Carbon 151 (2019) 181e191

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Carbon
journal homepage: www.elsevier.com/locate/carbon

Solid carbon production and recovery from high temperature methane

pyrolysis in bubble columns containing molten metals and molten
salts
Nazanin Rahimi a, Dohyung Kang a, John Gelinas a, Aditya Menon a, Michael J. Gordon a,
Horia Metiu b, Eric W. McFarland a, *
a
Department of Chemical Engineering, University of California, Santa Barbara, CA, 93106-5080, USA
b
Department of Chemistry and Biochemistry, University of California, Santa Barbara, CA, 93106-9510, USA

a r t i c l e i n f o a b s t r a c t

Article history: We study methane pyrolysis in a bubble column reactor consisting of a layer of molten NiBi alloy, and a
Received 30 March 2019 molten salt layer floating on the metal layer. The molten metal is a pyrolysis catalyst; the molten salt
Received in revised form layer is added for removing contaminants from the carbon product. Methane is introduced at the bottom
8 May 2019
of the reactor and the rising bubbles contain reactant and product gases together with metal vapor and
Accepted 16 May 2019
Available online 17 May 2019
flakes of solid carbon. When the bubbles rise through the molten salt layer the metal vapor condenses
producing dense liquid metal droplets, which sink to the metal phase; the low-density carbon rises to the
top of the salt layer. The carbon generated from the single-phase molten NiBi reactor has a different
structure from that produced in the two-phase NiBi/salt reactor. The amount of metal in the carbon
product is less than 5 wt %, in the two-phase reactor, compared to 83 wt % in the NiBi single-phase
reactor. After subsequent purification steps one obtains solid carbon with less than 2 wt % salt
contamination and no detectable metal contamination.
© 2019 Elsevier Ltd. All rights reserved.

1. Introduction with SMR [7].

Methane pyrolysis is the decomposition of methane into mo-
lecular hydrogen and solid carbon, CH4/Cþ2H2. The endothermic
reaction, DHo ¼ 74.8 kJ/mol and DGo ¼ 50.7 kJ/mol, in the gas phase
is thought to proceed from a methyl radical through a stepwise
dehydrogenation process with intermediates including ethane,
ethylene, and acetylene which eventually form oligomers then
solid carbon and hydrogen. Pyrolysis can produce hydrogen
without necessarily producing any CO2; however, recovering the
carbon co-product cost-effectively is challenging [1e3]. Methane
pyrolysis for the commercial production of hydrogen must compete
with steam methane reforming (SMR, CH4 þ 2H2O/4H2 þ CO2)
which stoichiometrically results in the production of carbon diox-
ide. In the absence of a carbon tax or other financial penalty for CO2
production, the solid carbon co-product from pyrolysis must be free
of contamination and have some commercial value in the growing
global carbon market [4e6] for pyrolysis to compete economically
* Corresponding author.
E-mail address: mcfar@ucsb.edu (E.W. McFarland).
Decades of research on pyrolysis has been done under a variety
of different reaction conditions, with different catalysts, and in
different types of reactors [8e13] to increase the reaction rate and
facilitate carbon removal. It is clear that carbon formation de-
activates solid catalysts (Ni, Fe, Co, Pt) [14e20]. Activity is recovered
by burning the carbon and this results in CO2 generation.
Pyrolysis of methane in a molten metal bubble column reactor
produces solid carbon in and around the rising gas bubble [4,21].
The main advantage of using molten metal bubble columns is that
separation of the produced carbon is possible in continuous oper-
ation as the low-density solid carbon floats on the surface of the
liquid. Previous studies of pyrolysis using molten metals have not
demonstrated sufficient carbon product purity for most commer-
cial applications and post-processing to clean the carbon could be
prohibitively expensive [5,22,23]. When a molten metal catalyst is
used, carbon contamination occurs from the liquid phase metal
interactions with the developing carbon as well as from metal va-
por depositing on all solid carbon surfaces. As reported by our
group [23], the purity of carbon recovered directly from the top of
Ni0.27Bi0.73 molten alloy reactors was only approximately 61 wt%.

