i n t e r n a t i o n a l j o u r n a l o f h y d r o g e n e n e r g y 4 8 ( 2 0 2 3 ) 1 4 2 1 0 e1 4 2 2 5

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Investigation of methane and ethane pyrolysis

with highly active and durable iron-alumina
catalyst to produce hydrogen and valuable nano
carbons: Continuous fluidized bed tests and
reaction rate analysis

Ranjani Siriwardane a,*, Jarrett Riley a,b, Christopher Atallah a,b,

Michael Bobek a,b
a
U.S. Department of Energy, National Energy Technology Laboratory, 3610 Collins Ferry Road, P.O. Box 880,
Morgantown, WV 26507-0880, USA
b
LRST, Research Support Contractor for NETL-DOE, 3610 Collins Ferry Road, P.O. Box 880, Morgantown, WV
26507-0880, USA

highlights graphical abstract

Novel Fe based catalysts showed

80% CH4 conversion to H2 for 160 h.

Ethane conversion was 100%.

Continuous H2 production
demonstrated in fluid bed tests.

Higher ethane conversion rates
than that with methane.

Reaction rate models were devel-
oped for methane and ethane
pyrolysis.

article info abstract

Article history: The goal of this research work was to evaluate a novel iron-alumina catalyst for methane
Received 6 October 2022 and ethane pyrolysis with high conversion rates to H2 with a long life time to address two
Received in revised form major issues reported with previous catalysts. Fluidized bed tests demonstrated contin-
28 November 2022 uous hydrogen production while collecting carbon containing fines. During the 230 h fluid
Accepted 22 December 2022 bed test the methane conversion rate to hydrogen at 700  C remained above 80% for 160 h
Available online 12 January 2023 while creating valuable nano carbons. Similarly high catalyst lifetimes with high methane
conversions have not been reported before. Ethane was more active than methane for
Keywords: pyrolysis with 100% conversion to H2. Transmission electron microscopy and Raman
H2 and carbon production analysis of the carbon showed single and multiwall nanotubes and conglomerate nano-
Natural gas pyrolysis for H2 and fibers. Ethane did not impact the allotrope of carbon formed. TGA was used to create a
nano carbon production data array that was used for kinetic analysis and reaction model parametric regressions.

* Corresponding author. U.S. Department of Energy, National Energy Technology Laboratory, 3610 Collins Ferry Road, P.O. Box 880,
Morgantown, WV 26507-0880, USA.
E-mail address: Ranjani.siriwardane@netl.doe.gov (R. Siriwardane).
https://doi.org/10.1016/j.ijhydene.2022.12.268
0360-3199/© 2023 Hydrogen Energy Publications LLC. Published by Elsevier Ltd. All rights reserved.
 i n t e r n a t i o n a l j o u r n a l o f h y d r o g e n e n e r g y 4 8 ( 2 0 2 3 ) 1 4 2 1 0 e1 4 2 2 5 14211

High performance methane Ethane had a higher rate of pyrolysis that was 2.3e2.8 times that of methane. Ethane py-
pyrolysis catalyst rolysis was found to be more sensitive to temperature with a higher activation energy of
H2 from methane pyrolysis 62 kJ/mol as compared to methane at 43 kJ/mol. The frequency factor, Ai , was significantly
Thermos-catalytic methane higher for ethane at 0.73 [[kmol/m3-sec]/[N/m2]n] compared to 0.03 for methane on the
pyrolysis same basis. Both gases had a functional partial pressure order dependence of ~0.6 based on
Methane and ethane pyrolysis the regression analysis.
© 2023 Hydrogen Energy Publications LLC. Published by Elsevier Ltd. All rights reserved.

The endothermic energy requirement for MP is 2.53 less

Introduction than that with SMR per mole of CH4 at 700  C. There are four
different approaches to pyrolysis: thermal non-catalytic,
Nomenclature thermal-catalytic, thermal-molten, and plasma based. Ac-
H- cording to reported system analyses, MP for H2 production is
XCH4 Methane conversion [%]
more cost effective when the carbon generated can be sold
XC2H6 Ethane conversion [%]
as a product to offset the costs associated with the produc-
YH2 Hydrogen yield [%]
tion of H2 making the process more advantageous compared
Rci CxHy pyrolysis reaction rate [gC/gcatalyst-sec]
to SMR [5e7]. The focus of this work is on the thermal-
Ea,i Activation energy [kJ/mol]
catalytic approach and follows up on a previous work con-
Ai Arrhenius constant (frequency factor) [kmol/
ducted on the simulation and TEA of a thermal catalytic
kgcat-sec]/[N/m2]ni
methane pyrolysis process [5]. The previous work identified
kci Arrhenius reaction rate factor [kmol/kgcat-
a number of data requirements based on the process simu-
sec]/[N/m2] ni
lation. These included the need to demonstrate comparative
ni Reaction order [unitless]
catalyst on-stream times in a fluidized bench scale reactor at
i Gas phase component, i ¼ 1 ¼ CH4 and
comparative conditions to gain perspective on achievable
i ¼ 2 ¼ C2H6
performance and to qualify the carbon product being
R 8.314 [J/mol K]
generated from the process. The carbon product has been
rb Catalyst bulk density [kg/m3]
identified as an important factor in the economic feasibility
of the process and therefore required examination to gain
perspective on allotrope. Secondly, natural gas (NG)
composition can vary widely amongst location and territory
ydrogen (H2) is an important chemical mainly used in pro- with ethane being the second most prominent gas constit-
duction of ammonia for fertilizers, production of methanol, uent at 1.8%e6.6% [8,9]. Therefore, it was of interest to
and as a clean environmentally benign energy source [1e4] for explore the use of ethane to determine pyrolytic properties
a vast array of applications. H2 is also used in oil refineries and with respect to the process and compare these properties to
fuel cells. Transportation and energy generation sectors are methane. To address these points, it was also relevant to
investigating H2 implementation as a way to reduce emis- establish background on the catalytic materials, their barrier
sions. In the United States, over 95% of the H2 generated is issues, and the rational for selected catalyst material used in
produced by steam methane reforming (SMR) of natural gas. the study.
SMR produces high H2 yields, but there are many disadvan- Catalytic MP processes show great promise in facilitating
tages. It is a highly endothermic reaction (206 kJ/mol), which MP at temperatures ranging from 600 to 800  C with nickel (Ni),
requires fuel combustion and associated carbon dioxide (CO2) iron (Fe), and carbon-based catalysts [10e12]. Catalyst devel-
generation. In addition, syngas initially produced by SMR opment has been a major barrier issue for catalytic MP pro-
must be processed via water gas shift reaction and pressure cess. Catalyst development issues have been reported in
swing adsorption to generate hydrogen, incurring additional several review papers [7,10,11]. Issues include chemical and
costs. As the demand for hydrogen increases, it is necessary to physical property issues that lead to catalyst deactivation and
develop methods for hydrogen production with minimal low CH4 to H2 conversion rates. Experimental operating issues
environmental impact. Encouraging technologies for clean limited the ability for continuous H2 production for extended
approaches to H2 generation are pyrolysis technologies for the periods coupled with separation of fines containing carbon.
conversion of natural gas (NG) to H2. Production of pure carbon has also been identified as a barrier
The major constituent of NG is methane. Methane pyrol- issue due to difficulty in separating carbon from the catalysts.
ysis (MP) is a non-oxidative thermal process that decomposes Catalysts reported in the literature had either low conversions
methane (CH4) to carbon and H2, as shown in reaction equa- of methane to H2 or short lifetimes if the conversions are high
tion (1). The technique serves as an alternative to SMR while (>80%) as described in the following sections.
providing H2 that is free from CO2 emissions. Nickel-based catalysts with various supports have been
explored due to high reactivity at low temperatures,
MP: CH4 / C þ 2H2 D H0 ¼ 88.8 kJ/mol @ 973.15K (E1) 500e700  C. Various supports and additives have been used
14212 i n t e r n a t i o n a l j o u r n a l o f h y d r o g e n e n e r g y 4 8 ( 2 0 2 3 ) 1 4 2 1 0 e1 4 2 2 5

