Advanced steady-state modelling and optimisation of Natural Gas

Reforming reactors
Vasco H. Manaçasa, Henrique A. Matosa, Štěpán Špatenkab
a
Chemical Engineering Department, Instituto Superior Técnico, Lisbon, Portugal
b
Process Systems Enterprise Ltd., London, United Kingdom
December, 2013

Abstract
Natural gas reforming (NGR) is an important sector in the chemical and petrochemical industry. It
is a source of hydrogen for the refining industry and the main source of synthesis gas for the
manufacture of chemicals such as ammonia and methanol. Production of synthetic fuels via
Fischer-Tropsch has great potential to become another major application of NGR. Demand for
NGR products will be increasing in the near future so it is important to develop accurate and
predictive modelling tools for decision support in reactor and process design and operation.
This dissertation presents initial developments on NGR modelling in gPROMS®. The two main
reformers, the steam methane reformer (SMR) and the autothermal reformer (ATR) were
modelled. The gPROMS® Advanced Model Library for Fixed-Bed Reactors (AML:FBCR) was used
for detailed modelling of the catalyst beds considering rigorous intra-particle mass and heat
transport. Simplified models were developed for the furnace of the SMR and for the combustion
chamber of the ATR.
Two industrial cases from the literature were studied. The one for SMR was simulated with a
fixed wall temperature profile and afterwards with heat fluxes calculated from a radiation fired
heater model. Both approaches revealed good agreement with plant data. The one for ATR was
simulated with the simplified combustion chamber and predictions had only minor discrepancies
from plant outlet data.
A set of operational conditions, of the SMR case study, were optimised for maximum hydrogen
throughput, at the expense of lower energy efficiency (more 0.9 kJ/mol H2 spent).

Keywords: Natural gas reforming, steam methane reforming, autothermal reforming, gPROMS,
modelling, optimisation.

growing and GTL is becoming an interesting source of

1 Introduction
clean, high quality fuels
Natural gas reforming (NGR) is a key sector in the
NGR processes have been established in industry for
chemical and petrochemical industry. It is the main
more than 50 years [2] but there is still room for
route to hydrogen and synthesis gas manufacture.
improvement. New concepts for reactor or process
These products have a wide range of applications:
design are still being developed and some were
hydrogen is extensively used in the refinery for
already successfully implemented.
hydrotreatment and hydrocraking operations helping
Considerable work was made on mathematical
produce cleaner fuels; synthesis gas is used in
modelling of reformer reactors: reaction kinetics [3];
ammonia production, methanol production and fuel
tubular steam reformer (SMR) and firebox [4–7];
production in gas-to-liquids (GTL) plants.
autothermal reformer (ATR) [8,9]; and heat
Environmental awareness is causing an increase on
exchanging reformer (HER) [10–12]. Optimisation
both supply and demand of the NGR market. On the
studies are also reported in the last two decades
supply side, gas flaring is becoming an outdated
[13,14].
practice and shale and tight gas are becoming
Most of the modelling efforts so far used over-
acceptable sources for natural gas [1]. On the
simplified approaches, especially for optimisation
demand side, hydrogen refinery demands are
studies. NGR reactors involve complex reaction