https://doi.org/10.1016/j.carbon.2019.05.041
0008-6223/© 2019 Elsevier Ltd. All rights reserved.
182 N. Rahimi et al. / Carbon 151 (2019) 181e191
Such large amounts of metal loss are economically unacceptable
and the carbon product would be unacceptable in the market.
Several industrial processes and electrochemical systems make
use of the immiscibility of molten salts for separation applications
[24e31]. Molten salt/molten metal extractions have been widely
used in metallurgical purifications for more than a century
[29,30,32]. In extractive metallurgical processes a two-phase liquid
system consisting of a metal-rich phase and a less-dense slag phase
is produced. Morani [33] used a molten salt-molten metal extrac-
tion for removal of tritium from molten lithium into a molten
lithium salt. Reidwald et al. [29] showed a two-phase molten
metal-molten salt reaction system for pyrolysis of waste circuit
boards, dense metals were extracted into the metal phase at the
bottom of the reactor, and lighter fractions and carbon char were
recovered in the less dense salt layer of LiCl/KCl.
The use of gas bubbles for flotation of solids in molten metals
and molten salts is also widely practiced [27,34e36]. When rising
bubbles cross the liquid-liquid interface, they carry a surface layer
of the denser liquid into the upper phase [37]. Bubbling gasses
through the dense phase causes one liquid to be dispersed into
another immiscible liquid generating a large interfacial area which
is responsible for the high reaction rates in emulsions [38e40]. The
entrainment of metal droplets (e.g. iron) into the less dense slag
phase can be either desirable or detrimental [38e46]. Although the
transport of iron droplets by rising gas bubbles can enhance both
heat and mass transfer between the two immiscible liquids, the
dispersed iron droplets in the slag phase can result in loss of the
iron product. This entrainment occurs at first in the form of a metal
film and finally into droplets where the bubble becomes detached
from the metal-salt interface [27,28,47]. In systems with small
density difference such as water/organic liquids two-phase sys-
tems, there is a greater possibility that the dense phase can fully
disperse as droplets in the less dense liquid at high gas flow rates
[47].
Wettability of solid surfaces by molten salts plays an essential
role in the salt carbon separation process. Wettability is determined
directly through the contact angle at the three-phase boundary of
the liquid, solid and gas which can be related to the surface tension
of the molten salt and adhesion energy between the carbon and the
molten salt using the Young-Dupre equation [48]. A semi-empirical
model for the adhesion energy between pure alkali halides and
carbon was proposed by Baumli et al. [49]. It was found that the
adhesion energy increases with the square of the cation radius, and
the inverse of the anion radius of the salt. According to the pro-
posed equation, the adhesion energies of NaBr and KBr with
graphite are 61 and 113 mJ m2 which indicate the higher wetta-
bility of graphite surfaces by KBr than NaBr [49e51].
In this communication, results are presented from the produc-
tion and analysis of carbon from pyrolysis of methane in multi-
phase bubble column reactors containing a molten metal alloy
(Ni0.27Bi0.73 alloy) and molten bromide salts (KBr and NaBr). The
carbon types produced and the efficacy of the salt phase to extract
in situ residual metal contamination from the developing solid
carbon is analyzed. Specifically, this work addresses the following
questions: (1) What is the activity of the multiphase bubble column
for methane pyrolysis? (2) Is metal contamination of carbon pro-
duced by pyrolysis in catalytic molten Ni0.27Bi0.73 reduced by the
use of a two-phase bubble column with a low-density molten
bromide salt on top of the immiscible catalytic molten metal? (3) Is
the purity of the carbon product dependent on the specific cation in
the bromide salt (Na and K)? And, (4) by what mechanism(s) is the
metal removed from the carbon? The findings are discussed in
terms of the adhesion energies and wettability of the carbon-salt
interface.
2. Experimental Methods and Materials
2.1. Reactors and Gas Analysis
Methane pyrolysis was performed in bubble columns with inner
diameters of 22 mm and total lengths of 300, 430 and 1000 mm.
The reactors were quartz tubes which are stable at reaction tem-
peratures and facilitate direct observation of the size and velocity of
bubbles in the molten metal/salt systems. The reactor headspace
above the hot melt surface was 80 mm in length and accounted for
approximately 2.7 ± 0.5% of conversion at 1000  C. The gas was
introduced into the reactors through a quartz tube with an inner
diameter of 2 mm, and an outer diameter of 3 mm. The tube is
introduced in the reactor from above and reaches deep into the
metal layer; the depth reached by the tube can be varied. The
temperature in the middle of the reactor was measured using a
type K thermocouple. The molten metal catalyst used was 27 mol %
of Ni (99.8%) dissolved in molten Bi (99.99%) (Ni0.27Bi0.73) [23]. Pure
halide salts (NaBr, KBr, and KCl, ACS reagent, 99.0%) were used for
the experiments.
A gas chromatograph (GC, HP 5890 SERIES II) fitted with a
Thermal Conductivity Detector (TCD) was used to analyse the
product gases using an ultra-high pure (UHP) nitrogen carrier gas.
UHP CH4 and Argon gas cylinders feed into a control system
which allows for gas flow control through mass flow controllers
(MFC, full scale 50 ml min1). From the flow controllers, the gas
stream can be cut off or fed into the reactor or bypass streams.
Solid Ni and Bi were weighed and added to the reactor and the
rest of the reactor was filled with the salt resulting in a two-phase
molten NiBi alloy-salt after melting the metals and salts (KBr and
NaBr). In all the experiments, the reaction temperature was
maintained at 1000  C with a PID controller unless otherwise
stated. The inlet feed gas, a CH4/Ar mixture with the desired mole
ratio, was introduced through a bubbler at the bottom of the reactor
and controlled by calibrated flow rate controllers. The product gas
was analysed by a GC-TCD using nitrogen as a carrier gas. GC was
calibrated for hydrogen and methane and all the conversions were
measured versus methane consumption.
In the first set of experiments, a reactor with an inner diameter
of 22 mm and a total length of 300 mm was filled with 42 ml's of
NiBi and 42 ml's of the NaBr, KBr, and KCl salts, (NiBi/(NaBr/KBr/
KCl)/(110/110)). For further study of the effects of column height on
purity and morphology of the produced carbon, the amount of NiBi
alloy and salts were changed and the experiments were continued
using reactors with heated lengths of (1) 240.0 mm NiBi and
110.0 mm KBr (NiBi/KBr (240/110)), (2) 110.0 mm NiBi and
240.0 mm KBr (NiBi/KBr (110/240)), and (3) 110.0 mm NiBi and
240.0 mm NaBr (NiBi/NaBr(110/240)) columns. In the final experi-
ment, a reactor with inner diameter of 22 mm and a total length of
1000 mm was filled with 660 mm NiBi and 260 mm NaBr (NiBi/
KBr(660/260)). The CH4/Ar ratio of 7/3 was bubbled from the bot-
tom of the reactor for 10 h at 1000  C. After cooling the bubble
column, the carbon generated in different halide salts was studied.
2.1.1. Carbon Recovery and Cleaning
The mixture of the carbon and salt was collected from the re-
actors and washed with deionized water. The carbon produced in
the headspace was not processed. The collected carbon was dried in
an oven at 90  C. For further cleaning, the water-washed carbon
was heated up under vacuum up to 1000  C for 12 h. After cooling
the reactor, carbon was recovered for characterization. In another
set of experiments, the water-washed carbon was further purified
by refluxing at 70  C in 1 M HCl for 24 h. The final products dried at
90  C for 24 h for characterization.
 N. Rahimi et al. / Carbon 151 (2019) 181e191 183