for performance enhancement [13e19]. Drawbacks of Ni- velocity. Using temperatures between 700 and 900  C and
based catalysts include higher cost compared to Fe based space velocities between 3 and 6 LN/(gcat$h), CH4 conver-
catalysts and safety concerns associated with use of a sus- sion in the range of 25e40% could be obtained during a 6 h
pected carcinogen. run. In addition, carbon was deposited in the form of
Co based catalysts have also been investigated [20,21] by nanofilaments (chain like nanofibers and multiwall nano-
various researchers. Co/Zr-Mg catalyst [20] showed the best tubes) with similar properties to those obtained in a fixed
performance at 700  C in fixed bed flow reactor studies with bed reactor. Pinilla et al. [28] also discussed the reactivity of
50e80% H2 yield within 350 min reaction time. Effect of La, Ce Fe based catalyst and the formation of carbon nano
and Nd oxides on Co-MgO catalyst [21] indicated that CoeLa/ products.
MgO had the best (80%) H2% for 220 min. Tri metallic cata- Carbon-based catalysts have also been investigated by
lysts containing alumina supported Fe, Ni and Co based various researchers [7,10,11]. Wang et al. [29] investigated the
catalysts are reported [22] and 15Coe30Fe/Al catalyst was mechanism of CH4-deuterium decomposition with H2 addi-
reported to be the best with H2 yield of about 70% for 180 min tion over activated carbon (AC) using in-situ pyrolysis-elec-
time period. tron impact ionization time of flight mass spectrometry
Iron-based catalysts have received attention because of combining with isotope tracing. During CD4 decomposition,
their lower cost and minimal environmental issues. Iron- breakage of the first C-D bond was found to be the rate control
based catalysts are reactive above 700  C, and CH4 conver- step, and the lifetime of CDx free radicals decreased with the
sion rates have been reported to be lower than that with Ni. removal of D atoms. When hydrogen was present, hydroge-
Inert supports have been used for performance enhancement. nation of the formed free radicals was observed due to the
Zhou et al. [23] conducted fixed bed tests with various sup- decrease in the collision among CD4 molecules. This stabilized
ported Fe catalysts, and the performance data at 750  C indi- the produced CDx free radicals, leading to the enhancement of
cated that Fe/Al2O3 had the best performance with 70% CH4 CH4 conversion and catalytic stability. Natural sand based
conversion for 400 min. They described a reaction mechanism catalysts [30] has also been investigated as a catalyst. Molten
for carbon formation via formation of super-saturated iron salts have also been explored as catalysts for CH4 decompo-
carbide. They also reported literature review data on the sition. Kang et al. [31] reported a molten KCl:MnCl2 mixture as
performance of various Fe-based catalysts prepared using an effective catalyst for MP. The KCl:MnCl2 melt showed 30%
different techniques. CH4 conversion, at 1050  C with high hydrogen selectivity
Pudukudy et al. investigated [24] cerium (Ce) and (99%). The pyrolysis activity of the KCl:MnCl2 melt remained
lanthanum (La) oxide supported Fe catalysts in fixed bed tests. stable for over 30 h and produced a separable, highly graphitic
The Fe/CeO2 catalyst showed high catalytic stability based on carbon solid that accumulated at the surface of the higher-
H2 yield, and the Fe/La2O3 catalyst showed the lowest stability. density salt melt. Microwave based methane pyrolysis
Based on 360-min tests, Pudukudy et al. indicated the studies focusing on lowering the temperature of decomposi-
improved surface stabilization and fine dispersion of Fe tion and associated energy input have been reported [32,
nanocrystals on the Ce matrix made it highly active and stable 33,34].
compared to the La-based catalyst for the CH4 decomposition In our previous work, the reactivity of Ni, Fe, and C cata-
reaction. lyst types were tabulated and compared with respect to MP
Fluidized bed tests have also been conducted with Fe- [5]. Upon examination of the literature and based on our
based catalysts. Keller et al. [25,26] reported fluid bed data previous findings Fe based catalysts show the greatest
with Fe-alumina and Fe-zirconia. The data with Fe/Al2O3 in- promise for fitting into the envisioned thermo-catalytic py-
dicates a general suitability of the material for the intended rolysis technology for a number of reasons. (1) Fe e based
methane cracking process as long as the amount of carbon catalysts can be of high reactivity at the desired pyrolysis
deposition is constrained to under approx. 10 wt%. The CH4 temperature of 700  C. (2) These materials are known to
exposure times were limited to 90e180 min at 750e850  C. The generate value added carbon products. (3) Fe based catalyst
fractional CH4 conversion to solid carbon decreased from 0.9 sourcing can be directly aligned with US domestic iron-ore
to 0.4 within the first 90 min. The kinetic data obtained can be sources and the iron processing industry. Availability, cost,
useful for design and scale-up of the CH4 cracking process in a and industrial alignment are significant considerations
fluidized bed. The reaction was found to be mass transfer influencing catalyst selection.
limited at temperatures higher than 800  C and was kinetically The novel patent-approved Fe based catalyst that we
controlled below 800  C. Catalyst deactivation was found to be report in this work was developed for both methane and
independent of reaction temperature. The tests with Fe/ZrO2 ethane pyrolysis. The catalyst material and data collection
were conducted for 180 min at 740e840  C. Methane conver- seek to address some of the barrier issues that were seen with
sion peaked around 89% within the first 4 min but decreased previous catalysts. Catalyst performance with CH4 and C2H6
to 5% within 16 min. A procedure to recover the ZrO2 support conducted using thermogravimetric analysis (TGA), long term
by oxidation with O2 at 450  C and with steam at 600  C is fluidized bed flow reactor tests with continuous carbon
reported. collection, and carbon analysis using Raman spectroscopy
Torress et al. [27] studied catalytic decomposition of CH4 and transmission electron microscopy (TEM) are discussed in
using a Fe/Al2O3 catalyst for H2 production in fluid bed tests. the current work. Kinetic analyses for both methane and
Reaction temperature and space velocity strongly affected ethane pyrolysis were conducted using a comprehensive data
catalyst performance. Methane conversion was increased set developed using TGA. A parametric regression was per-
by increasing the temperature and lowering the space formed to deduce the impact of the two gases on reaction rate
 i n t e r n a t i o n a l j o u r n a l o f h y d r o g e n e n e r g y 4 8 ( 2 0 2 3 ) 1 4 2 1 0 e1 4 2 2 5 14213

