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Date: Jun 27, 2007

To: "Antonius Indarto" indarto@korea.com
From: boehman@ems.psu.edu
Subject: Your Submission

Ms. Ref. No.: FUPROC-D-07-00038

Title: Kinetic modeling of plasma methane conversion in a dielectric barrier discharge
Fuel Processing Technology

Dear Anton,

Reviewers have now commented on your paper. You will see that they are advising that you revise your
manuscript. If you are prepared to undertake the work required, I would be pleased to reconsider my
decision.

For your guidance, reviewers' comments are appended below.

If you decide to revise the work, please submit a list of changes or a rebuttal against each point which
is being raised when you submit the revised manuscript. Please pay particular attention to both
reviewers' request for more significant discussion of the results (i.e., what the one reviewer referred to
as "scholarship) and to improving the English usage.

To submit a revision, please go to http://ees.elsevier.com/fuproc/ and login as an Author.

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On your Main Menu page is a folder entitled "Submissions Needing Revision". You will find your
submission record there.

Yours sincerely,

Andre L. Boehman
Editor
Fuel Processing Technology

Reviewers' comments:

Reviewer #1: Review of "Kinetic modeling of plasma methane conversion in a dielectric barrier
discharge" by Antonius Indarto, Nowarat Congwanitwong, Jae-Wook Choi, Hwaung Lee, and Hyung Keun
Song for Fuel Processing Technology

This paper contains interesting kinetic modeling results for methane conversion in a plasma reactor,
considering product reactions up to C4 molecules. The results are useful and relevant, but the analysis
is not as deep as it could be and some of the results are based on speculation. More analysis and
support of the proposed reaction mechanisms would be helpful. I recommend publication with major
revision. The English grammar is poor, which makes the authors' intended meaning unclear throughout
the paper. The English should be improved as part of the revision. (One example of many is the last
full sentence at the bottom of p. 7: "Except C2H2 (run 2) and C3H6 (run 5), the total C and H atom of
the products after plasma conversion were close to 100% means that all of reactant transformation to
the products could be obtained almost complete." I believe the authors are attempting to say that the
mass balance between the reactants and products approximately closed in all but two experiments, but
I am not sure.)

The following is a list of recommendations for the authors to consider in a revision:

In the Experimental section (page 5), the purity of only methane is listed and the source is not
described. Please include the reactant gas purities and sources/manufacturers for all reactants.

In the Experimental section (p. 5), the flame ionization detector is abbreviated as "TCD", when it should
be "FID".

In the Experimental section (p. 6), the authors state that they assume the reactions to be first order,
yet later in the paper, they discuss second order reactions to form the products (for example, reactions
12 and 13). What is the basis for this assumption? Please justify or support the assumption of first
order kinetics and describe or estimate the error introduced by this assumption.

Was temperature measured, either in the reactor or at the outlet? At 60 W of power input, I would
expect some heating to occur. This should be reported in Section 2.1. On p. 4 in the Introduction, the
model is described as being applicable to "ambient" temperature conditions. Is this 25°C? Please
define this, especially as related to the question about the actual reactor temperature. On p. 7 in
Results and Discussion, the reactor flow rate is listed as 30 ml/min. Is this at STP conditions or the
undefined "ambient" conditions of temperature and atmospheric pressure? Please explicitly identify
the temperature and pressure at which the volumetric flow was measured.

In the Experimental section, please define the selectivity used for all products, as there are several
definitions of selectivity in use. Also, please clarify whether conversion and selectivity are reported on
a carbon basis. Please consider including another table (similar to Table 1) showing the selectivities for
each experiment.

Table 1 is shown as the first item in the Results and Discussion section (p. 8), yet it is not discussed
until the next paragraph. Consider relocating this table. The authors discuss the carbon balance in the
text, but do not show this in Table 1. Please include a column for carbon balance in Table 1, showing
the sum of the measured species, instead of requiring the reader to sum the columns to check how
close the carbon balance is. Also, Table 1 is labeled "The reactant conversion . . .", yet conversion is
not shown in the Table. Please rename the table to correctly identify the contents, or better yet,
include a column showing the conversion of each reactant.

