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Autothermal Reforming of Methane: Design and Performance of a kW scale

reformer using pure oxygen as oxidant

Article · January 2006

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 WHEC 16 / 13-16 June 2006 – Lyon France

Autothermal Reforming of Methane: Design and Performance of a kW

scale reformer using pure oxygen as oxidant
Stefan Rabe, Thanh-Binh Truong, Frédéric Vogel

Paul Scherrer Institut

General Energy Research Department (ENE)
Laboratory for Energy and Materials Cycles
5232 Villigen PSI
e-mail: stefan.rabe@psi.ch, phone: 0041 (0)56 310 2640

ABSTRACT:
The autothermal low temperature catalytic partial oxidation of methane was investigated in a bench - scale
reactor (1 kWth power) over a structured ruthenium catalyst (metal monolith support). Pure oxygen was used
as the oxidant. Autothermal operation of the reactor was successfully demonstrated. The increase of the O/C
ratio increased the average reactor temperature resulting in higher methane conversions. Similar results
were obtained for the increase of the space velocity. The product gas generated was rich in hydrogen (65
%), nitrogen-free and contained comparably low amounts of carbon monoxide. The results reveal that the
oxygen-blown reforming at low temperatures is well suited for the production of hydrogen.
KEYWORDS :.Methane, Autothermal Reforming, Hydrogen, Catalysis

Introduction
The catalytic partial oxidation (CPO) of methane to produce hydrogen and carbon monoxide (Eq. 1) over
noble metal catalysts is one of the most studied reactions and has been reviewed several times [1-3].

CH4 + 0.5 O2 → CO + 2 H2 (1)

The low temperature catalytic partial oxidation (LTCPO) of methane which yields a product gas rich in
hydrogen and carbon dioxide was also studied [4-8].

CH4 + x/2 O2 + (2-x) H2O → CO2 + (4-x) H2; 0 ≤ x ≤ 2 (2)

The heat of reaction (∆HR) of this reaction depends on the reaction temperature and on the fractions of
oxygen and water (x in Eq. 2) In the ideal case, the reaction according to Eq. 2 runs autothermally if ∆HR = 0.

Many of the studies concerning the catalytic reforming of methane were performed on powder catalysts in
lab-scale microreactors or in-situ reaction cells using air or highly diluted oxygen as the oxidant. The
autothermal CPO of methane at temperatures of 1000 °C and above over Pt and Rh coated ceramic
monolith catalysts using air or pure oxygen as the oxidant was investigated by Hickman et al. [10-12]. A
comparison of different active metals on a monolith support was published by Torniainen et al. [13]. Rhodium
revealed high yields of carbon monoxide and hydrogen and an excellent catalyst stability. A study of the
CPO of methane over cordierite monolith supported platinum and palladium catalysts in a pilot plant using air
as the oxidant was presented by Hochmuth [14]. It was demonstrated that an equilibrium synthesis gas could
be produced. Recently, Lee et al. published a paper on the autothermal reforming in a kW scale integrated
fuel processor consisting of a reforming unit, a sulphur trap and a water-gas-shift unit [15]. Air was used as
the oxidant. The fuel processor was successfully operated over a period of 2300 h.

The results presented in the literature support the principle of the catalytic reforming of methane to produce
synthesis gas or hydrogen even on a larger scale. However, in most of the studies either air or a highly

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 WHEC 16 / 13-16 June 2006 – Lyon France

diluted feed gas was used as the oxidant. Thus, the product gas is diluted with nitrogen or other inert gases
and reveals a lower energy content. In some applications (i.e. Fischer-Tropsch synthesis of synthetic
transportation fuels) a diluted syngas cannot be used for an efficient process. The need for a reduction of
CO2 emissions leaded to a considerable interest in the development of fuel processing technologies which
include the sequestration of CO2. The dilution of the CO2 containing fuel gas with nitrogen creates problems
with respect to an efficient CO2 separation. The use of pure oxygen as the oxidant could overcome these
problems. However, to our knowledge, no autothermal operating syngas / hydrogen processor running with
pure oxygen has been described in the literature so far. We therefore investigated the low temperature
autothermal CPO of methane using oxygen and water (Eq. 2) at temperatures < 800 °C in a kW scale
experimental set-up.