parameters for models developed for the reaction rate ex- and was reduced in H2 at 800  C prior to reaction. The catalyst
pressions. Studies on ethane and methane pyrolysis collec- pellets were class Geldhart B with a particle density of 2.9 g/
tively with a single catalyst material are very limited, with cm3.
little to no work to date having been conducted on catalytic
ethane pyrolysis. Thermogravimetric analysis
In addition to examining the performance of the catalyst
material it was also of importance to qualify the carbon The catalyst material was tested with both CH4 and C2H6 for
product. Carbon produced in the process can be used for pyrolysis reactions in a Q600 -SDT-DSC (TA instruments)
various applications such as tires, batteries, polymers, thermogravimetric analyzer. The pellets (15e25 mg) placed in
plastics, and reinforced composite materials. The value of the sample pan were reduced with 20 vol. % H2 at 800  C for 1 h
carbon can range from $0.5e10/kg to >$100/kg [6] depending prior to CH4 or C2H6 introduction. Then 10% CH4 or C2H6 were
on the type of carbon. Graphitic carbons have a value of introduced at 100 sccm for 90e180 min at 600  C, 700  C, 750  C,
$þ10/Kg while highly specialized carbon nanotubes and fi- 800  C, and 850  C. Weight change due to carbon accumulation
bers have higher values ($þ25/kg). Based on ASPEN on the catalyst was recorded as a function of time. The system
modeling, Daggle et al. [6] reported that, for a small-scale had a balance purge set nominally at 50 ml/min U.H.P. argon
plasma system, the cost of H2 was estimated at $7.0/kg (Ar), and a sample gas port set nominally at 50 ml/min of the
assuming a natural gas price of $5/MMBtu without carbon sample gas, which enabled the blending of CH4 or C2H6 and Ar
credits, and decreased to $2.5/kg when selling carbon black to the desired concentration level. Prior to elevating the
at $1.35/kg [6]. The conclusion of our previous study [5] was sample temperature, the system was purged for at least
that the cost of pyrolytically produced CO2-free hydrogen 30 min via a programed method. This ensured that the reac-
can be potentially reduced to levels < $2/kg target with the tion chamber was free of oxygen prior to heating to prevent
co-production and sale of sufficiently high-value carbon interaction with the catalyst surface. Experiments were also
products. explored to examine the impact of gas concentration on py-
rolysis behavior, varying from 1 to 40 vol%. Temperature and
concentration effects were used as the major driving forces to
Experimental determine kinetic parameters and rate expression constants.
Temperature programed experiments were conducted with
Materials 10% CH4 from 50 to 1000  C at 20  C/min with particle ranges
from 180 to 600 mm.
The FeeAl2O3 catalyst was prepared by wet agglomeration
method which consisted of addition of water to solid powders Fluidized bed reactor test set up with continuous carbon
of Fe2O3 (Sigma - Aldrich) and Al2O3 (Sigma - Aldrich) in a collection
rotating drum [5] to create microspheres. The microspheres
100e1000 mm were heat treated above 1000  C for 8 h. The heat Fluidized bed tests were carried out using a fluidized-bed
treated product was sieved to the desired ranges of 75e180 mm reactor (shown in Fig. 1) manufactured by Autoclave Engi-
and 180e600 mm for testing. The catalyst had Fe/Al ratio >2 neers (HR-160 Reactor Assembly Model # 5010-2377). The

Fig. 1 e Fluidized bed reactor with continuous collection of carbon with dual filters.
14214 i n t e r n a t i o n a l j o u r n a l o f h y d r o g e n e n e r g y 4 8 ( 2 0 2 3 ) 1 4 2 1 0 e1 4 2 2 5

maximum bed height was 34.3 cm, and the diameter was beyond 750  C. This tightening of the grouping suggests an
6 cm. The reactor column was made from Inconel SB-564 to asymptotic rate increase as a function of temperature. TGA
withstand temperatures up to 900  C. A ceramic porous plate weight change corresponding to carbon formation with C2H6
with 15e40 mm pores was used as the gas distributor. The are also shown in Fig. 2. The catalyst had no reaction with
setup was equipped with three electrical heaters installed C2H6 at 600  C similar to that with CH4. At 700  C C2H6 reacted
around the reactor to heat the reactor to the target tempera- rapidly with the catalyst and the carbon formation rate
ture of 700  C. Dual filters with element size 0.01 mm, length continued to increase up to 800  C; no appreciable increase
17.8 cm, and I.D. 3.175 cm were installed at the outlet of the occurred beyond 800  C. Comparative data on weight change
reactor to capture the carbon-containing fines generated from corresponding to carbon formation with CH4 and C2H6 at
the reactor. The direction of gas flow was changed between 700  C and 800  C are shown in Fig. 3. The data indicated that
the two filters every 4 h and each filter was cleaned during that the carbon generation rate from C2H6 decomposition is higher
time. About 400e500 g of the catalyst was heated to the re- than that associated with CH4 decomposition. The fuel
action temperature (700  C) in Ar. Then, 5e10 vol.% CH4 or inherently has more carbon, and this response was
C2H6 was introduced at 700  C. The reactor effluent was anticipated.
monitored using a Prima mass spectrometer. The catalyst Effect of CH4 and C2H6 concentration on the weight gain
amount was selected to obtain the methane conversions of due to carbon formation at 700  C is shown in Fig. 3. A
80e90% with the methane concentrations and flow rates used consistent increase in carbon formation rate was observed
in the study. with increasing CH4 concentration.

Other characterization

X-ray diffraction and Raman spectroscopic analysis

X-ray diffraction (XRD) analyses were carried out using a
Panalytical PW 3040 X-Pert Pro XRD system equipped with a
60 kV PW 3373/00 Cu LFF high-power ceramic tube with a
copper (Cu) anode and a PW 3011/20 20 detector. XRD was
used to identify the metallic species in the catalyst and as a
confirmation technique for graphitic type carbon formation in
the carbon product.
A Horiba Jobin Yvon-LabRAM HR Evolution spectrometer
equipped with a confocal microscope was used for Raman
spectroscopic analysis. Excitation Ar-ion laser wavelength of
532 nm was used at spectral resolution, 0.65cm-1 with an
acquisition time of 5 min. Neutral density filters were used to
lower the 1 W laser to 100 mW during sampling. Raman
spectroscopic analysis were used as a qualitative means to
understand the carbon product. Specific Raman bands arise in
nano featured carbon materials that allow for allotropes to be
distinguished from one another. These are described in more
detail in the results section.