2.1.2. Carbon Analysis

The morphology of the recovered carbon product was analyzed
using a high-resolution ThermoFisher Apreo C scanning electron
microscope (SEM) equipped with an energy dispersive X-ray
analyzer (EDX) for elemental analysis, and by high resolution
transmission electron microscopy (HRTEM)) using an FEI Titan FEG
TEM/STEM system. X-ray diffraction measurements were per-
formed using a Panalytical Empyrean powder diffractometer using
Cu Ka radiation. The metal and salt concentrations in the produced
carbon were also measured by X-ray Fluorescence (XRF) (Rigaku
ZSX Primus, WDXRF). Raman spectra of the carbon from a 633 nm
excitation were obtained using a Horiba Jobin Yvon LabRAM Aramis
spectrometer.

3. Results and Discussion

3.1. Bubble Column Performance

Fig. 1. Methane conversion vs. depth of the outlet tube in the melt, measured at
The methane conversion, in the case that methane was bubbled 1000  C: NiBi/NaBr (110/110) two-phase reactor. The inlet feed as 7 sccm methane and
at a depth of 300, 430, or 1000 mm ranged from approximately 9 to 3 sccm Ar.
38%, Table 1. The ID/IG ratio of different carbon samples are also
listed in Table 1. The D to G band intensity ratio is a measure of
defects present in graphitic carbon. When the ID/IG ratio decreases,
the degree of graphitization increases.
In the NiBi/NaBr(110/110) bubble column reactor with a total
length of 300 mm, the conversion was measured as the gas inlet
tube was inserted from the top to the bottom of the reactor (Fig. 1).
There was a significant conversion in the reactor headspace due to
the relatively long residence time (~3 min). The inlet tube flow rate
was 0.17 cm3 s1 (10 ml min1) and the bubble rise time in the salt
is approximately 0.5 s. The conversion in the 110 mm salt column is
approximately 2% with an estimated first order rate constant of
k ¼ 0.010 ± 0.005 s1. Fig. 1 shows the conversion to increase more
rapidly when the inlet tube was further immersed into the molten
metal 110 mm from the interface with the salt to approximately 8%.
The bubble rise time through 110 mm of the molten metal was
approximately 0.7 s. The apparent first order rate constant is esti-
mated from the data assuming a constant bubble rise velocity as,
k ¼ 0.10 ± 0.05 s1. The activity of the molten NiBi phase for
methane pyrolysis is significantly higher than the molten NaBr salt
Fig. 2. Methane conversion as a function of methane volume flow rate at different
phase. The errors in the rate constant estimates in the two phases
temperatures in the 1000 mm two-phase bubble column reactor, NiBi/NaBr (660/260).
are relatively large due to the inaccuracies in estimating the bubble The inlet feed was pure methane.
size and rise velocities in the two phases with different densities
and surface tensions and the breakup of the gas bubbles entering
the salt phase (see section 3.5). flow rates [52], the time required to form the bubble at the end of
Methane conversion increased when increasing temperature the tube increased as the flow rate decreased. Therefore, the
and decreased with increasing methane volumetric flow rate highest CH4 conversion at the lowest flow rate was mainly attrib-
(10e30 ml min1) in the 1000 mm NiBi/NaBr, two-phase, bubble uted to the reaction during the formation of the bubble, not to the
column, for several temperatures between 920 and 1000  C (Fig. 2). time it took the bubble to rise through the melt. The experiment
Although the bubble size and rise velocity are not a function of the was performed continuously for 24 h without clogging.

