A NOVEL ROUTE FOR CONVERTING AROMATICS

INTO HYDROGEN VIA STEAM REFORMING.

F. Fuder

corresponding author; Aral Forschung, D44789 Bochum, Germany

D. Landwehr,
G. Geipel,
C. Herkt-Bruns

Degussa AG, Creavis Technology & Innovation, D45764 Marl, Germany

J. Weitkamp

Institute of Chemical Technology, University of Stuttgart, D70550 Stuttgart, Germany

Abstract

The hydrocarbons which are easy to reform into hydrogen are hydrocarbons with a chain length of less
than six carbon atoms. A new catalyst system which was jointly developed by the group at the University
of Stuttgart and Veba Oel opens up a novel route for production of mainly a n-paraffin feedstock with a
chain length of less than six carbon atoms from a feed with a high aromatic content.
The ratio between aromatic and paraffin compounds in the feed, controls the outlet temperature of the
reactor. The aromatics are converted by hydrocracking. The enthalpy of this step is only used as the
energy source, for the hydrocracking process including the evaporation of the feed. The aromatics which
tend to create problems in the usual steam reforming reaction, are the energy source in this process for
the evaporation of the liquid fuel. The crack reactor does not need any external heat and the outlet
temperature at around 400C is controlled by the ratio between aromatic and paraffin compounds in the
fuel itself.
The hydrocrack product can now be easily converted into hydrogen by the use of a membrane reactor
concept. The application of high pressure and a high hydrogen partial pressure enables the use of
membranes with a Pd layer of less than 10 m thick. This membrane was developed by our partner
Creavis. In comparison to conventional membrane process, this new route provides an economical benefit
in terms of Pd content and exchange area. The pressure for the process is mainly produced by liquid
pumps, this is also a great advantage in comparison to conventional partial oxidation for fuel cell systems.

Introduction

With the advent of the European Auto Oil Programme in 2005, the content of aromatics in
gasoline will have to be reduced from 42 vol.-% to less than 35 vol.-%. Comparable or even more
stringent legislation exists or will be implemented in other parts of the world, for example in
California the aromatics content of gasoline is limited to 22 vol.-%. The problem with aromatics in
gasoline is that the exhaust gas of internal combustion engines may contain small amounts of
aromatics. On the other hand, the high octane numbers of aromatics are very beneficial. Using
other components as octane boosters, e.g., methyl-tert.-butyl ether (MTBE), brings about other
problems. A potential way out of all these problems is a switch to diesel engines which, however,
inevitably leads into the problem of particulate emission. The ultimate solution for all these
environmental problems is often seen in the fuel cell technology.
Upon limiting the aromatics content of gasoline and introducing the fuel cell technology, two major
challenges will have to be mastered, viz.

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finding an outlet for the surplus aromatics and

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INTO HYDROGEN VIA STEAM REFORMING

producing hydrogen in a straightforward and economic manner from todays fuels.

Most fuel cell systems require hydrogen as an energy source, hence large efforts are currently
undertaken to make hydrogen available in cars. Among the routes discussed are steam reforming
and partial oxidation of conventional hydrocarbon fuels or the use of alternative liquid fuels, such as
methanol or liquefied hydrogen. The latter solutions would call for a completely new infrastructure
for fuel supply and/or a new technology for producing the large amounts of hydrogen. Obviously,
the introduction of such non-conventional fuels would require huge investments by the pertinent
industry.
Hydrogen as an automotive fuel could either be manufactured from conventional hydrocarbon
sources in refinery-like stationary plants or on board the cars by direct reforming. Arguments in
favor of the second alternative include the availability of a well established distribution network for
hydrocarbon fuels, the high energy density of the hydrocarbons to be transported as compared to
hydrogen and the low technical risk of hydrocarbon versus hydrogen transportation. We propose
here a novel route for the on-board conversion of aromatics-containing hydrocarbon fuels into
hydrogen.

Description of the The novel route for converting aromatics-containing hydrocarbon fuels into hydrogen takes
Reaction System
advantage of two effects: First, the hydrogenation of aromatics is highly exothermic, and use can be
made of this heat for the vaporization of the liquid feed and for its preheating to the entrance
temperature into the steam reforming reactor. Second, the application of high pressure for the
separation of hydrogen by means of a membrane enables at the same time the separation of
carbon dioxide via its liquefaction. This latter feature allows the recovery of an off-gas with a high
heating value from the membrane reactor. As shown in Figure 1, the process consists of two main
reaction systems referred to as the pretreatment step and the steam reforming step (Figure 1). The
steam reforming step is carried out in a membrane reactor.

