High-efficiency efficient direct dry reforming of biomethane withby [Remark 1] non-
equilibrium electric discharge at ambient temperature without gas- cleaning
Yasushi Sekine*, Junya Yamadera, Masahiko Matsukata, Eiichi Kikuchi
Waseda University, Dept. of applied chemistry, 3-4-1, Okubo, Shinjuku, Tokyo 169--8555.
RECEIVED DATE (automatically inserted by publisher); ysekine@[Link]
Biomethane is producible produced through by the 960 ppm of hydrogen sulphide (H2S). Input electric energy
fermentation of biomass-derived organic waste, such as like required for discharge was only 1.2 W. Waveforms of discharge
waste from stock-breeding waste. From the viewpoint of better and energy consumption were examined using a digital
energy utilization, biogas, which is a kind of biomass, so we oscilloscope and probes. [Remark 3] The produced gas was
should can be effectively used biogas effectively as an energy analyzed by using gas chromatography (GC); sulfur-containing
source. [Remark 2] Biomethane It contains about 40% carbon compounds such as H2Shydrogen sulphide and carbon disulphide
dioxide, and 60% methane., and Hhighly concentrated hydrogen were analyzed by using GC and sulfur detectors.
sulfide (H2S) of about (a few thousand parts per millionppm) is Both gases of the mixture, i.e., of CH4 and CO2, with and
also included in the gas. Existing processes for biogas utilization without H2S reacted byafter being the activationed ofby the non-
imply involve pre-desulfurization and CO2- separation due to the equilibrium discharge, irrespective of the addition of H2S, and
due to its high concentrations of H2S and CO2 in biogas. Dry formed syngas, as shown in eq. 1,. However, but the conversion
reforming of biomethane (eq. 1) is a promising process for levelpercentage for the both gases with H2S was slightly higher
utilization of utilizing biomethane,; but however, catalytic with H2S than that of the gas without H2Sit. Figure 1 shows The
reforming requires pre-the removal of impurities such as effect of H2S on the dry reforming of methane is shown in Figure
H2Shydrogen sulfide to prevent deactivation of the catalyst. 1:; the conversion of methane and carbon dioxide was ten percent
higher for the gas containing H2S showed 10 points higher
Dry reforming;: CH4 + CO2 ---> 2CO + 2H2 (eq. 1) conversion of methane and carbon dioxide than the gascompared
to that without H2S under identical reaction conditions. No
In addition, catalytic dry reforming of biomethane requires problems arose in either case, such as coking, or corrosion of
temperatures as high as 1000 K because of thermodynamic reactor and /electrodes by sulfuric compounds, were encountered
equilibrium limitations. Hundreds ofMany reports have in either case. These phenomena proved thatThus, inclusion of
described catalytic dry reforming of methane1, but almost all H2S in biomethane positively affects affected dry reforming by
results have indicated similar problems:, such as, requirement of non-equilibrium electric discharge. We infer that the
expensive catalysts, deactivation of the catalyst by due to the enhancement of in conversion was caused by the promotional
presence of small amounts of sulfur or metal sintering, expensive effect of the HS radical.
catalysts, coke formation, deactivation of catalysts due to 80
sintering of metal, and along with the need for a robust system
that enables high-temperature operation.1 70
Our previous study2 revealed showed that a non-equilibrium
60
pulsed discharge was a good means to convert of converting
methane by dry reforming; the process it could be conducted 50
performed at ambient temperature and atmospheric pressure with
Conv. / %
high energy efficiency. For this communicationHere, we report 40
on the successful, we succeeded in first direct conversion of
biomethane into syngas at ambient temperature and atmospheric 30
pressure without any gas cleaning. 20 CH Conv.
CH Conv.
Experiments were conducted performed using a flow-type 4
4
reaction apparatus equipped with two oppositely charged 10 CO
CO2 Conv.
2
Conv.
electrodes. The reactor configuration is described elsewherein
literature.34 A pulsed, high- voltage electric discharge was 0
With H S Without H S
applied within the electrode gap of the electrodes using a high- 2 2
voltage power supply. The reaction gas was a mixture of 59.7%
methane and 40.2% carbon dioxide. The experiments were Figure 1. Effect of H2S on the dry reforming of methane: current, 4 mA;
performed for two conditions of H2S, i.e., with orand without electrode gap distance, 8 mm; ambient temperature,; atmospheric pressure.
