, as illustrated in Fig. 15 [30].
The burner is the key element of the autothermal and secondary reforming techno-
logy. The burner provides the mixing of the feedstreams in a turbulent diffusion flame.
The flame core has a very high temperature, often above 2OOo”C,and transfer of heat
back to the burner from the flame core by radiation and by recirculation of hot gas
must be minimized. Hence, a burner design based on the understanding of the fluid
dynamic principles of the mixing and combustion processes is necessary to obtain
a safe operation and a satisfactory burner lifetime.
The combustion zone is the turbulent diffusion flame where the hydrocarbon and the
oxygen are gradually mixed and combusted. Normally, the principle of ‘mixed-is-
burnt’ can be assumed, because the exothermic combustion reactions consuming
oxygen are very fast reactions. The combustion proceeds as a substoichiometric
process with an overall oxygen to hydrocarbon ratio of 0.55-0.6. The combustion of
methane takes place through numerous radial reactions, but in a simplified model it
can be considered as one molecular reaction, i.e. the highly exothermic combustion of
methane to carbon monoxide and water with an oxygen to methane ratio of 1.5.
Excess methane will be present at the combustion zone exit after all the oxygen has
been converted. Combustion of higher hydrocarbons can be simplified by similar
reactions.
The so-called thermal zone is the part of the combustion chamber where further
conversion of the hydrocarbons proceeds by homogeneous gas phase reactions. The
main reactions are thermal methane reforming (1) and water-gas shift reaction (2), but
various pyrolysis reactions involving higher hydrocarbons also take place.
The combustion chamber is followed by a fixed catalyst bed, the catalytic zone, in
which the final hydrocarbon conversion takes place through heterogeneous catalytic
reactions. At the exit of the catalytic zone the synthesis gas will be in equilibrium with
respect to the methane reforming (1) and shift reactions (2). The catalyst will destroy
any soot precursors formed in the combustion and thermal zones.
Thermal Zone
Catalyst Bed I Catalvtic Zone
The top of the catalyst bed is exposed to the process gas leaving the combustion
chamber at temperatures of llOO-14OO”C, and high thermal stability of the catalyst
and the carrier system is required. A nickel catalyst supported by a magnesia-alumina
spine1 carrier has shown high stability and activity for operation in autothermal and
secondary reformers. The reactions are mainly controlled by film diffusion at the outer
catalyst pellet surface, meaning that the process can be carried out at very high space
velocities. In practice the catalyst volume is determined by optimal flow distribution
and pressure drop in the reactor.
A pilot plant was built for testing and demonstration of new process and reaction
engineering developments in the autothermal reforming technology. The plant was
designed for operation on natural gas and pure oxygen at a capacity corresponding to
100 Nm3/h natural gas producing synthesis gas (carbon monoxide + hydrogen) in
the range of 250-300 N m3/h. Mixtures of natural gas and butane are also applied as
feedstocks.
The scale of the pilot plant was chosen in order to enable reliable adiabatic tests
of the highly exothermic combustion process. In laboratory-scale equipment it is
difficult to carry out adiabatic as well as isothermal experiments on methane
oxidation.
Pilot plant testing also provides the advantages that development of the combus-
tion equipment (burner, combustion chamber and refractory) can be made at realistic
conditions which is required for the scale-up to larger industrial plants.
The pilot plant has been in operation for three years, and recent tests have shown
that trouble-free operation is possible at very low steam to carbon ratios, at high
equilibrium temperatures, as well as at high addition of carbon dioxide feed. Synthesis
gases with a hydrogen to carbon monoxide ratio below 1.0 have been produced [30].
In the design of the burner and the combustion chamber, the following reaction
engineering aspects are of general importance: (i) effective mixing at the burner
nozzles; (ii) low metal temperatures of the burner; (iii) soot-free combustion;
(iv) homogeneous gas and temperature distribution at the entrance to the catalyst
bed; (v) protection of the refractory from the hot flame core.
Recirculation of the reacted gas from the thermal zone back to the burner can
protect the refractory and the burner from the hot flame core and ensure a homogene-
ous gas and temperature distribution at the entrance to the catalyst bed.
The CTS burner technology can be used both for new plants and for revamp of
existing plants, e.g. for boosting the production capacity. In a modified version the
CTS burner may be used also in secondary reformers. Industrially, CTS burners have
been used in recent revamps of existing autothermal reformers. After 1 year in
operation the CTS burner at one of the plants was inspected. It showed no sign of
wear or corrosion indicating much improved burner performance and extended
burner lifetime.
Use of autothermal reforming is discussed in [30, 331.
7. Alternative processes
8. Conclusions
Steam reforming and autothermal reforming are the most important technologies
for production of synthesis gas. Important new developments with respect to both
process and equipment design have recently been introduced to the industry. Alterna-
tive processes such as selective oxidation of methane to carbon monoxide and
hydrogen and direct conversion of methane to products such as methanol or ethylene
are widely discussed, but have not yet been developed to a point where they are of
industrial interest.
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