164 CHAPTER 4 FLOW-SHEETING

0.9
0.8 22M propane
0.7 cyclopentane
0.6 cyclopentene
i-pentane
Fraction

0.5
n-pentane
0.4
dienes
0.3
acetylenes
0.2
pentenes
0.1 methyl butenes
0.0
400.00 500.00 600.00 700.00 800.00 900.00 1000.00
Temperature (°C)
FIGURE 4.9
Product distribution

EXAMPLE 4.2
Hydrogen can be made by steam reforming of methane, which is a highly endothermic process:

CH4 þ H2 O $ CO þ 3H2 ΔH° rxn ¼ 2:1 105 kJ=kgmol

Steam reforming is usually carried out in fired tubular reactors, with catalyst packed inside the tubes and fuel fired on
the outside of the tubes to provide the heat of reaction. The product gas mixture contains carbon dioxide and water vapour as
well as carbon monoxide and hydrogen and is conventionally known as synthesis gas or syngas.
Hydrogen can also be made by partial oxidation of methane, which is an exothermic process, but yields less product per
mole of methane feed:

CH4 þ ½ O2 ! CO þ 2H2 ΔH° rxn ¼ 7:1 104 kJ=kgmol

When steam, oxygen and methane are combined, heat from the partial oxidation reaction can be used to provide the heat
for steam reforming. The combined process is known as autothermal reforming. Autothermal reforming has the attraction
of requiring less capital investment than steam reforming (because it does not need a fired-heater reactor), but giving higher
yields than partial oxidation.
The yield of hydrogen can be further increased by carrying out the water gas shift reaction:

CO þ H2 O $ CO2 þ H2 ΔH° rxn ¼ 4:2 104 kJ=kgmol

The water gas shift reaction equilibrates rapidly at temperatures above about 450 °C. At high temperatures this reaction
favours the formation of carbon monoxide, whilst at low temperatures more hydrogen is formed. When hydrogen is the
desired product, the shift reaction is promoted at lower temperatures by using an excess of steam and providing a medium-
or low-temperature shift catalyst.
In an autothermal reforming process, 1000 kmol/h of methane at 20 °C is compressed to 10 bar, mixed with 2500 kmol/h
of saturated steam and reacted with pure oxygen to give 98% conversion of the methane. The resulting products are cooled and
passed over a medium-temperature shift catalyst that gives an outlet composition corresponding to equilibrium at 350 °C.
i) How much heat is required to vaporize the steam?
ii) How much oxygen is needed?
iii) What is the temperature at the exit of the autothermal reforming reactor?
iv) What is the final molar flow rate of each component of the synthesis gas?
 4.5 SIMULATION OF UNIT OPERATIONS 165

Solution
This problem was solved using Aspen Plus. The model must simulate the high temperature reforming reaction and also the
re-equilibration of the water gas shift reaction as the product gas is cooled. A Gibbs reactor can be used for the high tem-
perature reaction, but an equilibrium reactor must be specified for the shift reactor, as only the water gas shift reaction will
re-equilibrate at 350 °C. Because the methane compressor supplies some heat to the feed, it should be included in the model.
Since the question asks how much heat is needed to vaporize the steam, a steam boiler should also be included. The oxygen
supply system can also be included, giving the model shown in Figure 4.10.
The heat duty to the reforming reactor is specified as zero. The oxygen flow rate can then be adjusted until the desired
methane conversion is achieved. For 98% conversion, the flow rate of methane in the autothermal reactor product (stream
502) is 2% of the flow rate in the reactor feed (stream 501), i.e., 20 kmol/h. For the purpose of this example, the oxygen flow
rate was adjusted manually, although a controller could have been used, as described in Section 4.8. The results are shown
in Figure 4.11.
When the simulation model was run, the following values were calculated:
i) The steam heater requires 36MW of heat input.
ii) 674 kmol/h of oxygen are needed.
iii) The temperature at the exit of the reforming reactor is 893 °C

FIGURE 4.10
Autothermal reforming model
166 CHAPTER 4 FLOW-SHEETING

FIGURE 4.11
Autothermal reactor model results

iv) The molar flow rates at the outlet of the shift reactor (stream 504) are:

H 2504
HO 1956
CO 68
CO 912
CH 20

It should be immediately apparent from the model output that the process as simulated is far from optimal. The oxygen
consumption is larger than the 500 kmol/h that would have been needed for partial oxidation. The excess oxygen is needed
because the additional steam that is being fed must also be heated to the reactor outlet temperature, which requires more of
the feed methane to be burned. The corollary of this result is that the hydrogen yield, at roughly 2.5 moles per mole meth-
ane, is not much better than could have been obtained with partial oxidation followed by shift, despite the large excess of
steam used.
The designer has several options that could be examined to improve this process:
1) Increase heat recovery from the product gas to the feed streams to preheat the reactor feed and reduce the amount of
oxygen that is needed.
2) Reduce the amount of steam fed with the methane.
3) Bypass a part of the steam from the reformer feed to the shift reactor feed, so as to obtain the benefit of driving the
equilibrium in the shift reactor without the cost of providing extra heat to the reformer.
4) Reduce the conversion of methane so that a lower reactor conversion and lower outlet temperature are required.

In practice, all of these options are implemented to some extent to arrive at the optimal autothermal reforming con-
ditions. This optimization is explored further in problem 4.13.