Hydrogen production from methane in a dielectric barrier discharge using oxide zinc and

chromium as catalyst
Manuscript id: MS#070602

Author response to the 1st reviewer comments

Question: The temperature of the catalytic bed should be reported. In the absence of this is
difficult, if not impossible to explain any change in both methane conversion and product
selectivity.
Answer: Thank you, previously we would like to thank 1st reviewer for kindly reviewing this
manuscript as well as the comments in order to make this manuscript better for its publication.
Regarding the question of the bed temperature, unfortunately, it is rather difficult for us to
provide that data. Any electrical devices to measure the temperature, such as thermocouple, can
not work inside the plasma zone as it contains numerous amounts of neutral and non-neutral
ions or radicals. Using radiative infrared measurement, the catalyst bed temperature was as low
as room temperature (in the range of 28 to 30oC). This measurement was also having many
defects. As the catalyst was located inside the silver (outer) electrode, the measurement was not
exactly showing the temperature of the catalyst bed. Taken from the definition of DBD,
classified as non-thermal plasma, the bulk temperature is similar to the input gas temperature
(very low) while the electron and excited species temperature will be extremely high. As the
numbers of these species are numerous, much higher than theoretical Maxwell distribution
calculation, this condition can be useful to (i) initiate the reaction by collision between reactant
and active species and (ii) manipulate the surface property of solid by contact between active
species and solid surface. There are many publications already addressing these two important
applications of plasma, especially DBD (for example: see Song et al., 20041; Kim et al., 20072,
and a review by Istadi and Amin, 20063). What we want to say related to the reviewer question
is that it is possible to activate the catalyst in low bulk temperature process using DBD.
We measured the output of the product stream but as it is not exactly the temperature of the
catalyst bed, we were not put this information in the manuscript which can make wrong
interpretation. Based on the experimental results, the existence of plasma gives only small
increment of methane conversion means that direct ‘bond-breaking’ process is not occurred in
the surface of the catalyst. As the selectivity of H2 increase, the catalytic plasma process
1
Song, H. K., J. W. Choi, S. H. Yue, H. Lee, and B. K. Na, “Synthesis gas production via dielectric barrier discharge
over Ni/γ-Al2O3 catalyst,” Catal. Today, 89, 27 (2004).
2
Kim, S. S., H. Lee, J. W. Choi, B. K. Na, and H. K. Song, “Methane conversion to higher hydrocarbons in a
dielectric-barrier discharge with Pt/ γ-Al2O3 catalyst.” Catal. Comm., 8, 1438 (2007).
3
Istadi and N. A. S. Amin, “Co-generation of synthesis gas and C2+ hydrocarbons from methane and carbon dioxide
in a hybrid catalystic-plasma reactor: A review,” Fuel, 85, 577 (2006).
associates with ions or radicals – catalyst surface interaction.

Question: Methane decomposition under DBD conditions is not a selective process since many
radical reactions are taking place simultaneously. An attempt should be made to rationalise the
rates of formation of individual products in terms of the radical concentration and specific
reaction rates for individual reaction.
Answer: Yes, we also agree with the reviewer’s statement. Although the process is not really
selective reaction (some people say that it is a random-type reaction), but still, there is a
tendency that plasma reaction performs a certain pattern of kinetics. Recently, we published in
different report about the investigation of the radical kinetic of methane decomposition on DBD
(Indarto, et al., accepted4) and we successfully figured out the general pattern of global reaction
as well as the values of k (rate constant). A conclusion of this report has been written on the
revised manuscript to give the basic idea on the non-catalytic plasma kinetics. Based on the
study on the kinetics, we tried to go further to increase the selectivity of a specific product (by
addition of catalyst) and in this case is increasing the H2 production and lowering the carbon
formation using Zn-Cr oxide catalyst.