Experimental
A 1 kWth bench scale reformer (diameter: 3.7 cm, length: 20 cm) for the autothermal CPO of methane using
pure oxygen was constructed. A metal monolithic reactor system was chosen to minimize the pressure drop
along the catalyst bed and to reduce the formation of high hot spot temperatures. As a catalyst, a metal
monolith with an alumina washcoat and impregnated with ruthenium (150 mg Ru) was used. The reactor was
equipped with a thermocouple well and a moveable thermocouple in order to record the temperature profile
along the reactor axis. Three monoliths (diameter: 3.5 cm, length: 3.5 cm, 400 cpsi, Oberland-Mangold) were
used during the experiments. The scheme is shown in Figure 1.

TC

CH4, H2O(g)
O2
Thermal Insulation

Ru/g-Al2O3

blank
Heated Zone
Heated Zone

blank

Figure 1: Reformer scheme. TC: moveable thermocouple.

The first monolith was coated with Ru/γ-Al2O3, the remaining two were blank. A thermocouple well equipped
with a movable thermocouple was placed in the center of the monoliths in order to monitor the temperature
profile along the catalyst. De-ionized water was fed by an HPLC pump to a vaporizer. The water vapour was
subsequently mixed with methane. The water/methane feed mixture was further pre-heated to 275 °C.
Oxygen was added at room temperature at the reactor inlet section. The reactor was heated to the ignition
temperature of the feed mixture (approximately 450 °C). After ignition of the reaction, the external reactor
heating was turned off. Oxygen-to-carbon ratios (O/C = 2*O2/CH4) between 0.69 to 1 and steam-to-carbon

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 WHEC 16 / 13-16 June 2006 – Lyon France

ratios (S/C = H2O/CH4) of 3 and 3.8 have been applied. The metal monolith (Oberland Mangold, diameter:
3.5 cm, length: 3.5 cm, 400 cpsi) coated with an alumina washcoat was impregnated with an aqueous
solution of ruthenium nitrosyl nitrate. After impregnation and drying, the catalyst was calcined in air at 550 °C
for 4 hours.
For Gas-to-liquids (GTL) applications the synthesis gas produced should have a stoichiometry that matches
the final product. For processes which convert both CO2 and CO into liquid hydrocarbons this is expressed
by the module M = (H2-CO2)/(CO2+CO) [16]. For the production of Fischer-Tropsch liquids in the Diesel
range, M should have a value of 2.1.
Results and Discussion
In a first set of experiments the space velocity was varied from 80 to 120 gfeed/gcat/h. The methane
conversion increased from 65 % to 70 % (Figure 2, a). The M factor increased from 1.85 to 1.96 with
increasing space velocity. The corresponding temperature profiles reveal a higher hot spot temperature (up
to 708 °C) and a higher exit gas temperature(639 °C) at higher space velocities (Figure 2, b). Thus, the
increase of the methane conversion and of the M factor can be attributed to the greater heat release at
higher space velocities, which heats the catalyst bed resulting in a higher reaction temperature.

71 2.00
a)

70 1.95

69 1.90

M Factor
XCH4 / %

68 1.85

67 1.80

66 1.75

65 1.70
70 80 90 100 110 120 130
WHSV / h-1
750
b) WHSV = 119 h-1
700
WHSV = 105 h-1
650 WHSV = 91 h-1
600 WHSV = 80 h-1

550
T / °C

500 Flow
Catalyst Blank Blank
450
400
350
300
250
0 50 100 150 200
Length / mm

Figure 2: a) Methane conversion (XCH4) and M factor as a function of space velocity. b) Corresponding
temperature profiles. Reaction conditions: O/C = 2*O2/CH4 = 0.89, S/C = H2O/CH4 = 2.9, WHSV: 80 - 119
gcat/gfeed/h (GHSV: 9400 - 14000 h-1). M = (H2-CO2)/(CO+CO2).

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The product gas composition (dry gases) is shown in Table 1. The hydrogen concentration (63 - 65 %) is
higher compared to data published by Lee et al. (42 % H2) [15] because the dilution by nitrogen was avoided.
It should be noticed that the CO concentration of 5 % is comparable small. This can be attributed to the high
steam-to-carbon ratio (H2O/CH4) of 3 which increases the water gas shift activity and the comparable low
temperature. A low level of carbon monoxide is beneficial with respect to the refinery of fuel gas for PE fuel
cell applications [17].

Table 1: Composition of the dry product gas.

