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Cold plasma catalysis as a novel approach for valorisation of untreated waste

Published on 04 May 2018. Downloaded by UNIVERSITY OF ADELAIDE on 04/05/2018 12:05:17.
glycerol
Green Chemistry Accepted Manuscript

Received 00th Jonathan Harris1, Anh N. Phan1† and Kui Zhang1
January 20xx,
Accepted 00th
January 20xx Glycerol, a by-product from biodiesel production, is currently considered as waste
DOI: for disposal. Several attempts have been made to convert this wasted resource
10.1039/x0xx00000
x for high-value added products via either chemical or biological processes.
www.rsc.org/ However, complex steps are required to remove impurities and the selectivity of
desired product(s) is low. In this paper, cold plasma catalysis was for the first time
proposed to valorise untreated waste glycerol, greatly reducing the negative
environmental impacts of waste glycerol. The attractiveness of this approach is
that the process can be easily tuned toward specific products with high yields
with a very short reaction time (around 16 seconds) at near ambient conditions.
By altering the carrier gas, cold plasma power and packing material/catalyst, up
to 99 % of untreated waste glycerol was converted into either gas products
consisting of hydrogen (55 mol% or 7.02 wt%), hydrocarbons (C1-C4: 9-10 wt%),
CO (19 wt%) and CO2 (16 wt%), or high value liquid products such as acetol (up to
54 wt%). The findings of this work could open up new opportunities for
intensification of green chemical processes and biorefining of waste materials by
reducing pre-treatment steps, solvent requirements and amount of waste
generation.
Introduction
Depleting fossil fuels reserves, environmental concerns and a highly industrialised society make
sustainable clean fuels highly desirable. Bio-fuels (biodiesel from vegetable oils and bioethanol from
sugar cane, sugar beets etc.) has been increased yearly to meet individual national targets, i.e 10 %
renewable energy target for transport sector by 2020 set by the European Union, EU. 1 With the
increase in biodiesel production, large amounts of by-product glycerol have been produced,
approximately 2.5-3 million tonnes of by-product glycerol are generated annually worldwide.2
The by-product glycerol which varies in purity (ranging from 30-85 wt% purity depending on the
This journal is © The Royal Society of Chemistry 20xx J. Name., 2013, 00, 1-3 | 1
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feedstock and biodiesel production conditions 3-5) is currently considered as waste to be discharged. 4, 6, 7
The remainder of the waste glycerol is comprised of impurities such as methanol, alkaline hydroxide
catalyst, free fatty acids (FFA), soap and water. Therefore, complex purification and separation
processing are necessary for pharmaceutical and cosmetic applications. On the other hand, the large
surplus of by-product glycerol led to market saturation, causing more than 50 % reductions in the value
of pure glycerol globally,8 which makes the purification of by-product waste glycerol uneconomical,
particularly for small and medium scaled plants. 7, 9
Energy recovery via combustion of waste glycerol is an option but it can release toxic compounds10,

leading to extra costs for gas cleaning processes. A number of works have been carried out using waste
glycerol from biodiesel production as feedstock to produce value-added products such as acetol, 3-
hydroxypropanoic acid, glycerol carbonate or hydrocarbons 11 via either biological 12, 13 or chemical
processes.14-17 However, these methods have major issues with reactor fouling, making them largely
unviable. Using untreated waste glycerol in biological processes inhibits activities of microorganisms due
to the presence of alkaline hydroxides 18 and soap, making biological methods ineffective.15
Converting pure glycerol to acrolein19, acetol and propylene glycol20 was examined at a temperature
range of 240-305 oC. Despite many methods for producing gas phase products from waste glycerol being
known,11-16,19 very little work exists for direct conversion of untreated waste glycerol to liquid products.
Therefore, if untreated waste glycerol can be utilised for high-valued liquid products or hydrogen at mild
conditions with high yields, it could not only improve the economics of such processes and biodiesel
production but also contribute to waste management strategies.
Plasma, the 4th state of matter, contains electrically excited species such as energetic electrons, radicals,
ions and excited molecules. Based on the relative temperatures of the electrons, ions and neutrals,
plasmas are classified into "thermal plasma " and "cold plasma". In a thermal plasma, the gas bulk
temperature (i.e. 10,000-100,000 K) is approximately equal to the temperature of the electrons, which is
not chemically selective but suitable for hazardous waste treatment21and radioactive waste treatment.22
In contrast, in cold plasma, the bulk temperature is close to ambient but the average electron
temperature is in a range of 10,000 - 100,000 K, equivalent to an electron energy of 1-10 eV. Therefore,
cold plasma is suitable for catalytic chemical reactions. The cold plasma allows the process to be
optimised by changing the reactor design, carrier gas, packing material, applied voltage and frequency.
Cold plasma is also highly versatile, and can tolerate a very wide range of feedstocks without significant
fouling occurring. The ability to tune the process allows the desired product(s) to be selected more
easily than other processing methods. Cold plasma has also been successfully used for dry reforming of
methane 23-25 and synthesizing nanomaterials26-28. Certain types of cold plasma, such as dielectric barrier
discharge (DBD) 29, are resistant to fouling because its the electrodes are isolated from the reaction
mixture30, 31 and catalysts can be easily incorporated in a discharge gap. DBD reactors have been studied
at industrial scales for ozone generation32. Using cold plasma to remove oxygen from bio-oil was tested
previously.29, 33 Zhu et al. carried out the conversion of pure glycerol using cold plasma to hydrogen and
carbon monoxide.34 Additionally, since cold plasma has distinctive thermodynamic behaviour35 and its
properties are altered by operating conditions and reactor configuration 36, 37, the process can be easily
2 | J. Name., 2012, 00, 1-3 This journal is © The Royal Society of Chemistry 20xx