1
mechanisms controlled by the intra-particle diffusion
rates and with radial gradients of temperature and
composition on the catalyst tube side; complex
combustion or radiation phenomena takes place on
the heating side of the reactor.
Detailed and accurate modelling of natural gas
reformers would give better insight into process
design and operation [15] and would become a very
useful tool for managers and engineers to make
informed process innovation, design and operation
decisions.
The objective of this work is to start developing
modelling solutions for natural gas reforming with
the purpose of, in the future, creating a
comprehensive accurate and predictive modelling
pack for synthesis gas manufacture in gPROMS®.
2 Natural Gas Reforming
NGR processes and technology were reviewed. A
process example is showed in Figure 1 and only the
main reformer will be described hereinafter. For a
more in depth review please consult [15–17].
2.1 Feedstocks
Natural gas is the main feedstock for hydrogen and
syngas production [15,17]. Other possible
hydrocarbon feedstocks are naphtha with boiling
points up to 200 °C.
The usual reforming agent is steam, oxygen or air but
alternative compounds like carbon dioxide or even
methanol can be used. The choice of reforming agent
will depend on the reactor used and on the desired
outlet syngas composition: steam increases the
H2/CO ratio while carbon dioxide decreases it.
Figure 1 Illustration of hydrogen production process flow diagram with SMR [17].
2
2.2 Chemical Routes
In a natural gas reforming process stable molecules,
need to be broken into less stable, highly reactive
molecules. To accomplish this there are two main
routes: steam reforming and partial oxidation.
Methane steam reforming produces a syngas with a
H2/CO ratio of 3.0. Higher hydrocarbons react in a
similar way to steam reforming reaction (SR).
(1)
(2)
Along with the SR, water gas shift reaction (WGS)
also occurs.
(3)
These reactions are all reversible with exception for
steam reforming of higher hydrocarbons and all of
them require a catalyst, typically supported nickel.
Some natural gas reforming processes take
advantage of partial oxidation of hydrocarbons (POX)
which is an irreversible process. The reactions may,
or may not require a catalyst.
(4)
2.2.1 Undesired reactions
The main problem faced by natural gas reformers is
carbon formation. And it can be formed from one of
the following reactions:
(5)
(6)
(7)
In steam reformers carbon deposition, (6) and (7), is
the main source of fixed carbon. Steam and newly
developed catalysts minimize this issue. Reaction (5)
is known as the Boudouard reaction and it is
responsible for metal dusting corrosion [17].
Carbon formation can also occur via thermal cracking
of higher hydrocarbons at temperatures above 550
°C. The introduction of pre-reforming minimizes this
issue by removing higher hydrocarbons from the
main reformer [16].
Other sources of undesirable reactions are sulphur
poisoning and sintering of the catalyst [15,16].
2.3 Reactors
The main, and most wide-spread, reactor designs for
NGR are steam methane reforming (SMR) and
autothermal reforming (ATR). While these two will be
described hereinafter, other important reforming
technologies include catalytic and non-catalytic
partial oxidation and, more recently developed, heat
exchange reformers (HER) and oxygen membrane
reformers, and are addressed in [15].
Two-step or combined reforming reactors are also
important reactor configurations. Two of the referred
reactors, usually ATR, SMR or HER, are arranged in
series or parallel.
2.3.1 Steam methane reformer – SMR
As the name suggests, the steam methane reformer
(SMR) follows the SR reactions. This reformer is often
called tubular fired reformer because of the reactor
design.
In SMR the reaction proceeds inside a number of
reformer tubes while heat is being transferred from a
furnace radiant chamber. This radiant chamber has
burners installed on the walls where the fuel is
burned releasing heat. Only 50% of this heat is
transferred to the reformer tubes, the remainder is
recovered on the convection section of the furnace
for pre-heating duties and steam generation. Flue gas
temperatures are brought down close to 200 °C and
overall thermal efficiencies of 95% can be attained
[17].
Reactor operation is limited by tube material
maximum allowed temperature, as increasing this
temperature will decline expected tube lifetime.
Recent metallurgical developments allow maximum
tube wall temperatures of 1050 °C [17].
Since most reformers operate near or at equilibrium
outlet conditions, the key variables that define outlet
gas composition are: hydrocarbon feed composition,
inlet S/C ratio, outlet temperature and pressure.
Typical conditions are inlet S/C ratios of 2-5,
3
operating pressures of 10-40 bar and outlet