Question: A critical issue in this process is the quantification of the amount of carbon formed. A
mass balance, including the unknown products, should be made. A simple balance: C deposited
= C inlet – C outlet will provide an idea on the extent of carbon deposited.
Answer: Thank you for the comment related to the unknown products. Yes, we did and we
reported in our manuscript. In Figure 3b and 4b, it is clearly seen that some portions of the bar
in those two charts are shown the un-known product. In our calculation, we used H balance
instead of C balance for some reasons. First, using H balance, we can exactly know the
unknown products occurred in the gas phase directly. Second, this will allow us to check
whether the un-known products consist only C solid material or it also consists CmHn molecules
(molecule contains C and H atom which could not be detected using our Gas Chromatograph).
As the total calculated H atoms in the product was less than the total H atom in the input, it can
be concluded that the un-known products consist CmHn molecules and C solid material. That is
the reason why we did not put the value of deposit carbon using the equation proposed by
reviewer. However, as shown in Fig. 3b and 4b, the selectivity of un-known compound is
relatively small and the deposit carbon attached on the wall of the reactor was detected after
long time plasma operation. As carbon is the major factor for the deactivation of the catalyst 5, in
4
Indarto, A., N. Coowanitwong, J. W. Choi, H. Lee, and H. K. Song, “Kinetic modeling of plasma methane
conversion in a dielectric barrier discharge,” Fuel Process. Technol., accepted.
5
Venugopal A., S. N. Kumar, J. Ashok, D. H. Prasad, V. D. Kumari, K.B.S. Prasad, and M. Subrahmanyam,
“Hydrogen production by catalytic decomposition of methane over Ni/SiO2,” Int. J. Hydrogen Energy, 32, 1782
(2007)
this research, we really want to reduce its selectivity.

Question: There are several sentences and words along the text to be clarified. As probably
English is not the mother language of author, revision by a native speaker is also recommended.
Answer: Thank you for the comment related to the English language in this manuscript. We
tried our best to clean up the grammatical and linguistic problem occurred in the manuscript. We
hope that the current version will be enough to be accepted as a scientific paper.
Author response of the 2nd reviewer

Question: The applied power was given in W in the text (page 7) while it was in kW in Figure
1. Please correct it.
Answer: Thank you very much for the correction from the reviewer. The correct unit should be
W (watt) instead of kW (kilo watt). We put the correct unit of Figure 1 in the revised
manuscript.

Question: The word “reused” should be replaced by either “regenerated” or “reactivated’. It is

very hard to follow the text in page 11 and Figures 6a and 6b.
Answer: Thank you very much for the comment. As the treatment of the catalyst is a part of
experimental variable in order to activate the catalyst, we did many possible treatments to find
the best method to do it. The term ‘reused’ is applied for the 2nd time/cycle catalyst after
‘regenerated’ by only using drying treatment. This treatment proposes to remove the moisture or
liquid product in the surface of the catalyst (if it exists). In order to avoid the name problem, we
changed to use alphabetical system: ‘a’ for the fresh catalyst and ‘b’ for (2nd cycle) used catalyst
+ drying. The first run is mentioned for the fresh catalyst with calcinations treatment, the 2 nd run
is applied for the used catalyst (2nd cycle) after re-calcination, and the 3rd run is for the no-
treatment (non-calcined) catalyst.

Question: Figure 3b is very hard to see because the similar shades were used.
Answer: Thank you very much for the suggestion. We changed the shade of the bar in Figure
3b and we hope it will be better to read.

Question: Figure 6 did not specify the studied conditions. Please add the studied conditions in
the figure.
Answer: Thank you very much for the suggestion. All of the data in Figure 6 are obtained at
total gas flow rate of 30 ml/min and supplied power of 80W. This value was obtained from the
optimized value of the non-catalytic process. We put this information in the revised manuscript
in the section of result and discussion catalytic-process as well as in Figure 6.

Question: Please explain how the catalyst was only able to enhance the hydrogen selectivity.
Answer: As we know, this is the first time of the use mixed Cr-Zn oxide catalyst for H 2
production from methane. We found unintentionally when we did a screening to the catalyst that
able to affect the product distribution of methane conversion in plasma DBD. The reviewer can
access soon our investigation as it was published already in the J. Chin. Chem. Soc. (Indarto et
al., 20076). This study contains not only the catalyst which able to increase the production of H2
from methane but also other compounds, such as C2, C3, and C4 hydrocarbons. Next after we
found the best catalyst, we tried to modify the content of the catalyst with the help of literatures.
Unfortunately, we did not find an exact comparison to the used of Cr and Zn for methane
conversion. However, refers to the other literatures in different applications of Cr and or Zn
oxide catalyst, we tried to bring a short and general explanation on how the catalyst can increase
the hydrogen selectivity from methane. We will not go in detail since the mechanism can be
totally for methane conversion in plasma process.