Results and discussion

TGA data on impact of reaction conditions on the pyrolysis

of CH4 and C2H6

The TGA weight percent data during CH4 and C2H6 exposures
to the catalyst at different temperatures (600e850  C) are
shown in Fig. 2 with 10 vol% CH4. The point at which weight
gain began corresponds to when the reaction gas was intro-
duced to the sample. The flat regions near the end of data
collection correspond to when the reaction gas was turned off
and the sample chamber was purged with inert gas and
cooled. The reactivity at 600  C was very low with no appre-
ciable weight gain. However, at 700  C weight gain occurred at
an appreciable rate due to carbon formation from MP. Activity
initiates at some point between 600 and 700  C. Carbon for-
mation rate continued to increase at 750  C, but the increase Fig. 2 e TGA data at 10 vol% CH4 (a) & C2H6 (b) at
was not that significant when the temperature was increased temperatures ranging from 600 to 850  C.
 i n t e r n a t i o n a l j o u r n a l o f h y d r o g e n e n e r g y 4 8 ( 2 0 2 3 ) 1 4 2 1 0 e1 4 2 2 5 14215

The rate increased from 10 vol.% C2H6 to 15 vol.% C2H6, but proceeds only via R3, then the mass change would asympto-
some mass was lost due to carbon overflowing the sample ticly approach that of R1 and a prevalence of CH4 would be
holder. The rate also increased from 15 to 20 vol.%. The data seen in the effluent gases. In fluid bed experiments (discussed
clearly indicated that, compared to CH4, carbon forms faster in section 3.2.4) when C2H6 was used as the reactive gas, only a
from C2H6 decomposition and the rate difference is higher at small amount of CH4 was also observed in the effluent gas
higher concentration. stream in addition to H2, which indicated that R3 takes place
Per mole basis ethane has more carbon than methane. in addition to R2 due to the presence of more H2 in fluid bed
More carbon formation with ethane during TGA tests with tests. Mechanisms that generate ethylene (R4) are not ther-
higher rates is partially due to that but still ethane has to modynamically favorable at temperatures below 790  C. The
decompose breaking all the bonds including CeH bonds and pyrolysis reaction with ethylene (R5) would be favorable based
CeC bonds to form the carbon. Therefore, bond dissociation on the Gibbs free energy and the exothermicity depicted by
energies of ethane and methane have to be considered. The the enthalpy curve, but its formation from C2H6 would be
bond dissociation energies of CH4 and C2H6 [35] are listed in challenging based on the low thermodynamic favorability of
Table 1. CH3eH bond dissociation energy associated with the R4 depicted through the Gibbs Free energy curve. One aspect
primary abstraction of the first H atom is generally higher to note concerning the thermodynamic calculations is that
than the HeCH2CH3 or HeCH2CH2 (H abstraction from C2H6 although the DG is negative for most of the species at 500  C or
and ethyl) bond dissociation energies. H bond dissociation above, the reaction still requires a catalyst to complete for-
energies for methyl bonds are also higher than that with ethyl ward progression at an appreciable rate.
bonds. Bond dissociation energies for the methyl-methyl bond
in C2H6 are the ~14% lower than the HeCH3 bond in CH4. Bond Fluidized bed flow reactor performance: optimization of
dissociation energies increase as more H2 is abstracted from reaction conditions and comparison of methane and ethane
the radical. performance
The Gibbs free energy and reaction enthalpy for the three
main pyrolysis paths and coupled side reactions (R1-R5) are Batch fluidized bed tests were conducted to understand the
depicted with CH4 and C2H6 in Fig. S1 (supplementary infor- performance of the catalyst material with critical components of
mation) and Table 2. natural gas. The batch experiments are a snapshot of perfor-
Similar to the conclusions associated with bond dissocia- mance in relation to a commercial continuous system. Effluent
tion energies, the Gibbs free energies of mechanisms concentration of CH4, C2H6, CO2, CO, H2, ethylene and oxygen
involving C2H6 decomposition are at lower energy levels (more were measured during the fluidized bed tests with CH4 and C2H6.
negative), suggesting that thermodynamically they would be Methane conversion, C2H6 conversion and H2 yields were
more easily achieved as compared to CH4; however, the calculated using equations (2)e(4). CH4 In and C2H6 In are the
complete pyrolysis of C2H6 is more endothermic than the re- inlet CH4 and C2H6 concentrations to the reactor, which were
action with CH4. This is consistent with what is observed with measured during blank tests. CH4 Out, C2H6 Out and H2 Out are
the TGA data shown previously. The reaction with ethane is the effluent gas concentrations measured during the tests.
more productive in generating carbon and has a steeper slope
compared to CH4 alone suggesting that the mechanism pro- XCH4 (Methane Conversion [%]) ¼ (CH4 In e CH4 Out) x 100/CH4
ceeds mainly through R2 to completion. If C2H6 pyrolysis In E2

XC2H6 (Ethane Conversion [%]) ¼ (C2H6 In e C2H6 Out) x 100)/

C2H6 In E3

YH2 (Hydrogen Yield) ¼ H2 Out x 100/(2 x CH4 In þ 3 x C2H6 In)

E4

Performance data with particle size 160e600 mm and 5%

methane at 700  C
The flow rate used for the fluid bed tests was 21.5 SCFH
which is 1.4 x minimum fluidization velocity (MFV ¼ 15.1
scfh) with 160e600 mm particles. When 4e5% CH4 was
introduced to 425 g of catalyst at 700  C, the major gases
observed initially were H2 and CH4 with a small amount of
CO. After 4 h, the only gases observed were H2 and CH4 with
high H2 concentration, indicating that CH4 is only converted
to H2 and carbon. As shown in Fig. 4, CH4 conversion to H2
was close to 90% initially and it remained above 80% for 50 h.
Methane conversion was above 60% for 65 h of the test.
Similar long-term fluidized bed tests with high CH4 to H2
Fig. 3 e TGA data on effect of CH4 and C2H6 concentration conversions are not reported in the literature. Carbon con-
on weight gain from carbon formation at 700  C. taining fines were collected in the filters continuously during
14216 i n t e r n a t i o n a l j o u r n a l o f h y d r o g e n e n e r g y 4 8 ( 2 0 2 3 ) 1 4 2 1 0 e1 4 2 2 5