temperatures of 800-950 °C. Inlet temperatures to
the reformer tubes are limited by thermal cracking of
higher hydrocarbons so the typical range is 450-550
°C [16]. The upper limit rises up to 650 °C when a pre-
reformer is installed.
Synthesis gases produced by SMR from natural gas
have H2/CO ratios between 2.8 and 4.8 [16].
2.3.2 Autothermal reformer – ATR
An autothermal reformer (ATR) is a refractory lined
vessel composed by a burner, a combustion chamber
and a catalyst fixed-bed. As the name suggests, the
reformer is thermally self-sufficient and operates
adiabatically with exothermic POX reactions
providing the necessary heat for the endothermic SR
reactions.
In the combustion chamber flame temperatures over
3000 °C can be achieved. As homogeneous SR
reactions occur, gas temperatures at catalyst bed
inlet drop down to 1100-1300 °C [15]. Outlet
reformer temperatures are usually around 900-1100
°C [15]. Typical operating pressures are higher than
for SMR and can reach 30-50 bar. Oxygen is fed at
sub-stoichiometric conditions, typically at oxygen to
methane ratios (O2/C ratios) of 0.5-0.6 [2]. Carbon
free operation requires a small amount of steam
corresponding to S/C ratio lower than 1.0.
Hydrocarbon feed can be natural gas or partially
reformed gas (from a primary reformer). The latter is
usually called secondary reformer. The concept is the
same but operating conditions are different and
require different a different reactor design [17]
The oxidant used can be pure oxygen or (enriched)
air and both have advantages and draw backs. Air-
blown ATR doesn’t need an air separation unit but
requires larger equipment and compression costs
and so it is only used when nitrogen is needed in the
syngas such as in ammonia production
ATR reforming of natural gas can provide lower
H2/CO outlet ratios (1.8-3.8) than SMR due to the
introduction of oxygen instead of steam [16].
3 Modelling
3.1 gPROMS Libraries
The gPROMS Advanced Model Library for Fixed-Bed
Catalytic Reactors (AML:FBCR) was used to model
reactor sections with fixed catalytic beds.
The two main reactor models used from this library
were one and two dimensional catalyst beds with
rigorous mass and heat transport inside the catalyst
pores: Catalyst_Pellets_Section and
Catalyst_Pellets_Section_1D_Adiabatic.
The library uses a set of user-specified sub-models,
where kinetic equations or other correlations can be
defined. These customisations are discussed in the
following sections.
A full description of these models’ equations won’t
be presented because it wasn’t a model developed
during the course of this work and because of
intellectual property rights.
It is important to understand how the radial heat
transfer is modelled in the two-dimensional model.
Both convective and diffusive heat transfer are
considered. The diffusive heat transfer uses an
effective radial conductivity, λe,r, and wall heat
transfer coefficient, αw.
(8)
[ ] (9)
The gPROMS Process Model Library for Steady State
(PML:SS) conversion reactor and signal models were
used to model the combustion chamber of the ATR.
3.2 Physical properties
General physical properties were predicted using
GERG 2008 corresponding states model which is
specific to natural gas applications.
3.3 Reaction kinetics
The reaction kinetics model used was the one
developed by Xu and Froment [3]. They established a
Langmuir Hinshelwood model that has been
extensively used throughout the literature.
The kinetic model considers three global reactions
(10): steam reforming of methane to carbon
monoxide, SR(I), and to carbon dioxide, SR(II) and
water gas shift, WGS. It was assumed the natural gas
does not contain higher hydrocarbons so no reaction
kinetics are needed for them.
(10)
The reaction rate expressions and coefficients can be
found in the original paper.
Equilibrium was calculated from:
∑ For natural gas, it is common to approximate partial
(11)
Besides kinetic rate equations some key performance
indicators were also calculated: the effectiveness
factor and the approach to equilibrium:
4
∫ ( ) ⁄ (12)
∏
(13)
3.4 Bed properties
Bed porosity was predicted according to Reichelt and
Blass.
Radial heat transfer parameters correlations were
customised to the ones used in [4] and also can be
found in [18]. These parameters are used in
equations (9) and (8), and have static and dynamic
contributions. The static contribution relates to heat
transfer in the hypothetic situation of zero flow and
the dynamic relates accounts for hydrodynamics.
(14)
(15)
The dynamic correlations for in AML:FBCR include an
adjustable parameter that allows the user to adjust
the correlations to their own experimental data.
3.5 Fired heater
Detailed modelling the heat transfer from the firebox
to the reformer tubes is a challenge. Modelling
radiative heat transfer requires intensive