Table 1
Bubble path length, methane conversion and ID/IG ratio of collected carbon from metal/salt two-phase reactors. The methane conversion values shown include the conversion
that occurred in the 80 mm of reactor gas headspace, which is approximately 2.7 ± 0.5%.

Metal alloy/Salt Flow ratio (CH4/Ar) Total reactor height (mm) Metal phase height (mm) Salt phase height (mm) Methane conversion (%) ID/IG ratio

1 NiBi 7/3 430 350 none 27.0 ± 1.0 1.30 ± 0.04

2 NiBi/KBr 7/3 300 110 110 10.0 ± 0.5 1.45 ± 0.07
3 NiBi/NaBr 7/3 300 110 110 10.0 ± 0.5 1.34 ± 0.03
4 NiBi/KCl 7/3 300 110 110 10.0 ± 0.5 1.34 ± 0.03
5 NiBi/KBr 7/3 430 110 240 15.0 ± 0.5 1.35 ± 0.03
6 NiBi/KBr 7/3 430 240 110 21.0 ± 0.5 1.28 ± 0.03
7 NiBi/NaBr 7/3 430 110 240 15.0 ± 0.5 1.26 ± 0.01
8 NiBi/NaBr 10/0 1000 660 260 37.5 ± 0.5 1.16 ± 0.07
184 N. Rahimi et al. / Carbon 151 (2019) 181e191

3.2. Carbon from Methane Pyrolysis

Photographs of the cooled salt phases were obtained after

conversion of approximately 1.0 gms of methane in the NiBi/
NaBr(110/110) and NiBi/KBr(110/110) columns at 1000  C
(Figure 3(a) and 3(b)). In the NaBr salt phase, Fig. 3(a), there is a
clear demarcation of the solid carbon phase at the top of the NaBr
melt; in contrast, in the KBr salt phase the solid carbon remains
dispersed, Fig. 3(b). The molten NaBr has a relatively high density
(~2.0e2.2 g cm3) [53] and low adhesion energy, 61 mJ m2 [49]
with carbon. On the other hand, KBr has higher adhesion energy,
113 mJ m2 [49], with carbon and a lower density (~1.91 g cm3)
[53].
A photograph of the carbon accumulated on top of the salt phase
and in the reactor headspace is shown in Fig. 4. This was produced
by methane pyrolysis in the NiBi/NaBr(660/260) reactor, for 10 h, at
1000  C, with 20 ml min1 of methane. After producing approxi-
mately 2 gms of carbon, the reaction was stopped and the carbon
was analyzed.