Figure 1: Schematic of the reaction system

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INTO HYDROGEN VIA STEAM REFORMING

The Pretreatment Step (Ring Opening Reaction)

VEBA OEL AG and the Institute of Chemical Technology, University of Stuttgart, jointly developed
a new catalyst which allows the conversion of aromatic hydrocarbons with hydrogen into C2+-nalkanes consisting mainly of ethane, propane and n-butane 1,2,3. These hydrogen-rich, light paraffins
can easily be converted into hydrogen via steam reforming. Table 1 shows results of experiments in
which a toluene/n-decane model mixture was catalytically converted in an autothermal fixed-bed
reactor at a hydrogen pressure of 40 bar.

WHSV
Temperature
Methane
Ethane
Propane
Butane
Residual>C4

[1/ h]
[C]
[vol.%]
[vol.%]
[vol.%]
[vol.%]
[vol.%]

0.6
381
1.9
2.8
78.2
11.8
5.2

1.0
370
3.4
5.6
41.6
32.4
17.0

2.0
312
0.2
1.0
79.7
8.7
10.4

Table 1: Results of the cracking of toluene and decane with hydrogen, autotherm.

The ratio between these two compounds is so that the reaction produces enough energy to heat
the gas up to 400C. The results are shown in table 2. We measured the heating consumption of
the reactor system to show this effect. The temperature is independent from the amount of fuel
which goes through the reactor system. The systems work autotherm. The line with base load
means the energy consumption without reaction. This system evaporates the fuel which is called
Chemical Evaporator it can also evaporate commercially available liquid fuels. Therefore, if
the content of aromatic compounds is too low, the reactor must be heated. The advantage of the
aromatics is, that the reactor needs only a small electric heating system and this makes the whole
system smaller because the reactor needs no combusting heating system like a gas burner. One of
the big tasks is, in the whole system is hydrogen and after the Pre-treatment step wont be aromatic
molecule in the stream, so there no cooking effects in the system.

WHSV
Temperature
Toluene/n-Decane
Hydrogen
Power
Base load

[1/h]
[C]
[g/h]
[g/h]
[W]
[W]

0.49
343
157
13.2
82
126

0.24
338
78
6.7
109
133

0.73
345
237
20
88
126

0.49
343
158
13.2
89
126

Table 2: Energy consumption during the crack reaction

To find a solution for the aromatic rich pyrolysis gasoline by naphtha steamcracking, we developed
a new process together with Linde and Sued Chemie. This commercial process presently available
convert pyrolysis gasoline into a high-value synthetic steamcracker feedstock. This process is called
ARINO (Aromatics Ring Opening) process. The commercial catalyst therefore was developed by
Sued Chemie.

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The Steam Reforming Step

The gas consisting of C2+-n-alkanes leaves the pretreatment step with a temperature of about
400C. In a separate water evaporator, water is vaporized and heated to the same temperature.
Both gas streams are above their critical temperatures, so their mixing will be free from problems. A
conventional steam reforming catalyst is used in the reactor, the active component being nickel or a
noble metal, depending on the sulphur content of the feedstock. The reaction temperature
required in the steam reforming reactor is well above 500C.
The thermodynamics of the steam reforming reaction are strongly influenced by the pressure, as
shown in Figure 2. It is evident that methane formation is favored at high pressures.

Figure 2: Thermodynamic concentration as function of the pressure (Propane:Water=1:7@750C).

For economic reasons, the membrane reactor must be operated at high pressure, the ultimate
reason being the high cost of palladium. As shown in Figure 3, the economic requirements can be
met at a membrane thickness of about 10 m and a pressure above 40 bar. The data in Figure 3
were calculated on the basis of a palladium price of 14 US $/g, a PEM efficiency of 50% and
experimentally determined permeation rates of hydrogen through the membrane.

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Figure 3: Costs for the palladium per kW of installed electrical power of the PEM.

Among the main advantages of a membrane reactor is the possibility to exceed the thermodynamic
yield limitations. This allows to operate the steam reformer at a high pressure. As shown in Figure 2,
higher pressures result in decreased CO concentrations, i.e., the concentration of CO 2 is higher
which is important for the separation unit. A very important point is the quality of the hydrogen
produced. The hydrogen from the membrane reactor can be directly used in a fuel cell, i.e., no
additional steps like sulphur removal or treatment of carbon monoxide are required. Furthermore,
a lower surface area of the fuel cell can be employed, since there is no nitrogen which must
normally pass through the fuel cell. The off-gas from the membrane reactor consists of carbon
dioxide, methane, carbon monoxide, water vapor and hydrogen, the concentration of the latter
depending mainly on the membrane area and the reaction temperature. An open reactor with the
membrane inside is shown in Figure 4.
The off gas separation step.
The are two possibilities to produce a gas with a high heating value from the membrane reactor offgas. Firstly, carbon dioxide can be directly liquefied at high pressure, whereby a heating gas is
simultaneously produced. Secondly, upon passing the gas through a nozzle, carbon dioxide partly
solidifies, which brings about a separation as well. It is noteworthy that the off-gas from the
membrane reactor itself has a higher heating value than the off-gas from a normal partial oxidation,
because the former is not diluted with nitrogen. The off-gas from the membrane reactor can hence
directly be used to heat the steam reformer.
Since the off-gas from the membrane reactor serves as the energy source for the steam reformer,
methane is needed as a component due to its high heating value. This is why the higher yields of
methane due to the higher pressure are not a disadvantage. In other words maximizing the
conversion to hydrogen is not aimed at, instead the conversion has to be optimized such as to leave