calculations, taking into account geometry view
factors, gas emissivities and burner geometry. In this
work a simplified approach to the furnace was used
and a typical radiation heat flux equation was
considered. Equation (16) is used to calculate heat
flux or tube wall temperature and applies two
effective parameters: an effective emissivity and an
effective temperature.
This approach assumes radiation is the only form of
heat transfer, neglecting convection contributions.
The effective emissivity lumps geometry effects
(number and location of burners, flame size, firebox
size and number of burners); and emissivities from
the different sources present (furnace, reformer
tube, fluid and flame). While the effective
temperature reflects the heating intensity (fuel
flowrate, flame temperature).
( ) (16)
3.6 Combustion chamber
combustion reactions in ATR as a one molecular
reaction. Since a secondary reformer may receive
partially reformed gas with some hydrogen content,
hydrogen combustion was also considered [9].
(17)
(18)
The combustion chamber was modelled using the
conversion reactor from PML:SS The model was set
adiabatically with reaction stoichiometry.
Conversion needs to be set for both reactions and
the signal library from PML:SS was used to that
purpose. Complete oxygen conversion is considered,
and selectivity is set between methane partial
oxidation and hydrogen combustion reactions.
3.7 Steam methane reformer
A possible configuration for the SMR is showed in
Figure 2. There are two material stream sources, one
for natural gas and another for steam; a junction
(mixer); two catalytic reactor beds, one connected to
a fired heater and the other working in adiabatic
mode.
The methods used in catalyst section model from
AML:FBCR need to be configured. The radial heat
transfer was considered through fluid. Real mixture
partial enthalpy calculations were. Intra-particle
diffusion is calculated using the Dusty-gas model as
Knudsen diffusivity is used in [4]. Finally, solid-fluid
heat and mass transport uses the correlations from
Hougen (1961), the default in AML:FBCR.
Some key performance indicators are automatically
calculated by the model, like outlet methane
conversion and outlet H2/CO ratio.
3.8 Autothermal reformer
The ATR model uses the combustion chamber model
in PML:SS and the SMR catalyst bed model in
AML:FBCR. A “gML to PML” connector model is
required to change the reference state from pure
elements (PML:SS) to compounds (AML:FBCR).
A possible configuration for the SMR is showed in
Figure 3. There are two material stream sources, one
for the feed (natural gas or reformed process gas)
and another for oxygen or enriched air; one mixer;
Figure 2 SMR model topology using a fired heater.
5
one catalytic reactor bed: one connected to a fired
heater and the other working in adiabatic mode.
The methods used in this adiabatic one dimensional
catalyst section model from AML:FBCR were
configured to the same corresponding options as in
the SMR two-dimensional model.
Some key performance indicators are automatically
calculated by the model, like inlet O/C ratio, outlet
methane conversion and outlet H2/CO ratio.
4 Simulation Results
4.1 Steam Methane Reforming
The example used for this case study comes from the
work by Xu, Froment and Plehiers [4,6] where an
industrial steam reformer was modelled. Their
reactor tube model consists of a one dimensional bed
model with one dimensional pellet model accounting
for intra-particle diffusion. The firebox is modelled
using a detailed zone method model.
4.1.1 Reactor configuration
Reactor and catalyst dimensions were taken from the
original papers, as well as the major properties.
Missing parameters, like conductivities or emissivities
were taken from other literature examples.
4.1.2 Thermodynamic results
Methane equilibrium conversion is shown in Figure 4
at different temperatures, pressures and S/C ratios.
These results clearly depict equilibrium constraints
on steam reforming reactors. These are important
restrictions which explain why steam reforming
reactors need to operate at such high temperatures.
Figure 3 ATR model topology.
 100 According to these results the model suggests plant
Methane conversion (%)
90 data conversion is better than equilibrium
80 conversion, which is impossible. The ideal gas
70 assumption for reaction rates and reaction
60
equilibrium may be invalid, and vapour fugacity
50
40 rather than vapour concentration should be used. Yet
30 it is also possible the reported plant measurements
20 are inaccurate as a result of temperature or pressure
10
drops in the reactor outlet system or from non-
0
800 1000 1200 1400 1600 uniform operation between different catalyst tubes
Temperature (K) inside the reformer.
1200
20 bar, S/C 4 30 bar, S/C 4 20 bar, S/C 2