Some discussion of accuracy, reproducibility, and experimental error is necessary to interpret the
significance of the data in the tables. Table 1 reports data to four significant figures. Should the reader
infer that the results are accurate and reproducible to the two decimal places shown? This information
on experimental error and accuracy is required to properly analyze the results.

On p. 9 in Results and Discussion, reactions 9 and 10 are not stoichiometrically balanced (for example,
reaction 9 is shown as 4 C2H2 + H2 = i-C4H10, but should be 2 C2H2 + 3 H2 = i-C4H10).

On p. 9 just before reactions 13 and 14, the authors state, "In the case of C3H6 compounds, the
reactions occurred by two main parallel ways." What evidence is there to support this statement?
Many possible pathways exist among the radicals present in the reactor to form these products. How
were these two reactions identified as the main pathways?

In general, the reactions shown throughout the paper do not appear to be based on experimental
evidence. They appear to be reasonable, but certainly not the only possible reactions. How were they
selected? What basis was used to make the selections? (There are dozens of possible radical
reactions. Some of these reactions are discussed and analyzed by Zhao et al. in the Chemical
Engineering Journal, 125, 67-79, 2006.)

On p. 10 and in Table 2, what are the units of the rate constants? Since they are all first order, they
must have units of inverse time, but is it per s, per minute, or what unit? Please show in both the text
and the table.

On p. 11, the authors state, "Low value of k13 (CH4 C2H4) and k12 (CH4 C2H2) shows that acetylene
and etylen was not coming from methane conversion." k13 and k12 are not zero (unless the reported
results are zero within the accuracy of the fitting method), so this statement is not accurate. It should
be softened to say that acetylene and ethylene are not predominantly formed directly from methane.
("Ethylene" is misspelled in the text, as shown above.)

Were mixtures of the reactant gases ever tested in the reactor? For example, if an equimolar mixture
of all 8 reactants were feed simultaneously, the model should be able to predict the product
composition. If this were verified experimentally, it would strongly validate the model. Even results for
binary mixtures of reactants could help prove the model accuracy.

Is Figure 2 meant to show only the major reaction pathways? This should be clarified in the caption
because there are no zero values in Table 2 (other than the diagonal self-reaction rate constants),
which indicates that any product can be formed from any reactant, at least to some degree. Again, a
discussion of the accuracy or confidence intervals of the data would help to establish the significance of
the data.

In the Conclusions on p. 12, the authors state that "C2H6 has an important role in the global
mechanism." However, on p. 11 and in Figure 2, C2H4 is identified as the important intermediate. Is
this a typographical error in the Conclusions and should they state that "C2H4 has an important role in
the global mechanism"?

Reviewer #2: This paper describes experiments and kinetic simulations of methane conversion to
hydrocarbons using a plasma via dielectric barrier discharge. The paper is well organized and
interesting but suffers from poor English usage and poor scholarship.

Title: Only need to provide one version (the complete and descriptive one).

Throughout the manuscript there are awkward and confusing statements. To assist the authors with
revision of the manuscript, a marked copy of the manuscript is attached to this review with specific
suggestions and identification of awkward wording.

The problem of scholarship is that the authors do little to discuss their results in the context of the
literature, whether from work on plasma conversion of methane or other methods for methane
conversion. It would be very worthwhile for the authors to compare and contrast their analyses of
reaction kinetics and reaction pathways with other techniques for methane conversion, to highlight how
the plasma influences the process. But, in the Results and Discussion section, only one reference is
cited by the authors that was not written by H.K. Song and co-workers. This must be addressed before
the present manuscript will be suitable for publication.

The reviewer(s) may also have uploaded detailed comments on your manuscript as an attachment. To
access these comments, please go to: http://ees.elsevier.com/fuproc/
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You will find your submission in the folder entitled "Submission Needing Revision".
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