3.3. Carbon Analysis

3.3.1. Carbon impurities by X-ray Fluorescence

The carbon produced by pyrolysis, recovered from different
reactor configurations, showed significant differences in contami-
nation by Ni, Bi metals and KBr salt. The semi-quantitative XRF
analysis of the samples recovered from NiBi(350) and NiBi/KBr(110/
240) bubble columns showed the ratio of the Ni and Bi metals, with
and without the salt phase layer, are as follows: Bi(NiBi/KBr)/
Bi(NiBi) ¼ 0.00 and Ni(NiBi/KBr)/Ni(NiBi)¼ 0.008 (Fig. S1). A sig-
nificant decrease in the Ni and Bi contaminations was observed
using two-phase reactors.
Table 2 summarizes the quantitative XRF elemental analysis of
the carbon samples obtained from NiBi/KBr(110/240) and NiBi/
KBr(240/110) reactors. The carbon was less contaminated by Ni and
Bi when produced in the NiBi/KBr(110/240) bubble column.
3.3.2. Carbon morphology and EDS spot analysis
SEM images of the microstructure of the unwashed carbon
collected from the top of the NiBi (350) single-phase molten metal
reactor are shown in Figures 5(a) to 5(d) at different magnifications.
Fig. 4. Carbon layers produced in the NiBi/NaBr(660/260) reactor after methane py-
rolysis at 1000  C with 20 ml min1 of methane. (A colour version of this figure can be
viewed online.)
In Fig. 5(a), spots A and B, show granular particulates with droplets
consistent with the presence of Bi particles in the carbon. The EDS
analysis on spots A and B is shown in Table S1.
Whereas carbon with various morphologies was present, sheet-
like structures were the predominant form observed in all the
carbon samples, as exemplified by the micrographs obtained from
the NiBi/KBr(110/240), NiBi/KBr(240/110) and NiBi/NaBr(110/240)
columns shown in Fig. 6.
The EDS data obtained during microscopy, together with the
XRF measurements, provide an overall picture of the elemental
composition of the impurities present in the solid carbon products,
which is summarized in Table 3 for the series of the experiments at
1000  C with a CH4/Ar ratio of 7/3. The lowest levels of impurities

Fig. 3. Photographs of the cooled salt phase containing the carbon produced after conversion of approximately 1.0 gms of methane in 42 ml's of molten Ni/Bi and 42 ml's of salt at
1000  C (a) NiBi/NaBr(110/110), (b) NiBi/KBr(110/110). (A colour version of this figure can be viewed online.)
 N. Rahimi et al. / Carbon 151 (2019) 181e191 185

Table 2
XRF analysis on carbon produced from methane pyrolysis in the metal/salt two-phase reactors.

Sample C(wt%) Ni(wt%) Bi(wt%) K(wt%) Br(wt%)

NiBi/KBr(110/240)-water washed 68.00 0.04 0.62 12.66 18.68

NiBi/KBr(110/240)-water washed-vacuum heated 82.83 0.05 0.00 6.94 10.18
NiBi/KBr(110/240)-water washed-acid washed 79.61 0.00 0.00 8.48 11.91
NiBi/KBr(240/110)-water washed 78.25 0.55 3.30 7.69 10.21
NiBi/KBr(240/110)-water washed-vacuum heated 96.00 0.57 0.00 1.21 2.22
NiBi/KBr(240/110)-water washed-acid washed 95.39 0.00 0.00 1.38 3.23

Fig. 5. SEM micrographs of carbon samples from NiBi(350) single-phase bubble column reactor. (a) The presence of metal particles in spots A and B, (b), (c) and (d) carbon flakes
recovered from NiBi single-phase reactor with different magnifications.

were observed in the NiBi/NaBr(110/240) sample after water
washing and vacuum heating. The vacuum heating process
improved the purity of the carbon recovered from the KBr and NaBr
salts by approximately 18% and 40%, respectively. According to the
results, the total amount of Ni and Bi impurities is almost the same
in the carbon from NiBi/NaBr(110/240) and NiBi/KBr(110/240) re-
actors, which indicates the importance of the salt height in the
cleaning process. Regarding the influence of different salts on car-
bon purity, it was found that carbon produced from NiBi/KBr(110/
240) had higher salt contamination than the carbon obtained from
NiBi/NaBr(110/240) reactor. This salt dependence of the carbon
purity can be explained by the fact that KBr has higher adhesion
energy towards carbon than NaBr [49]. Moreover, the lowest
amount of Ni impurities in the sample from NiBi/KBr(110/240)
reactor are a consequence of higher wettability of the carbon to-
wards KBr than NaBr (see section 3.5).
The XRD data from the carbon obtained in the NiBi(350), NiBi/
NaBr(110/240) and NiBi/KBr(110/240) melts, further show the ef-
ficiency of the salt cap in reducing metal impurities in the carbon
products (Fig. S2). Carbon from NiBi(350) reactor contains a sig-
nificant amount of crystalline Ni and Bi contamination which is
illustrated in Fig. S2(a). Moreover, in addition to the peaks arising
from carbon, NaBr and KBr peaks were detected in the XRD patterns
of the water-washed samples (Fig. S2 (b) and (c)).
When the height of the KBr salt column on top of the molten
metal increased from 110 mm to 240 mm, the metal impurities in
the carbon product were significantly reduced, Table 3. The longer
transit time in the salt column allows more time for NiBi metal film
to be washed off by the salt and returned to the metal bath. On the
other hand, the NiBi/KBr(240/110) column has less salt contami-
nation than the NiBi/KBr(110/240) reactor due to the shorter bubble
residence time in the salt. The ID/IG ratio (Table 1) of carbon
generated in the NiBi/KBr(240/110) column shows a more graphitic
structure which had significant metal contamination; it is possible
that metal vapor deposited on the carbon traps within the devel-
oping layers of the graphite carbon; such metal would have a
slower rate of evaporation under the vacuum heating at 1000  C.
Table 3 summarizes the EDS analysis of carbon from the series of
methane pyrolysis experiments in different systems. Data for NiBi/
KCl(110/110) is shown in Table S2 for comparison.
The XRD data shown in Fig. 7, of the carbon produced by py-
rolysis in the NiBi(350), NiBi/KBr(110/240) and NiBi/KBr(240/110)
reactors, was taken after water washing and drying. The diffraction
pattern of the carbon produced in the NiBi/KBr(240/110) shows
186 N. Rahimi et al. / Carbon 151 (2019) 181e191