30 bar, S/C 2 20 bar, S/C 1 30 bar, S/C 1

1100

Temperature (K)
Figure 4 Methane equilibrium conversion as a function of
1000
temperature at different pressures (20 and 30 bar) and at
different S/C ratios (1, 2 and 4).
900
4.1.3 Case I: Fixed temperature profile
Here the reactor from this case study was modelled 800

using the developed SMR model with fixed outer

700
tube wall temperature from plant data in [6]. 0 2 4 6 8 10 12
In order to match plant outlet conditions (pressure Axial distance (m)
and temperature) the heat transfer adjustable
coefficients and bed porosity had to be adjusted. The Wall, outer Wall, inner

heat transfer correlations were reduced to 48.9% and Fluid radial average Fluid at wall

Fluid at tube centre Fluid, Plehiers 89

the final value for bed porosity was 0.48.
Table 1 SMR simulation results comparison with paper.
Plant data
Conversion 64.5% - 70.2%
H2/CO 7.41 - 7.98
Outlet T (K) 1038.0
Outlet P (bar) 24.4
Simulation results in Table 1 reveal the model
developed in this work has better agreement with
plant data than the one used by the original authors.
It is also interesting to see that although predicted
conversion is closer to plant data, there is still a small
gap between these two.
The difference in predicted conversion could be due
to reactor operation away from equilibrium but
predicted reaction rates are close to zero at reactor
outlet, so the reaction mixture at the outlet of the
adiabatic section must be close to equilibrium. In
fact, according to Figure 4, in order to achieve
conversions like the ones reported in plant data the
reactor would need to operate at lower outlet
pressure, higher inlet S/C ratio or higher outlet
temperature.
Figure 5 SMR Case I axial temperature profiles.
Present work Plehiers, 89
The predicted radial average fluid temperature in
61.6% 47.0% Figure 5 can be compared to the one dimensional
7.88 7.86 temperature profile from the original paper. The two
1038.0 1033.0 profiles are close to each other and are similar in
24.4 25.6 trend with exception of the entry region, the first 2
meters of catalyst bed. In this region a temperature
drop, of around 30 K at tube centre, is observed in
the two dimensional model, which is due to the
strongly endothermic reactions in SR and isn’t
detectable in Plehiers’ profile. Radial fluid
temperature differences around 50 K also give a clear
idea of how energy demanding and endothermic this
process is.
Other key phenomena in steam reforming are pellet
heat and mass transport limitations. The model
predicts external heat transfer limitations: a
temperature drop of 9-10 K over the gas film
surrounding the particles at wall position is detected
and agrees with literature. It also predicts internal
mass transfer limitations with effectiveness factors
under 10%. Figure 6 shows the reaction occurs
almost only at the catalyst surface – only 15% of the

6
active layer is used. These results agree with other 4.2 Autothermal Reforming
literature findings [15]. The example used for this case study comes from the
0,3
work by Al-Dhfeery et. al. [9] where an industrial
secondary reformer was modelled.
In [9], their reactor model consists of a global mass
Reaction rate (mol/kg-cat s)

0,2 and energy balance for the combustion zone, and of

a one dimensional bed model with effective reaction
rates calculated from a Thiele modulus.
0,1
4.2.1 Reactor configuration
Reactor and catalyst characteristics used came from
0,0
the original paper or from AML:FBCR defaults.