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tuned to select for any given desired product(s). In the presence of a catalyst, the product distribution
can be controlled to a degree that thermal reactors cannot achieve. Potentially, one component could
be decomposed without affecting the other components in the reactor via the control of the plasma
properties, which could simplify the downstream processing. Therefore, the aim of this work is to
investigate the potential of cold plasma and the synergetic effect of cold plasma and packing
materials/catalysts in valorising waste glycerol obtained from the biodiesel production process. In order
to tune the products, a full understanding of the effect of operating conditions on the process such as
carrier gas and plasma power in is crucial.

Materials and Methods
Materials
The waste glycerol was kindly donated by Harvest Energy at Seal Sands, Teesside, UK. A Thermoscientific
X series ICP-OES was used to determine the concentration of metal in the sample. The sample contained
more than 20 elements, of which potassium, sodium and calcium contributed a large percentage,
comprised approximately 4.06 wt%, 0.21 wt%, and 0.03 wt% respectively while the others were at ppm
levels. The presence of these elements would potentially either foul catalysts in contact with the waste
glycerol38 or act as catalysts for decomposition. The water content of the waste glycerol was 9.45±0.05
wt % determined by Karl-Fischer titration.
The CHN analysis of the waste glycerol sample was performed using a Carlo Erba 1108 Elemental
Analyser according to the standard BS ISO 29541. The sample had an empirical formula of . .
.
The higher H/C and O/C ratios in waste glycerol than in pure glycerol were due to high water content
and the presence of other oxygenated compounds as a product of biodiesel production. Compositions of
the waste were glycerol (58.96 wt%), fatty acids (FFA, 33.38 wt%), glycerides (2.13 wt%) and some
metal salts as shown in Table 1.
Table 1: Waste glycerol composition
wt% , dry
basis
Glycerol 58.96
FFA 33.38
Glycerides 2.13
Methanol 1.18
Potassium 4.06
Sodium 0.21
Calcium 0.03
Others 0.05
Hydrogen, nitrogen and helium used in this work were high purity gases (>99.999% purity, BOC Ltd.).
Barium titanate (BaTiO3) beads (99% purity obtained from Alfa Aesar) had a particle size range of 0.5-1
mm. Nickel on supporting alumina (Ni/Al2O3) was synthesized from high surface area alumina pellets

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(180 m2/g surface area purchased from Alfa Aesar) and nickel nitrate hexahydrate (99.9% purity
obtained from Sigma Aldrich) via a wet impregnation method proposed by Bartholomew and Farrauto.39
Approximately 100 g of Al2O3 pellets was added to 100 ml of 1M solution of nickel nitrate hexahydrate.
The mixture was stirred vigorously at 60 rpm for 1 hour to remove air bubbles. The pellets were
extracted and dried in a furnace set at 110 °C for 24 hours. The dried sample was calcinated at 550 °C in
air for 5 hours and then hydrogenated at a hydrogen flow rate of 20 ml/min and 550 °C for 24 hours to
reduce nickel oxide to nickel. The sample was reduced to 0.5-1 mm in size.
Experimental Method