Fig. 6. SEM micrographs of carbon samples from NiBi/KBr and NiBi/NaBr two-phase bubble column reactors. (a) and (b) NiBi/KBr(110/240), (c) and (d) NiBi/KBr(240/110), and (e)
and (f) NiBi/NaBr(110/240) bubble column reactors. (a), (c) and (e) Carbon microstructure containing both (b), (d) and (f) tubular, spherical and sheet-like carbon nano and
microstructures.

Table 3
SEM/EDS spot analysis on carbon produced from methane pyrolysis in the metal/salt two-phase reactors.

Sample C(wt%) Ni(wt%) Bi(wt%) Na(wt%) K(wt%) Br(wt%) Cl(wt%)

1 NiBi(350) 17.36 ± 0.01 12.98 ± 0.10 69.66 ± 0.10 N.A. N.A. N.A. N.A.
2 NiBi(350)-vacuum heated 51.82 ± 0.05 1.84 ± 0.01 46.34 ± 0.03 N.A. N.A. N.A. N.A.
3 NiBi(350)-acid washed 58.81 ± 0.06 4.09 ± 0.01 37.10 ± 0.01 N.A. N.A. N.A. N.A.
4 NiBi/KBr(110/110)-water washed-vacuum heated 85.63 ± 0.02 0.82 ± 0.01 1.10 ± 0.02 N.A. 3.73 ± 0.03 8.72 ± 0.02 N.A.
5 NiBi/KBr(240/110)-water washed 85.68 ± 0.02 0.22 ± 0.02 0.66 ± 0.01 N.A. 4.38 ± 0.01 9.06 ± 0.01 N.A.
6 NiBi/KBr(240/110)-water washed-vacuum heated 98.22 ± 0.01 0.23 ± 0.02 0.32 þ 0.01 N.A. 0.36 ± 0.01 0.87 ± 0.01 N.A.
7 NiBi/KBr(110/240)-water washed 74.19 ± 0.01 0.06 ± 0.01 0.42 ± 0.01 N.A. 8.07 ± 0.01 17.26 ± 0.01 N.A.
8 NiBi/KBr(110/240)-water washed-vacuum heated 88.47 ± 0.03 0.10 ± 0.01 0.0 N.A. 3.60 ± 0.01 7.83 ± 0.02 N.A.
9 NiBi/KBr(110/240)-water washed-acid washed 84.63 ± 0.02 0.0 0.0 N.A. 4.98 ± 0.02 10.39 ± 0.01 N.A.
10 NiBi/NaBr(110/240)-water washed 95.06 ± 0.02 0.18 ± 0.01 0.56 ± 0.01 1.06 ± 0.01 N.A. 3.14 ± 0.01 N.A.
11 NiBi/NaBr(110/240)-water washed-vacuum heated 97.40 ± 0.01 0.18 ± 0.01 0.0 0.59 ± 0.01 N.A. 1.83 ± 0.01 N.A.
12 NiBi/NaBr(110/240)-water washed-acid washed 97.34 ± 0.01 0.0 0.0 1.15 ± 0.01 N.A. 1.51 ± 0.01 N.A.