4.2.2 Sensitivity analysis: Combustion

-0,1 chamber
0 0,5 1 1,5 2
The industrial ATR is a secondary reformer and a
Pellet radial distance (mm)
choice has to be made regarding selectivity of oxygen
SR(I) WGS SR(II) for methane partial combustion and hydrogen
combustion. So a sensitivity analysis was performed,
Figure 6 SMR Case I reaction rates radial pellet profile, at monitoring catalyst bed fluid temperature profiles.
radial wall position and 2.9 m axial position.
1500
4.1.4 Case II: Fired heater
The same industrial case used for Case I was 1450
modelled using the fired heater model described in
Fluid temperature (K)

section 3.5 with the objective of calculating heat flux 1400

rather than fixing temperature.
Table 2 SMR Case II: Fired heater predicted parameters. 1350
model prediction
Effective emissivity 0.13 1300
Effective temperature (K) 1741.4
In Table 2 the value for effective temperature is 1250
1 0,0 0,5 1,0 1,5 2,0 2,5
between the adiabatic flame temperature (~2223 K)
Axial distance (m)
and flue gas temperature (1273-1325 K) reflecting
heat contributions from walls, flame and flue gas. 1.00 0.75 0.50 0.25 0.00
Regarding the value for effective emissivity, it falls
outside the usual emissivity values (0.6-0.95) because Figure 7 ATR combustion selectivity analysis, catalyst bed
this is a lumped model parameter where the axial temperature profiles with varying CH4/H2
geometry view factors are taken into account. combustion selectivity.
The simplified furnace model used in this case study From Figure 7, it is seen combustion reaction
is able to predict reasonable temperature and heat selectivity has mainly influence on fluid inlet
flux profiles for this industrial side-fired reformer, temperature. The predicted temperatures fall in the
that agree with reported plant data. It is not a range reported in literature [15]. Since there is no
replacement for a detailed furnace model, but it will plant data available for the combustion zone
be used for optimisation. selectivity was set to reaction (17).
Even though inlet temperature to the bed changes
from 1360 K to 1500 K, there is practically no change
to reactor outlet conditions. This is because the
reactor model always achieves equilibrium and being
an adiabatic vessel, the global energy balance
1
Value for methane/air adiabatic flame temperature, remains unchanged.
the major component of the fuel used in [6].