Table 1 e Bond Dissociation Energies of Species Derived from CH4 and C2H6 (adapted from Ref. [35]).
Species Dissociating Bond Bond Dissociation Enthalpies Normalized Dissociation
[kJ/mol] @ 298.15 K Enthalpy
Methane, CH4 HeCH3 438.9 1.00
Methyl, CH3 HeCH2 (to eqCH2) 463.1 1.06
HeCH2 (to 3CH2) 463.1 1.06
HeCH2 (to 1CH2) 500 1.14
Ethane, CH3CH3 HeCH2CH3 421.7 0.96
CH3eCH3 376.66 0.86
Ethyl, CH3CH2 HeCH2CH2 150.59 0.34
CH3CHeH (to eqCH3CH) 452.61 1.03
CH3CHeH (to 3CH3CH) 452.59 1.03
CH3CHeH (to 1CH3CH) 464.84 1.06
CH3eCH2 (to eqCH2) 418.03 0.95
CH3eCH2 (to 3CH2) 418.03 0.95
CH3eCH2 (to 1CH2) 455.55 1.04

spectroscopy analysis of the carbon, shown in Fig. 10b, further

Table 2 e Pyrolysis reaction routes. confirmed this finding but elaborated on the allotrope and
Reaction # Formula DG [kJ/mol] DH [kJ/mol] structure in further detail. The Raman band peak data can be
(@700  C) (@700  C) used to infer properties and allotrope presence. Sharp D, G and
G' bands represent carbon nanomaterials. The presence of the
R1 CH4/Cþ2H2 16.5 88.8
R2 C2H6 / 2Cþ3H2 104.8 104.5 D band indicates the presence of carbon nanotubes and dif-
R3 C2H6 / CH4þC þ H2 88.2 15.7 ferentiates the material from graphite and graphene. The D/G
R4 C2H6 / C2H4þH2 12.1 142.9 band ratio suggests the formation of carbon nanotubes [36].
R5 C2H4 / 2Cþ2H2 116.9 38.4 The presence of the RGM mode in a small quantity suggests
the formation of single-wall nanotubes, which tend to only
appear in the ring breathing mode. This mode is typically
the tests. The filters were periodically measured as they hindered by multiwall formation as the outer wall restricts
became full during testing. During the first 10 h of testing the breathing of the tube wall [36]. The G/G0 band ratio indicates
filters accumulated marginal amounts of carbon containing that the tubes formed can range in a diameter greater than
fines, indicating that much of the carbon generated was still 100 nm. For smaller diameter tubes of 1e2.5 nm, the G/G0 ratio
within the bed. After 10 h the carbon containing fines began tends to approach 5 while reducing to 2 for multiwall tubes
to steadily elutriate as the test progressed when more carbon (MWCNTs) of 20e30 nm. The spectrum suggests that a mixed
accumulated in the reactor. allotrope of nanotubes (some being large enough to qualify as
TEM of the carbon is shown in Fig. 5a. All the carbon ma- fibers) are formed and that the tubes can range in diameter up
terials were identified as nanofibers and nanotubes with the to 100 nm. Coalescence of the tubes is likely to create the
resultant materials being a mix of the nano allotropes. Raman larger diameter fibers (~150e200 nm) observed in the TEM

Fig. 4 e Percentage of CH4 conversion to H2 during 65 h fluid bed test with 5% CH4.
 i n t e r n a t i o n a l j o u r n a l o f h y d r o g e n e n e r g y 4 8 ( 2 0 2 3 ) 1 4 2 1 0 e1 4 2 2 5 14217

Fig. 5 e Characterization of generated carbon (a) TEM and (b) Raman spectra of carbon produced by fluidized bed MP.

imaging. The darker areas in the TEM images indicate higher Performance data with particle size 75e180 mm and 10% CH4 at
density and/or molecular weight. These areas indicate the 700  C
seed sites from which the carbon products accumulate, orient, TGA data indicated that a particle size less than 300 mm had a
and grow into the ordered structures. The size of the seed site better MP rate than the bigger particles (Figure supplement 3),
appears to impact the tube diameter based on what is and fluidized bed tests were conducted to investigate the
observed in the literature [37] and from the TEM imaging with effect of particle size. The fluidized bed data with catalyst
the mixed allotrope displayed in this work. The shoulders on particle size 75e180 m, which is smaller than what was used
the G’ band, (D þ D00 , ~2500 cm1 and D þ G, ~2900 cm1) are in the previous tests (160e600 m), using 9e10% CH4 with 500 g
secondary Raman scattering and are characteristic of of the catalyst is shown in Fig. 6. The flow rate of 7 scfh used
MWCNTs and, in the case of D þ D”, characteristic in multi- was 3 X MFV. When the particle size was small, the minimum
layer graphene [38]. Generally, within the literature, the D/G fluidization velocity was lower and the catalyst particle
band ratio for MWCNTs is closer to 1e1.5. The results encountered less CH4 per unit time. Similar to the previous
observed further indicate that the carbon product is of a tests, only H2 and CH4 were observed in the effluent gas
mixed allotrope. stream during the test. The catalyst was able to maintain the
X-Ray diffraction data of the fresh catalyst indicated the CH4 conversion to H2 above 80% for 165 h, which is signifi-
presence of Fe0 and FeO and after the reaction with methane, cantly higher than the reaction time with particle size
Fe0, Fe carbide and graphitic carbon were observed. 160e600 m. The CH4 conversion rate of the catalyst remained
above 60% for 224 h and above 30% for 270 h. This result is
Performance data with particle size 160e600 mm and 10% very significant because similar long-term tests with high CH4
methane at 700  C conversions to H2 are not reported in the literature [23]. As
When 10% CH4 was introduced, the only effluent gases reported by Torres et al. [27], a fluid bed test done with Fe/
measured were H2 and CH4. The CH4 conversion to H2 and H2 Alumina sample lasted for 6 h with 18% CH4 conversion. The
yield data with 344 g of catalyst (180e600 mm) during the flu- longest performing catalyst reported by Wang et al. [39]
idized bed test using 8e10 vol.% CH4 is shown in Fig. S2. The demonstrated 210 h of fixed bed test with 40% CH4 conversion
CH4 conversion and H2 yields were similar, indicating that the using NieAl Fe catalyst. The Fe catalyst reported in this work
CH4 fully converted to H2. The CH4 conversion to H2 was lower maintained 80 to 60% methane conversion to H2, for 224 h
than that with 4e5% CH4 (Fig. 9) because of the higher inlet which is significantly higher than that with the best per-
CH4 concentration and lower amount of catalyst (344 g) used forming catalyst reported in the literature.
in this test series. The highest CH4 conversion to H2 was about A TEM image analysis, shown in Fig. 7, of the carbon
80% and it remained above 60% for about 34 h, which is lower generated during the tests from 75 to 180 mm particles (Fig. 6)
than the 65 h with 5 vol.% CH4. Higher CH4 concentration per and that of 160e600 mm particles (Fig. 4) were compared to
unit weight of the catalyst contributed to the lower rate of CH4 deduce if there was a difference in the general size distri-
conversion to H2 which may be due to the higher carbon bution of the carbon product based on the catalyst size. The
accumulation on the catalyst. data were taken from single samplings of the residual bed
material after the completion of the test. It was determined
Performance data with particle size 160e600 mm and 10% CH4 that the general size distributions favored nanotubes and
at 750  C fibers of similar size with both catalyst size fractions. The
When the fluidized bed test was conducted with 10% CH4 and nanomaterials favoring diameters of 20e140 nm with a
375 g of the catalyst at 750  C, the CH4 conversion to H2 was mean of ~50e60 nm and some fibers conglomerating to
between 80 and 90% for 28 h (data not shown), which is better 200e300 nm in diameter. The limited sampling, frame of
than the 70e80% conversion observed at 700  C with 10% CH4. reference, and difference in on-stream time between the
After 28 h the CH4 conversion dropped to 20%. runs makes it challenging to understand the effect of
14218 i n t e r n a t i o n a l j o u r n a l o f h y d r o g e n e n e r g y 4 8 ( 2 0 2 3 ) 1 4 2 1 0 e1 4 2 2 5