minor Ni and Bi peaks; no such peaks were observed from the
carbon produced in the NiBi/KBr(110/240) reactor. These XRD
measurements are consistent with the EDS ones, which showed
less metal contamination in carbon obtained from the NiBi/
KBr(110/240) bubble column, which had a smaller metal height and
higher salt height.
3.3.3. Raman spectroscopy
Raman spectra of the solid carbon collected from the top of the
NiBi single-phase and NiBi/KBr two-phase reactors are shown in
Fig. 8. It is known that D-band (1295-1300 cm1) shows the
structural defects in the graphitic sp2 network which confirms the
presence of amorphous carbon. G and Gˊ bands (1592 and
 N. Rahimi et al. / Carbon 151 (2019) 181e191
Fig. 7. X-ray diffraction patterns of carbon samples collected from (a) NiBi, (b) NiBi/
KBr(240/110), and (c) NiBi/KBr(110/240).
Fig. 8. Raman spectra of carbon samples collected from (a) NiBi, (b) NiBi/KBr(240/110),
and (c) NiBi/KBr(110/240).
2650 cm1) are signatures of existing the graphitic sp2 materials. In
addition, the relative intensity ratio of the D and G bands ID/IG
corresponds to the degree of the graphitization. ID/IG ratio of the
carbon from the NiBi(350) single-phase reactor, NiBi/KBr(240/110)
and NiBi/KBr(110/240) were 1.30 ± 0.04, 1.28 ± 0.03, and
1.35 ± 0.03, respectively. According to the measured ID/IG ratios, the
carbon recovered from NiBi/KBr(110/240) has the most amorphous
structure which is consistent with the fact that the degree of
graphitization is highly dependent on the residence time of the
bubble in the molten metal phase.
3.4. TEM analysis
HRTEM of the carbon produced in the NiBi single-phase reactor,
Fig. 9, shows the presence of flakes of graphitic carbon (arrows). On
the other hand, the carbon produced in the NiBi/KBr(240/110) two-
phase reactor appears to have uniformly distributed 20-50 nm
diameter spherical morphologies and a few aggregates 100-200 nm
in size, Fig. 10, consistent with structures observed in other systems
[54,55]. Reported by International Carbon Black Association typical
187
carbon black aggregates have approximate diameters in the range
of 85e500 nm. It was also shown that when the aggregation stops,
larger clusters known as agglomerates are produced with di-
ameters in the range of 1e100þ mm. The HRTEM images of the
carbon show perturbed graphitic layers e referred to as turbostratic
structures [56e58].
HRTEM images of the carbon recovered from the NiBi/KBr(110/
240) and NiBi/NaBr(110/240) two-phase reactors, Fig. 11, show a
segmented, bamboo-like, carbon nanotubes in both samples. As
carbon blacks are formed from aggregates of graphitic plates, they
are also thought to be a potential precursor for the formation of
other carbon nanostructures including carbon nanotubes and
bamboo-like carbon nanotubes [59,60]. Therefore, it can be inferred
that structural and microstructural changes could occur in two-
phase reactors (comparing to the NiBi single-phase reactor) when
the bubble rises through the salt phase to the liquid surface [61].
Faceted layer planes and few closed-shell structures could be
obtained when CB was treated at high temperature however car-
bon undergoes structural transformation when it comes in contact
with metal catalysts at high temperature. The degree of trans-
formation and morphology of resulting nanostructure depends on
many factors which this project takes into consideration and
studied.
3.5. Proposed carbon extraction mechanism
The carbon formation pathway is shown schematically for a
molten metal bubble column, Fig. 12(a), and in a two-phase molten
metal bubble column capped with a salt layer, Fig. 12(b). Without
the salt layer, the metal film around the bubble remains until the
bubble gets to the surface and collapses. Thus, metal droplets will
have contaminated all carbon surfaces. In the two-phase bubble
column reactors, when a gas bubble detaches from the metal-salt
interface, the metal surface film ruptures and small metal drop-
lets are generated which sink back to the metal phase due to their
high density. This process is further enhanced by the rapid bubble
volume increase at the interface due to the surface tension gradient
between molten metals and molten salts which causes bubble
breakup and controls the bubble size distribution in the salt phase
[62]. The carbon produced and contaminated in the catalytic metal
region within the bubble can evaporate off metal and the vapor will
condense on the salt wall and return to the liquid phase. In addi-
tion, carbon can disperse into the salt phase and migrate to the
surface.
A potential pathway for the removal of metal contamination
from the carbon in the two-phase system proceeds as follows: the
gas bubble containing the methane reactant, gas-phase products,
and condensed phase carbon rises to the metal-salt interface, the
liquid NiBi, and condensed phase carbon can be stripped off at the
bubble surface and dispersed into the salt. The dense molten alloy
sinks back to the metal phase while the low-density carbon would
rise to the salt surface (NiBi/salt density ratio  4.6 for NaBr, KBr
and KCl at 1000  C).
Due to the different densities of KBr and NaBr at 1000  C
(~1.91 g cm3 and ~2.14 g cm3, respectively), carbon will float on
the NaBr surface while dispersing within the KBr melt. It is known
that when the liquid does not wet solid particles, they can be
transported to the surface by the gas through flotation [63]. Thus,
besides the importance of the salt density difference with solid
carbon, the adhesion energy between alkali halide salts and carbon
plays an important role in separating carbon from the molten salt
through wetting. The wettability of the carbon surface by NaBr, KBr,
and KCl molten alkali halide salts has been reported as 61, 113 and
122 mJ m2, respectively [49]. Therefore, the NaBr is the least likely
to wet the carbon allowing it to facilitate flotation to the surface,
188 N. Rahimi et al. / Carbon 151 (2019) 181e191

Fig. 9. HRTEM images of (a) and (b) carbon samples produced by methane pyrolysis in the NiBi(350) single-phase bubble column reactor. The arrows show graphitic carbon layers.