7
4.2.3 Case I be adjusted by changing pellet tortuosity, porosity or
Results shown in Table 3 reveal good prediction in mean pore radius from AML:FBCR default values to
terms of outlet composition and only slight increase internal diffusion limitations. Without plant
deviations in temperature, pressure and conversion. measurements inside the reactor it’s not possible to
Outlet pressure difference relates to combustion confirm how the reactor bed behaves.
zone and burner pressure drops, as well as inert Another possible explanation is that ATR catalysts
catalyst sections that weren’t considered. Outlet may have lower activity than SMR catalysts, so the
temperature deviations between this model and Al- kinetic parameters would need to be adjusted.
Dhfeery and co-workers’ model can relate to Moreover, it is unlikely the reactor operates with two
different thermodynamic models, but the deviation thirds of inactive bed. Other possible explanations
to plant data might relate to heat losses. ATR could reflect that the catalyst bed is essential to
reformer vessels are considered to be adiabatic, but stabilize the reaction mixture after the combustion
they operate at such high temperatures that a water zone – the catalyst bed can be slightly over-
cooling jacket may be used to stabilize external wall dimensioned.
temperature. In fact, Aasberg [15] refers that outer
metal skin temperatures are reduced to 100-200 °C
5 SMR Optimisation
The SMR model used in section 4.1.4 with a fired
so it is possible that minor heat losses are present.
Table 3 ATR Case I combustion and catalyst zone outlet heater model operational conditions were optimised.
results. Those results were starting point for optimisation.
Plant Present Al-Dhfeery, unit 5.1 Problem formulation
data work 12
s The reactor system was optimised for maximum
Combustion zone
hydrogen production at a fixed natural gas feed
Outlet T - 1361.8 1369.8 K flowrate. The objective function is:
Outlet P - 32 32 bar ( ) (19)
Catalyst The control variables included in are:
zone
Outlet T 1242.2 1264.8 1282.8 K { ⁄ } (20)
Outlet P 31.6 31.9 31.9 bar These correspond to four key design variables of the
Conversion 95.6% 97.4% 95.5% reactor: inlet temperature to the reactor tube, ;
H2/CO 4.39 4.45 4.44
inlet pressure to the reactor tube, ; fired heater
effective temperature, ; and inlet ⁄ .
H2/N2 2.51 2.50 2.51
The problem was subject to the following constraints:
(H2+CO)/N2 3.08 3.06 3.08
(21)
Molar composition at combustion and catalyst zone
(22)
outlets shows almost no difference with plant data or
Maximum temperature constraint reflects a material
the paper’s predictions. Although these differences
constraint and maximum pressure drop was assumed
are very small, Predicted conversion deviates from
to be 120% of the base case scenario.
plant data due to a small absolute difference in
-4
The region where an optimal solution was searched
methane outlet composition, 8x10 , which
for is defined on each design variable by:
corresponds to a significant relative error of 69%.
(23)
Predicted axial profiles suggest that almost only one
(24)
third of the reactor is being used for reaction (see
Figure 7) and are quite different from the original (25)
paper, where the whole catalyst bed is active. ⁄ (26)
Al-Dhfeery and his co-workers used effectiveness The upper bound on inlet temperature to the
factors of around 0.003, predicted from the Thiele reformer is a real material constraint to avoid
modulus for spherical pellets, while the present thermal cracking of hydrocarbons. The fired heater
model calculates effectiveness factors around 0.03, effective temperature is an indirect model parameter
from detailed diffusion inside a hollow cylindrical for heating intensity. In real operation the fuel
pellet. This difference can explain the different axial flowrate and air excess would be adjusted to get
profiles. The profiles predicted with this model could required process gas outlet temperature.

8
The optimisation problem had 109837 equations and
111261 variables. A total of 1420 variables were
assigned and the remainder 4 degrees of freedom
correspond to the four design variables considered.
The optimal solution was found in 499 seconds using
an Intel® Core™ i7-3770S CPU with 16.0 GB of RAM.
Since the WGSR will convert more carbon monoxide
to hydrogen more energy can be recovered. This
should compensate the SMR energy efficiency
decrease towards hydrogen production. The
downside is that this heat will be recovered in the
form of steam and this may be undesired.