Fig. 6 e Percentage of CH4 conversion to H2 during 280 h fluid bed test with 10% CH4 (cycles denoted by data points).

catalyst particle size on nanocarbon size. It's likely that these nanomaterial diameter distribution. This indicated that ~35%
are consequential of the sampling, time on-stream and a of the tubes generated were ~50 nm in diameter with larger
more comprehensive data set would be needed to form a materials (fibers) approaching 300 nm in diameter. Due to the
quantitative conclusion. frame of reference used for the TEM imaging, quantifying the
nanomaterial lengths was challenging. Lengths appear to
Performance data with a mixture of C2H6 (~2 vol%) and CH4 range from 0.5 to 5 mm or greater within the frame of refer-
(7e8 vol.%) ence, which was limited and could potentially skew the
TGA data indicated that C2H6 has a higher rate of decom- distribution.
position than CH4 and a fluidized test was conducted to Separate short-term fluidized bed experiments were con-
understand the effect of C2H6, which is a component of ducted with C2H6 as a sole feed component at 4 and 8 vol% to
natural gas and flare gas, on MP. The fluidized bed test data examine the feed component's sole impact. The tests indi-
on CH4 and C2H6 conversion to H2 when a mixture of 8 vol.% cated that CH4 was a minor product of C2H6 pyrolysis. When
CH4 and 2 vol.% C2H6 was introduced to the catalyst with 4% C2H6 was exposed to the catalyst, 0.5% CH4 was observed.
particle size, 180e600 mm is shown in Fig. 8. The test data When 8% C2H6 was used, ~1% CH4 was observed. The data
depicts a ~32 h test. C2H6 conversion remained at 100% for indicated that the reaction R3 in Table 2 takes place partially,
28 h while CH4 conversion remained around 60% for about in addition to the prominent reaction of R2. The measured CH4
24 h. The catalyst preferentially converted C2H6 to H2 over breakthrough indicated that R3 accounts for about ~12.5% of
CH4, which is consistent with the TGA data in Fig. 3 that also the consumption of C2H6 while R2 accounts for the balance of
showed higher C2H6 conversion rates. The H2 yield remained ~87.5% of the C2H6 consumption, indicating the predominant
above 50% for 28 h, as shown in Fig. S4. Fig. S4 also depicts reaction. Yin Chin et al. noted this behavior with a NieSiO2
the gas concentrations of selected components. Initially a catalyst for the decomposition of C2H6 for H2 generation [40].
minor amount of C2H6 and CH4 broke through, but after the They noted that the C2H6 pyrolysis reaction mechanism tra-
first 4 h the only gases detected were H2 and CH4. Ethane was verses in part through both R2 and R3 but, in situations where
not detected after this initial 4 h period indicating 100% a high concentration of H2 is present, recombination can occur
consumption of the C2H6 feed component during the 30 h of with the deposited carbon or CHy intermediates from initial
the test. The CH4 to H2 conversion at the end of the test pyrolysis reaction forming CH4.
approached 0% while the C2H6 reduced in magnitude from
90% to 55% in the 30 h period. Kinetic analysis for the reactions with CH4 and C2H6
The TEM of the carbon collected during the test are shown
in Fig. 9. The carbon collected from the test with a mixture of Thermogravimetric data acquired on a Q500 TGA (TA In-
C2H6 and CH4 consisted of carbon nanotubes and nanofibers struments) was used to develop a basic reaction rate expres-
similar to what was obtained with CH4 tests. A histogram was sion and extrapolate kinetic parameters for the primary
generated from a grouping of images to deduce a respective reactions of interest in this work. The data used to develop the
 i n t e r n a t i o n a l j o u r n a l o f h y d r o g e n e n e r g y 4 8 ( 2 0 2 3 ) 1 4 2 1 0 e1 4 2 2 5 14219

Fig. 7 e TEM of carbon produced by fluidized bed MP experiments with different catalyst particle sizes and measured carbon
nanomaterial diameter distributions.

Fig. 8 e Percentages of C2H6 and CH4 conversion to H2 with 500 g catalyst during the catalyst test with 8% CH4 and 2% C2H6 at
700  C.
14220 i n t e r n a t i o n a l j o u r n a l o f h y d r o g e n e n e r g y 4 8 ( 2 0 2 3 ) 1 4 2 1 0 e1 4 2 2 5

Fig. 9 e TEM of carbon produced by fluidized bed MP and measured carbon nanomaterial diameter distribution.

rate expressions was partially displayed in prior sections (Figs. small fraction of the weight gain observed from pyrolysis
2e4) where weight change data was obtained with concen- (~7 wt%). As shown in Fig. 10, the P1 phase is clearly seen with
trations ranging from 1 to 40 vol% of both CH4 and C2H6 while a 5% CH4 concentration for about 10 min and appeared as a
holding the isothermal temperature of 700  C. Temperature spike for a short duration with 40% CH4 concentration. The
effects were explored with a conservative concentration of the steady state phase has a lower rate of carbon generation, but
gas species (~10 vol%). Fig. 10 displays the rate and resultant at a steady pace with continual carbon growth, that can ac-
weight % curves generated from TG experiments with count for nearly 200þ% weight gain due to carbon accumu-
1e40 vol% CH4 at 700  C with the catalyst material. Two pri- lation in under 60 min* (depending on concentration,
mary regions (P1 and P2) indicated carbon growth: (1) P1, the temperature and time on-stream). The steady state phase is
rapid carbon growth corresponding to initial surface coverage more important than the initial phase, based on extended
of carbon at the reaction initiation, and (2) P2, the “steady fluid bed experiments carried out as bench-scale demonstra-
state” growth of carbon. The P1 and P2 markings correspond tions of catalyst effectiveness. The time periods are limited in
to the 5 and 40 vol% CH4 experiments. The P1 phase is func- the TGA, based on the catalyst loading and crucible volume
tionally dependent on temperature and concentration, much (~100 ml), unlike the fluid bed that had a carbon removal
like the P2 phase, and is slow in rate at 1% CH4. The initial mechanism (elutriation). In the TGA, carbon accumulates and,
surface coverage clearly has a higher rate than the steady if reaction conditions are held for extended periods, spills over
stage regime, but this initial phase only accounts for a very from the crucible and skews the data. Therefore, shorter