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INTO HYDROGEN VIA STEAM REFORMING

enough heating value in the off-gas. This is an essential point which makes the system control easier
and reduces the amount of catalyst and the membrane area required.

Figure 4: View of a palladium membrane reactor.

The membrane
manufacturing
process.

Based on woven stainless steel with a first Al2O 3 layer microfiltration membranes could be
achieved. By further coating with nanoscale metal oxide particles smaller pore sizes for ultra- and
nanofiltration applications are realized. Thus membrane foils, less than 80 micrometers thick, are
produced in a continuous process, realizing variable pore sizes down to small nanometer scale. The
degree of chemical and temperature stability required determines which material is used for the
support.
The Ceramic foil production is a continuous process. The production unit coats the woven fabric
with the inorganic suspension, the fabric is dried and hardened. A visual detector excludes defective
material. After the ceramic coating process a PVD-process is attached for finishing the membrane
with a palladium coating. In dependence of the process parameters thickness of the palladium layer
is controlled.
The structure of the hydrogen separation membrane is shown in Figure 5. The TEM detail displays
the surface of the coated membrane.

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Microfiltration: Pores 50500 nm

Ultrafiltration: Pores 550 nm
Nanofiltration: Pores 0.55
nm
Catalytic membranes

Woven Fabric Support

80 m

Figure 5: Hydrogen separation membrane

The blending of
To determine the ratio of aromatic and paraffinic hydrocarbons to be blended, it is useful to classify
aromatic and partheir carbon atoms into various groups. The main criterion is the number of hydrogen atoms bound
affin compounds.
to the carbon atoms. The ratio between aromatic and paraffin components determined the outlet
temperature of the reactor.

Parameter [kJ/mol] 26.41

Component
Paraffin
CH3
n-Decane
n-Octane
Ethylcyclohexane
Ethylbenzene
o-Xylene
n-Heptane
Methylcyclohexane
Toluene
Benzene
n-Hexane
Cyclohexane

4.95
Paraffin
CH2

-9.59
Paraffin
CH

8
6
6
1
0
5
5
0
0
4
6

0
0
1
0
0
0
1
0
0
0
0

2
2
1
1
2
2
1
1
0
2
0

-29.12
-39.78
Aromatic Aromatic Reaction
CH
C
Enthalpy
0
0
0
5
4
0
0
5
6
0
0

0
0
0
1
2
0
0
1
0
0
0

92
82
45
-155
-143
78
43
-158
-175
73
31

Model
Enthalpy
[kJ/mol]
92
82
46
-154
-143
78
42
-159
-175
73
30

Table 3: Structure parameter and model parameter for blending purpose.

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Composition
[mol]
1.00
0.58
1.58

Component
n-Decane
Toluene
Total

Concentrations
[Vol.%]
0.63
0.37
1.0

Enthalpy
[kJ/mol]
92.4
-92.4
0.0

Table 4: Example mixture for testing purpose.

Conclusion

The system described in this paper offers the opportunity to produce hydrogen on a small scale. It
does not require complex gas treatment systems, and it can be operated with proven state-of-theart catalysts in a conventional shape, e.g., pellets. The pressure can be generated by means of liquid
pumps which is a significant economical advantage. Just the hydrogen needs a gas compressor, but
only 10 to 15% of the total hydrogen produced must be recycled into the system. However, this
compressor decouples the system from the fuel cell, thus providing the opportunity to store
hydrogen in a pressurized tank. A huge number of small fuel cell applications is forecasted to come,
and they will all need their own hydrogen sources at the customer. Unfortunately, a price has to be
payed for all these advantages of the system, namely a relatively large amount of palladium.
Palladium is needed both in the membrane and in the catalyst for ring opening. The question as to
whether the system is cost-efficient compared to other fuel cell systems can only be answered by a
detailed economic analysis. In Table 5, a comparison is made between the novel system and a unit
based on partial oxidation.

Table 5: Comparison between partial oxidation and the new concept.

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