Figure 2 shows The interrelationship between the input
Table 1. Energy balance and efficiency of dry reforming of
current and the the conversion of methane and carbon dioxide is biomethane by non-equilibrium electric discharge at ambient
shown in Figure 2. With increased input current, mMethane and temperature.
carbon dioxide conversion increased proportionally with input
current. The ratio of hydrogen to carbon monoxide ratio was
Consumption rate Formation rate Heating value
about 1.7–1.8; the value decreased slightly with increased input -1 -1
/ mmol min kJ min
current caused by a slight increase of in the selectivity to C2 CH4 0.305 0.271
hydrocarbon. Figure 3 shows The interrelation relationship CO2 0.149 0.000
among the input current and concentrations of sulfur-containing Electricity / W 1.2 0.072
products on and the dry reforming of biomethane by non- E input--(a) 0.343
equilibrium discharge at ambient temperatureis shown in Figure CO 0.297 0.071
3. H2SHydrogen sulfide decreased monotonously uniformly with H2 0.484 0.135
increased input current from 960 ppm to 120 ppm; transient C2H4 0.004 0.006
behavior was observed in the formation of CS2 formed transiently C2H6 0.001 0.001
from the reaction ofbetween H2S and CH4. Gradually, tThe yield C2H2 0.058 0.075
E output--(b) 0.289
of solid sulfur gradually increased by the following successive
Energy efficiency / % ----> (b)/(a)*100 84.1
series of reactions:
H2S ==> CS2 ==> solid sulfur (S8) These results show that H2S in the biogas gradually was
decomposed gradually by the electric discharge and formed
70 4 sulfur-containing radicals. The radicals reacted with carbon
atoms once [Remark 4] to form CS2. Subsequently, CS2 was also
60 decomposed by the electric discharge., It was eventually
CH or CO conversion / %
3 converted into solid sulfur, and deposited on and around the
50 CH Conversion
4 electrodes.
H /CO ratio / -
CO Conversion We evaluated the energy efficiency for of this novel reaction,
2
40 wherein the following two processes occur of simultaneously: (1)
2 dry reforming of biomethane and (2) desulfurization. Table 1
2
30 shows tThe calculated results for the energy efficiency based on
the lower heating value of methane and the products, and input
2
20 electric power are shown in Table 1. Its value is Energy
4
1
efficiency was as high as 84.1%.
10
In conclusionTherefore, we achieved developed a novel
0 0 reaction process for converting biomethane to syngas and
0 1 2 3 4 5 6 7 desulfurization under ambient conditions [Remark 5] without any
Current / mA pre-treatment or the presence of a catalyst. The Total energy
efficiency was very high as (84.1%), and hydrogen sulphideH2S
Figure 2. Conversion ratios of methane and carbon dioxide: and hydrogen to was directly converted into solid sulfur directly.
–carbon monoxide ratio during dry reforming of biomethane: in presence of
960 ppm of hydrogen sulphideH2S included; 4-mm electrode gap distance;
atmospheric pressure; ambient temperature. (1) (a) F. Fisher and H. Tropsch, Brennstoff Chem., 1928, 9, 39; (b) J. R.
Rostrupnielsen and J. H. B. Hansen, J. Catal., 1993, 144, 38-–49; (c) K.
Nagaoka, K. Takanabe, and K. Aika, Chem. Commun., 2002, 1006-–
1007; (d) J. Wei and E. Iglesia, Phys. Chem. Chem. Phys., 2004, 13,
1000 3754-–3759; (e) C. J. Liu, B. Xue, B. Eliasson, F. He, Y. Li, and G. H.
Initial H S Concentration = 960 ppm Xu, Plasma Chemistry and Plasma Processing, 2001, 21, 301-–310;.
Sulphur-based concentration / ppm
2
(2) S. Kado, K. Urasaki, Y. Sekine, and K. Fujimoto, Chem. Commun., 2001,
415-–416.
800 (3) Y. Sekine, K. Urasaki, S. Kado, M. Matsukata, and E. Kikuchi, Energy
Fuels, 2004, 18, 455-–459.
600 Solid Sulfur Yield
400
H S concentration
2
200
CS Yield
2
0
0 1 2 3 4 5 6 7
Current / mA
Figure 3. Concentrations of sulfur-containing compounds from for
simultaneous desulfurization during on the dry reforming of biomethane: in
presence of 960 ppm of hydrogen sulphideH2S included; 4 -mm electrode
gap distance; atmospheric pressure; ambient temperature.