Fig. 10 e Carbon generation rate and weight percent curves from TG experiments with 1-~40 vol% CH4 at 700  C.
 i n t e r n a t i o n a l j o u r n a l o f h y d r o g e n e n e r g y 4 8 ( 2 0 2 3 ) 1 4 2 1 0 e1 4 2 2 5 14221

reaction periods are employed to capture the behavior. Re- dependence, ni , for the reactions [43]. The Arrhenius relation
actions with C2H6 also showed both the P1 and P2 reaction (E8) was applied with a targeted data array (fixed CxHy con-
phases (data not shown). The analysis in this section focused centration while varying temperature isothermally) to
solely on the steady state (P2) regime because it has more extrapolate the activation energy and the Arrhenius constant
relevance to the overall carbon generation mechanism. for each reaction. Similarly, a power law relation was applied
A conservative model outlined in E5-7 represents the rate of to extrapolate the partial pressure dependence, n, from a
carbon production as a function of the Arrhenius reaction rate targeted data array (fixed temperature while varying partial
factor kc;i , partial pressure of CH4 PCH4 , or C2H6 PC2 H6 and the pressure of the reactive gas through controlling the vol%
power depence ni . Other researchers have also applied a power within the TGA feed gas).
law-based model representation to emulate the utilization of
Ea
CH4 in the catalytic pyrolysis reaction [41,42], which is assumed Arrhenius relation ln k ¼ ln A  (E8)
RT
to hold true for C2H6. This same methodology was applied in our
previous work [5] for a prior iteration of the catalyst material. Fig. 11a shows the Arrhenius relation for the pyrolysis re-
The power law forms assume that the prevailing reactions are actions with CH4 and C2H6 for the steady state pyrolysis re-
R1 and R2 (see Figure supplement -Table 2), leading to the gion. Values for kc;i were initially extrapolated from the
complete pyrolysis of the two feed gases to carbon and H2. experimental data (assuming an order dependence of unity)
and tabulated with respect to temperature. The slope of the
Power Law R1 Rc;1 ¼ kc;1 PCH4 n1 (E5) Arrhenius relation was used to extrapolate the activation
energy (EA ) while the intercept was used to determine the
Power Law R2 R;2c ¼ kc;2 PC2 H6 n2 (E6) reaction Arrhenius constant (A). The rate of carbon generation
was determined from the experimental data and tabulated

 with respect to the partial pressure of the gas reactant. The
EA;i
=RT order dependence was determined by performing a power law
Arrhenius form kc;i ¼ Ai e ; i ¼ 1; 2 (E7)
fit to the extrapolated data points, displayed in Fig. 11b.
Conventional strategies were used to fit the activation en- The determined parameters were iteratively refined until a
ergy EA , Arrhenius constant Ai and partial pressure solution (for EA;i , Ai , and ni ) minimized the error between the

Fig. 11 e Arrhenius factor with coupled activation energy determination (a) and reaction partial pressure dependence (b) for
catalytic CH4 and C2H6 pyrolysis to carbon and H2. (c) Depiction of model predictive behavior when compared to
experimental data for reactions at 700  C.
14222 i n t e r n a t i o n a l j o u r n a l o f h y d r o g e n e n e r g y 4 8 ( 2 0 2 3 ) 1 4 2 1 0 e1 4 2 2 5

model function (E5 & E6) and the experimental data

[kmol/kgcat-sec]/[N/m2]n (gC/gcatalyst sec)

(comprehensive data array). This technique employed a non-
linear least squares regression analysis that employed a cor-

0.00023
0.00053
Rc;i relation coefficient used to evaluate the effectiveness of the
Calculation (@700  C, CxHy

model and parameter fitness [44]. A minimum of 50 data

Comparative Rate

points were used when evaluating the fit, which compared the
[N/m2] ¼ 20265)

experimentally measured mass and theoretical model pre-

dicted mass. The technique is similar to what was used in our
previous works [5,45]. Integrating the rate function (E5/E6)
with respect to time yielded E9, which was used to predict the
4.98E-08
1.15E-07
Table 3 e Determined reaction rate parameters for model description of the complete pyrolysis of methane and ethane mediated by catalyst.

mass of the catalyst material plus accumulated carbon with

kc;i

respect to on-stream time, model rate parameters, and known

operating conditions (reactant gas concentration/partial
pressure and temperature). Examples of the model emulation
compared to the experimental data for 10 vol% CxHy at 700  C
are displayed in Fig. 11c, which shows the conservative fit.
0.6
0.6
Ai (Catalyst mass basis) ni

Model emulation falls within R2 values of 0.98 or greater but

Energy [kJ/mol] [kmol/m3-sec]/[N/m2]n [kmol/kgcat-sec]/[N/m2]n

rarely equivalent to 1. In the instance where a fit cannot match

the experimental data perfectly (e.g., R2 ¼ 1), a conservative fit
that slightly underpredicts the behavior was used. Often, this
Regressed Rate Parameters and Other Pertinent Properties

1.037E-05

is the majority of cases that employ a simplified representa-

0.00025

tion to emulate complex phenomena.

h ini  mg   
mpredicted ðtÞ½mg ¼ kc;i PCx Hy ðt½secÞ mi;cat ½mg
mgcat sec
 
þ mi;cat ½mg
(E9)
Ai (vol. basis)

Table 3 displays the optimized solutions for the model rate

parameters. Methane is found to have a lower functional
0.03
0.73

temperature dependence over 700e850  C when compared to

C2H6, as demonstrated by the lower activation energy of 43 kJ/
mol for CH4 compared to 62 kJ/mol for C2H6. Although CH4 has
a lower activation energy, it is still not as active of a reactant
as C2H6, recalling that the rate of carbon generation is a
Catalyst EA;i Activation

function of both the activation energy and the Arrhenius

constantalso referred to as the frequency factor or turnover
43.18
62.23

frequency. The difference in activation energy simply dem-

onstrates that “within the current frame of reference,” C2H6
has a steeper functional dependence to alterations in tem-
rb [kg/m3]

perature. If either gas was unaffected by temperature the

Density,
Bulk

2900
2900

activation energy would tend to be zero and the turnover

frequency would drive the reaction. The turnover frequency of
C2H6 results in carbon generation rates greater than CH4
700e850  C, 1-~40 vol% C2H6, 1 atm

alone. If both gases were equivalent in reactivity, the carbon

700e850  C, 1-~40 vol% CH4, 1 atm

generation rate for C2H6 would be expected to be 2 times that

Relevant Conditions

of CH4 solely based on the available carbon content in C2H6.