Input Power WHSV GHSV CH4 CO2 CO H2

(kW th) (h-1) (h-1) (%) (%) (%) (%)
1.09 119 14095 10.6 18.5 5.2 65.4
0.97 105 12474 11.1 18.6 5.2 65.0
0.84 91 13349 11.9 18.9 4.9 64.2
0.73 80 9474 12.9 19.1 4.6 63.3

Reaction conditions: pabs = 0.21 MPa, O/C = 0.89; S/C = 2.9.

The results obtained for different reaction conditions are summarized in Table 2. Autothermal reforming
efficiency (RE) can be defined as the ratio of the lower heating value (LHV) of the hydrogen produced and
the LHV of the fuel used [9]. Since RE depends on the methane conversion, a specific reforming efficiency
(RE* = RE/XCH4) was also calculated.

Table 2: Results of the autothermal catalytic partial oxidation over a Ru coated monolith catalyst.
Input Power WHSV GHSV RE RE*
O/C S/C XCH4/(%) YCO(%) YCO2(%) YH2(%)
(kW th) (h-1) (h-1) (%) (%)
0.84 94 11114 0.89 3.00 60.3 10.6 46.3 48.9 44.2 73.7
0.84 92 11031 0.79 3.02 57.9 9.0 44.5 48.5 43.9 75.8
0.84 91 10995 0.69 3.05 51.8 6.8 41.1 44.1 39.9 77.0

0.84 112 13349 1.00 3.84 70.6 11.9 54.8 59.1 53.4 75.6
0.84 111 13243 0.89 3.85 65.2 9.6 50.7 54.7 49.4 75.7
0.84 108 13037 0.79 3.82 59.7 8.0 46.9 50.7 45.9 76.9
0.84 107 12949 0.69 3.83 51.9 5.8 42.0 44.0 39.1 76.7

1.09 119 14095 0.89 2.90 70.3 14.6 51.7 60.8 55.0 78.2
0.97 105 12474 0.89 2.89 69.7 14.2 50.7 59.1 53.4 76.6
0.84 91 10824 0.89 2.89 67.7 13.2 51.3 58.2 52.6 77.7
0.73 80 9474 0.89 2.91 65.3 12.3 51.7 57.0 51.5 78.9

XCH4: Methane conversion, YCO; YCO2; YH2: Yields of CO, CO2, H2, S/C = H2O/CH4, O/C = 2*O2/CH4
RE: Reforming efficiency (RE = LHV oh H2 produced / LHV of methane supplied) x 100. RE*: specific
Reforming efficiency (RE* = RE / XCH4) x 100. All experiments were conducted at a total pressure of 0.21
MPa.
C, H, O balances: 0.96 - 1.02.

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 WHEC 16 / 13-16 June 2006 – Lyon France

The results reveal a strong impact of the O/C ratio on the catalyst performance. An increase of the O/C ratio
increases the methane conversion (Table 2: an increase of O/C from 0.69 to 1.00 at S/C = 3.8 increased the
conversion from ≈ 52 % to ≈ 71 %). As expected, the reforming efficiencies RE are strongly correlated with
the methane conversion. Due to the incomplete conversion, a maximum efficiency of 55 % was observed
which is fairly low compared to the theoretical maximum of 93.9 % [9]. The specific reforming efficiency RE*
was also lower (74% to 79 %) than the theoretical maximum. The lower efficiency can be attributed to heat
losses and to the formation of carbon monoxide which is also produced. However, the efficiency can be
strongly increased by improving the methane conversion and by a shift of the remaining carbon monoxide.
Summary and Conclusions
The autothermal low temperature catalytic partial oxidation of methane was investigated in a bench - scale
reactor (1 kW th power) over a structured ruthenium catalyst (metal monolith support). Pure oxygen was used
as the oxidant. Autothermal operation of the reactor was successfully demonstrated. The increase of the O/C
ratio increased the average reactor temperature resulting in higher methane conversions. Similar results
were obtained for the increase of the space velocity. The product gas was rich in hydrogen, nitrogen-free
and contained comparable low amounts of carbon monoxide. These results obtained reveal that the oxygen-
blown autothermal methane reforming at low temperatures is probably well suited for the production of
hydrogen, especially in combination with a CO2 sequestration. For Gas-to-liquids (GTL) applications, the
high carbon dioxide content requires an improved Fischer-Tropsch technology which is able to convert CO2
as well.

Acknowledgements
Financial support by BBW, project no. 02.41 and EU, project no. NNE5-2002-00424 (New GTL based on low
temperature CPO) is gratefully acknowledged. The authors also thank E. DeBoni, T. Marti and P. Binkert for
the construction of the reformer set up.

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