5.2 Results and discussion 6 Conclusions

Optimisation results are summarised in Table 4. The two main natural gas reforming reactors (NGR),
Hydrogen production and methane conversion the steam methane reformer (SMR) and the
increases of 32.2% and 40.2%, respectively, were autothermal reformer (ATR), were successfully
accomplished by increasing energy use in both modelled with detailed fixed-bed reactor models and
furnace and feed preheating. The total energy simplified models for other key components.
demand increase was 33.3%. Constraints (21) to (24) Simulation results were compared against two
are active. industrial case studies and both models are able to
Table 4 Optimisation results, objective function, control predicted plant profiles and outlet conditions with
variables and KPI’s.
some deviations on outlet composition and
Base Optimal units
conversion due to model assumptions (e.g. ideal gas
Objective function 3.287 4.346 mol/s
assumption on equilibrium calculations) or to
Control variables inaccurate reported plant data (temperature,
Tin 793.15 923.15 K pressure and equilibrium composition).
in
P 29 32 bar The predicted radial profiles for the SMR case study
Teff 1742.35 1872.04 K show pronounced differences from tube centre to
S/C ratio 3.358 3.664 wall (e.g. temperature) even for small diameter
KPI's tubes, which reveals the need for accurate two-
Conversion 61.6% 86.3% dimensional bed models when diagnosing
H2/CO 7.89 5.66 performance or designing this type of reactor and is
Tout
1038.00 1143.92 K
in agreement with literature [15].
Pellet radial profiles predicted in both SMR and ATR
Table 5 Total energy consumption (in furnace and feed
cases clearly demonstrate the need for detailed
preheating duties) per mole of hydrogen produced and
per mole of methane converted. multi-component diffusion inside catalyst particles
Base Optimal Change units for this type of systems. In spite of the presence of
EH2 117.6 118.5 0.8% kJ/molH2
light gases that should show high diffusion rates, the
reaction rates are even higher, rendering observed
ECH4 437.1 415.6 -4.9% kJ/molCH4
reaction rates below 10% of the intrinsic reaction
5.3 Optimisation conclusions rates; the fact that hydrogen and methane have very
Optimised conditions provide higher hydrogen different diffusivities also supports this necessity as it
production and methane conversion at the expense makes a reaction like water gas shift proceed in one
of higher energy demand. The global energy direction at catalyst surface and in the reverse
efficiency of the single reactor is slightly worse direction inside the catalyst particle – see Figure 6.
towards hydrogen production (more 1.1 kJ is spent Finally, the SMR model with the fired heater model
per mole of H2 produced) and somewhat better was used for operational optimisation where
towards methane conversion (less 31.5 kJ spent per hydrogen throughput was maximised by increasing
mole of methane converted). thermal preheating and furnace duties. Optimal
The impact on downstream equipment is such that solution revealed slightly less energy efficient
water gas shift converter section (WGSR) will handle operation towards hydrogen production but
more hydrogen production from CO, producing more considering total methane conversion it revealed
energy from the exothermic reaction. Upstream of somewhat more efficient.
the SMR a pre-reformer will be needed to allow
reformer inlet temperatures of up to 923.15 K.

9
6.1 Achievements
The objective of this work was to initiate the
development of models for NGR reactors with the
purpose of creating accurate and predictive
modelling solutions for hydrogen and synthesis gas
manufacture in gPROMS®. This was achieved with the
SMR and ATR reactor case studies.
The simplified approaches to furnace and combustion
chamber modelling proved to reasonably represent
real profiles.
Finally, the operating conditions of the SMR industrial
case were optimised using the detailed SMR reactor
model with fired heater. This demonstrated that
optimisation of complex accurate models is possible,
within the same modelling environment.
6.2 Future work
In order to further complete this work towards a
comprehensive accurate and predictive modelling
pack for synthesis gas manufacture there are still
several steps to be taken.
Kinetics modelling can be improved by tackling the
ideal gas assumption and implementing fugacity
calculations. Steam reforming of higher hydrocarbons
also needs to be considered. The undesired coking
reactions can also be modelled.
The SMR furnace model needs to be improved,
ideally accounting for detailed radiation and
convection heat transfer.
Modelling of NGR related equipment such as the pre-
reformer and the WGSR will allow modelling of the
complete NGR process. Developing models for other
type of reactors like the heat exchanging reactors will
provide different options for process design
optimisation.
Finally, complete process modelling and
optimisation, considering reactor or process design,
with detailed high-fidelity models would be a proof of
the power and capabilities of advanced process
modelling to provide decision support and help
achieving the best process innovation, design and
operation decisions.
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