However, the observed turnover rate was 2.3e2.8 times that of
CH4, with higher values at elevated temperature, demon-
strating that the gas is more reactive. Both gases have a
similar partial pressure dependence ~0.6. The fact that ~2x the
amount of carbon is generated also confirms the prevailing
mechanism reaction, indicating clearly that full pyrolysis of
C2H6 occurs, by contrast to other mechanisms leading to
partial pyrolysis and side products. The reaction environment
Gas Reactant

in TGA experiments is believed to enable this by limiting the

amount of gas phase H2 present due to continuous removal of
Methane

H2, which could potentially shift the mechanism towards R3

Ethane

to some degree as noted previously in the fluid bed experi-

ments and based on observations by other researchers [40].
 i n t e r n a t i o n a l j o u r n a l o f h y d r o g e n e n e r g y 4 8 ( 2 0 2 3 ) 1 4 2 1 0 e1 4 2 2 5 14223

Previous works on the non-catalytic thermal decomposi- gas, is an extension of our previous TGA study with the Fe-
tion of these reactants indicate that CH4 decomposition can based catalyst. TGA was used for kinetic analysis and reac-
range with an activation energy from 355 to 460 kJ/mol [46] (at tion model parametric regressions, and the data were used to
780e980  C) down to 147e165 kJ/mol (at 1025e1225  C) [47]. determine the activation energy (EA;i ), frequency factor (Ai ),
The non-catalytic thermal decomposition of C2H6 is reported and partial pressure order dependence (ni ) for CH4 and C2H6.
to occur with an activation energy of 275e309 kJ/mol over a Ethane was found to be more reactive with a higher rate of
lower temperature range of 550e640  C [48]. Temperature pyrolysis to carbon and H2 that was 2.3e2.8 times that of CH4.
differences in two studies make it difficult to compare the Ethane pyrolysis was found to be more sensitive to tempera-
activation energies for MP and C2H6 pyrolysis, but C2H6 ap- ture with a higher activation energy of 62 kJ/mol as compared
pears to have high activation energy even at lower tempera- to CH4 at 43 kJ/mol. The frequency factor, Ai , was significantly
tures. In the two cited studies [47,48], CH4 exhibited a turnover higher for C2H6 at 0.73 [[kmol/m3-sec]/[N/m2]n], compared to
frequency of ~5  106[s1] while C2H6 was reported to be on the 0.03 for CH4 at the same volume. Both gases had a functional
order of ~1  1015. Works on non-catalytic thermal decom- order dependence of ~0.6 based on regression analysis. Fluid-
position show similar trends in activation energies and turn- ized bed bench-scale tests demonstrated that the CH4 con-
over frequencies as those observed in this catalytic study. In version rate with the catalyst remained above 80% for 160 h,
temperature regions where thermal pyrolysis is active for above 60% for 224 h, and above 30% for 270 h, creating signifi-
both species, C2H6 tends to have a higher activation energy cant amounts of carbon and hydrogen and demonstrating
with a higher turnover frequency, indicating a higher rate of extensive time on-stream, which alludes to catalyst lifetimes
turnover with a greater degree of temperature sensitivity. greater than 160 h. Similar catalytic activity with high con-
In our previous work [5], the kinetics of Ni [41] and Fe versions for a long period of time is not reported in the litera-
[49,50] transition metal catalyst from the literature were ture. Ethane was shown to be preferentially more active than
summarized with regard to CH4. These catalytic materials CH4 in both TGA and fluidized bed tests. Fluid bed tests were
resulted in activation energies ranging from 50 to 70 kJ/mol shorter when C2H6 was incorporated with CH4 in the feed gas
(similar to this work). Activated carbon has an activation en- due to the increased rate of carbon formation with C2H6. TEM
ergy of ~200 kJ/mol [42], which was valid at 900e1050  C. In and Raman analysis of the generated carbon show a mixed
their thermal decomposition study of CH4, Palmer et al. [46] allotrope of nanocarbon products of single, multiwall nano-
noted the presence of carbon acted heterogeneously to further tubes and conglomerate nanofibers with diameters ranging
promote and propagate the reaction because of the nucleation from 24 to 230 nm with morphologies ranging from straight to
sites the carbon created. Information on the kinetics of C2H6 curved in spring-like orientations. Ethane did not appear to
pyrolysis was only available for the non-catalytic decompo- impact the allotrope of carbon formed nor did the catalyst size.
sition, as discussed in the previous paragraph. Catalytic The mechanism of carbon growth and carbon selectivity is still
parametric discussion was not available for direct comparison unclear and represents an area of interest for future research.
to this work. Kinetics analyses were based on direct MP (R1) and direct C2H6
Examining the trends from the literature and those found (R2), which were found to be the predominant reactions.
in this work, it can be inferred that non-catalytic thermal However, CH4 formation from C2H6 pyrolysis (R3) can partially
decomposition has a higher activation energy than heterog- occur, specifically when H2 is present; examination of R3 will
enous pyrolysis for both CH4 and C2H6. Pyrolysis with the be incorporated in reaction modeling in a future study.
transition metal catalyst resulted in activation energies lower
than that of activated and product carbons. The transition
metal catalyst generated carbon species of a different allo- Disclaimer
trope than conventional thermal decomposition and carbon-
mediated pyrolysis. Potentially, these allotropes should be This work was funded by the Department of Energy, National
considered further as their thermodynamic properties are Energy Technology Laboratory, an agency of the United States
different than those of carbon black or graphite. A work by Government, through a support contract with Leidos Research
Muratov et al. [51] suggests that the heat capacity of MWCNTs Support Team (LRST). Neither the United States Government
deviates from graphite above 150 K but the study only ex- nor any agency thereof, nor any of their employees, nor LRST,
tends to 300 K, which is lower than the temperature used in nor any of their employees, makes any warranty, expressed or
this study. implied, or assumes any legal liability or responsibility for the
accuracy, completeness, or usefulness of any information,
apparatus, product, or process disclosed, or represents that its
Conclusions use would not infringe privately owned rights. Reference
herein to any specific commercial product, process, or service
The research presented in this work combined the use of by trade name, trademark, manufacturer, or otherwise, does
various characterization techniques to demonstrate the py- not necessarily constitute or imply its endorsement, recom-
rolysis conversion potential of the primary gases in natural mendation, or favoring by the United States Government or
gas, CH4 and C2H6, to carbon and H2 with a novel Fe-based any agency thereof. The views and opinions of authors
catalyst material. This work, which included both lab and expressed herein do not necessarily state or reflect those of
bench-scale experimental work with components of natural the United States Government or any agency thereof.
14224 i n t e r n a t i o n a l j o u r n a l o f h y d r o g e n e n e r g y 4 8 ( 2 0 2 3 ) 1 4 2 1 0 e1 4 2 2 5

in thermocatalytic decomposition of methane. Int J

Declaration of competing interest Hydrogen Energy 2019:7205e15.
[14] Zhang J, Xie W, Li X, Hao Q, Chen H, Ma X. In situ generation
The authors declare that they have no known competing of nickel/carbon catalysts by partial gasification of coal char
financial interests or personal relationships that could have and application for methane decomposition. Int J Hydrogen
Energy 2019:2633e44.
appeared to influence the work reported in this paper.
[15] Lamacz A, Labojko G. CNT and H2 production during CH4
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