Fig. 10. HRTEM images of the carbon produced by methane pyrolysis in the NiBi/KBr(240/110) two-phase reactor. (a), (b), (c) Carbon black aggregates with different magnifications,
and (d) Carbon black single particle.

whereas the KBr and KCl salts will wet favoring dispersion within
the melt. Accordingly, the clear demarcation between the salt and
carbon was observed in the sample obtained from NiBi/NaBr
reactor while the salt was completely intermixed with the carbon
in the NiBi/KBr and NiBi/KCl two-phase reactors even after cooling.
4. Conclusions
Conversion of methane to molecular hydrogen and solid carbon
is demonstrated in bubble column reactors containing molten
Ni0.27Bi0.73 alloy and bromide salts that remains stable for over 20 h.
The addition of the molten salt as a second phase over a catalytic
molten metal produced a solid carbon product with less than 0.1 wt
% of metal contaminants. The concentration of contaminants in the
solid carbon product decreases with increasing height of the salt
phase layer. Removal of the carbon within the multiphase reactor
likely occurs through several mechanisms. As the rising bubble
enters the molten salt phase a thin film of molten metal exists at
the gas liquid interface which ruptures allowing liquid metal
droplets to return to the metal phase. Further remaining metal on
the carbon continues to be removed as its vapor condenses at the
liquid salt interface and is dispersed back into the liquid. Further-
more, the affinity of the bromide salt to wet the carbon allows
further dislodgement of metal from the carbon as the solid carbon
 N. Rahimi et al. / Carbon 151 (2019) 181e191 189

Fig. 11. HRTEM images of the carbon produced by methane pyrolysis in the NiBi/KBr and NiBi/NaBr two-phase reactors. (a)-(b) Bamboo-like carbon nanostructure recovered from
NiBi/NaBr(110/240) reactor with different magnifications, and (c)-(d) Bamboo-like carbon nanostructure recovered from NiBi/KBr(110/240) reactor with different magnifications.
The arrows show graphitic carbon layers.

Fig. 12. Schematic diagrams of bubbles passing through molten NiBi and NiBi/NaBr bubble columns. (a) Bottom-flow CH4 without a salt cap, and (b) bottom-flow CH4 with the NaBr
salt cap.

in and around the bubble surface enters the salt phase. The specific
interaction properties between the salt and the carbon are impor-
tant in determining the final carbon purity. KBr has greater
wettability of carbon during the formation and aggregation of the
solid carbon particulates. Moreover, KBr and carbon have similar
densities and maintain association as the carbon aggregates within
the salt bulk. NaBr wets solid carbon less and has a greater density
which favors greater carbon flotation to the salt-gas interface and
less salt incorporation within the carbon particulates.
HRTEM analysis of the carbons revealed structural differences
between carbon generated in the NiBi single-phase and NiBi/salt
two-phase reactors. The carbons produced in the metal/salt two-
phase reactors contained carbon black aggregates and carbon
nanotubes structures while in the NiBi reactor flakes of graphitic
carbon were only detected. It can be inferred that structural and
microstructural changes could occur in two-phase when the bubble
rises through the salt phase to the liquid surface.
Acknowledgements
This work was primarily supported by the Energy & Biosciences
Institute through the EBI-Shell program. Partial support for the
190 N. Rahimi et al. / Carbon 151 (2019) 181e191
work was also provided by the U.S. Department of Energy, Office of
Science Basic Energy Sciences Grant number DE-FG03-89ER14048.
We made use of The MRL Shared Experimental Facilities are sup-
ported by the MRSEC Program of the NSF under Award No. DMR
1720256; a member of the NSF-funded Materials Research Facilities
Network (www.mrfn.org). All data are reported in the main paper
and supplement. The authors are grateful for the indispensable
technical assistance of Mr. Richard Bock of the UCSB Chemistry
Department who prepared all the quartz reactor components and
their modifications.
Appendix A. Supplementary data
Supplementary data to this article can be found online at
https://doi.org/10.1016/j.carbon.2019.05.041.
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