Question: Please explain why the activity of the catalyst was almost zero after the third cycle in
use.
Answer: Before answering the reviewer question, it is better to explain clearly the experiment
regarding the variations of catalyst treatment. The catalytic-plasma experiments were conducted
only up to 2nd twice. The first cycle was using the fresh catalyst with three different treatments:
(i) the fresh catalyst after calcinations, (ii) the used catalyst after regeneration by calcinations,
and (iii) the catalyst without any treatments. The third cycle mentioned by reviewer probably
refers to the use of catalyst without treatment.
As we mentioned in XRD spectrum explanation in the experimental and setup section, the
calcinations is important to change the phase of Zn and Cr into ZnO and ZnCr2O4 as those states
distinguished as the active site of the catalyst7. This also could be the reason why un-calcined
catalyst did not show any activity when it was used in the process.

Question: It will be better to compare the energy consumption at different residence times and
with and without catalyst.
Answer: Thank you very much. For the experiment using catalyst, we performed a set of
experiment at similar supplied energy of 80W and flow rate of 30 ml/min. As we mentioned
above, this values are obtained from the optimization of highest yield and energy efficiency of
H2 production. This is simply to make us enable to do data comparison. Regarding the energy
consumptions vs residence times, as we mentioned in the manuscript, we maintained the
supplied power similar for all experiments ranges (80 W). So, in this case, it is not necessary to
provide the data about energy consumption vs residence times.

6
Indarto, A., J. W. Choi, H. Lee and H. K. Song, “A Brief Catalyst Study on Direct Methane Conversion Using a
Dielectric Barrier Discharge,” J. Chin. Chem. Soc., accepted (2007).
7
Simard, F., U. A. Sedran, J. Sepúlveda, N. S. Fígoli and H. I. de Lasa, “ZnO-Cr2O3 + ZSM-5 Catalyst with very low
Zn/Cr ratio for the Transformation of Synthesis Gas to Hydrocarbons,” Appl. Catal. A: Gen., 125, 81 (1995)
Author response of the 3rd reviewer

Question: The paper was studied in hydrogen production form methane in a dielectric barrier
discharge using oxide zinc and chromium as catalyst. The author used the plasma method to
produce hydrogen. The advantages of this method are short operating time and (may) low cost.
However, the hydrogen production from methane in the literature is well-known higher than
70%. The concentration is below than 40%. That is, the hydrogen is not main product in this
process. On the other hand, the hydrogen production was only enhanced 10% in the presence of
oxide zinc and chromium as catalyst. Which role did the catalyst play in this system? How to
improve their system to allow hydrogen to become a main product did not show in the text by
the author. Hence, the objective of this paper is low. Therefore, I don’t recommend it to publish
in this Journal.
Answer: Thank you very much for the reviewer to examine our manuscript. First we would like
to address the objective of our research. It is clearly written in the abstract and introduction part
that we would like to produce hydrogen (which could be use for fuel cell system) with low
carbon formation. Why? Because the carbon formation is clearly make the deactivation of the
catalyst (see Venugopal et al., 20075) by covering the catalyst surface. Regarding the comment
on the reviewer that the concentration of H2 was lower than 40%, kindly, we want to correct it.
In figure 3b and 4b, we used the ‘selectivity’ instead of ‘concentration’. This value will give
different value each other. Following the Eq. 2, the selectivity calculation includes the number
of H in the molecule which will affect on higher selectivity value of molecules that have more
than two H, e.g. i-C4H10 or C3H8. However, when the product concentration was used as the
parameter, the concentration of H2 is nearly to 65-70% due to normalization of concentration
calculation from selectivity by number of H in the atom. Moreover, we are also easily able to
increase the production of H2 by increasing the supply power of electrical generator to the
reactor, as we performed in our previous experiment8. But it will be meaningless for some
reasons: (i) more H2 production with more carbon production will reduce the lifetime of
catalyst; (ii) more supplied power to the reactor will reduce the efficiency of the process. We
want to optimize those variables allowing us to produce significant H2 production with low
carbon production. Another correction: it is clearly seen in Fig. 6b, that the selectivity of H2 is
more than 40%. The value of 40% should refer to the non-catalytic plasma process.
Regarding the comment on the main product whether it is H2 or not, what we can explain is as
follows. Carefully look at the Eq. 2 where the selectivity calculation calculated on the basis of H
atom; we include the coefficient of total number H in the molecule, means that in the reality the

8
Indarto A., J. W. Choi, H. Lee, and H. K. Song, “Kinetic Modeling of Plasma Methane Conversion Using Gliding
Arc,” J. Natur. Gas Chem., 14, 13 (2005)
concentration of each compound should be divided by the number of hydrogen atom. For
example, i-C4H10 with selectivity of 20%, the production yield will be only less than 4%.