A schematic setup is shown in Figure 1. The plasma reactor was a coaxial type dielectric barrier
discharge reactor with a discharge gap of 1 mm and a plasma zone of length 12 cm, providing a total
volume of 11.17 cm3. Plasma power supplied to the reactor was varied up to 50 W, at a frequency of 22
kHz. The outer electrode was galvanised steel wire mesh, while the inner electrode was 1 mm thick
aluminium foil inside a quartz glass cover. The liquid waste glycerol flow rate was controlled using a
syringe pump (errors: ±0.01 ml/min) while the gas flow rate was controlled using a Bronkhorst mass
flow controller (errors: ± 0.03 ml/min).
Prior to each experiment, the reactor was continuously purged by a selected gas (hydrogen, helium or
nitrogen) for 30 minutes to ensure the system was air-free (confirmed by GC analysis). As soon as the
system was air-free, the gas flow rate was adjusted to a desired flow rate. A known flow rate of liquid
waste glycerol was continuously injected and mixed with the selected carrier gas at a T-mixer (Figure 1)
to obtain consistent slug flow behaviour into the plasma zone. The volumetric ratio of gas to liquid was
fixed at 40:1 (v/v) to ensure that liquid was constantly covering the inner electrode, while preventing
the reactor from flooding with liquid. Each experiment was repeated at least three times for
reproducible purposes.
The outlet reactor was fitted to two condensers cooled at 60 oC and 0 oC to collect liquid products. The
gas was collected and analysed online every 15 minutes for 100 minutes. The liquid was collected at the
end of the run for off-line analysis and for determining its yield, and the gas yield determined by relative
flow rates in and out of the reactor.

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Figure 1: Experimental setup for cold plasma assisted waste glycerol decomposition
Analysis
Non-condensable gas outflowing directly from the quenching system was analysed online using a 3
channel Varian 450- Gas Chromatogram (GC). The GC was equipped with 2 ovens, 5 columns, 1 Thermal
conductivity detector for permanent gases and 2 flame ionisation detectors for hydrocarbons and
alcohols. One oven housed 3 columns (Hayesep T 0.5 m x 15 m x1/8" ultimetal, Hayesep Q 0.5 m x 1/8 "
ultimetal and Molsieve 13 m x 1.5 m x 1/8" ultimetal) for permanent gas separation. The second oven
housed a CP-SIL 5CB FS X.25 column for hydrocarbon analysis and a CP-WAX 52CB FS 25 m X 0.32 mm

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(1.2 μm) column for alcohols. The liquid yield was determined by comparing the rate of liquid input to
the reactor and the volume of liquid collected at the outlet.
Quantitative analysis of the liquids was performed using a GC-MS equipped with an elite-5 HP capillary
column using a heating profile: at 50 °C held for 4 minutes, increased to 180 °C at 15 °C/min, then 7
°C/min to 230 °C, then 10 °C/min to 340 °C and held for 25 minutes. The identified compounds were
quantified using a HP6890 GC with an elite-5 HP capillary column with helium as carrier gas. Glycerol
and glycerides content was determined according to BS EN 14105-2011.

FTIR analysis was also used to identify functional groups in the liquid fraction, and to confirm the results
of GC analysis. FFA content was determined by titration of 0.05 ml of waste glycerol diluted to 2 ml in
chloroform containing a pH indicator solution with 0.05 M NaOH in chloroform. Water content in the
liquid fraction was determined using Karl-Fischer titration, in an automatic C30 Compact Karl Fischer
Coulometer (errors: ± 0.03 wt%)
The conversion of waste glycerol (X) is defined as:
ℎ − " "
(%) =
ℎ
× 100
Where unreacted waste glycerol means the mass of glycerol, FFA, and glycerides remaining in the
output stream. Conversion is therefore the total conversion of glycerol, glycerides and FFA to other
species.
The process yields are defined as:
'
& ' (%) = × 100
ℎ
Results and discussion

Effect of operating conditions in the presence of cold plasma on waste glycerol conversion
Table 2 shows that increasing plasma power increased the conversion of waste glycerol. This is due to
high energy level electrons contributing to the collisions with gas molecules, creating different energy
levels of excited species37. However, the degree of conversion and product yields strongly depends on
the carrier gas. The degree of decomposition was in the order: He> H2~N2 for FFA but N2>>He>H2 for
glycerol. Therefore, if acetol is the desired product, the process should be operated in N2 environment
whereas H2 and He are the preferred choice of carrier gas if hydrocarbon gases are desired.
Purification of liquid products such as acetol and other products (formic acid and propenal) from
unreacted feedstock would be straightforward due to the large differences in boiling points of the
compounds40. Other methods such as solvent extraction41 and membranes42 can be also applied.

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It is known43 that in N2 plasma environment, excited nitrogen atoms and molecules (N* (4S, 2D, 2P) and
N2*(A 3Σu+) were generated. These excited states were generally quenched rapidly at atmospheric
pressure and are unlikely to contribute significantly to the reaction, with the possible exception of the
triplet meta-stable state of nitrogen, N2 *(A 3Σu+) and excited nitrogen atoms, N* (2D), which could
initiate the decomposition of glycerol. The wide range of excited states offers a wide range of available
energies, permitting a greater variety of reactions.44 Helium, with its very high energy excited state (>19
eV45), the highest first excited state possible of any element, produces some extremely energetic species
that can allow reactions that are otherwise impossible. Hydrogen has a low energy excited state (around

3.7 eV46, 47) and is easily converted into hydrogen radicals, allowing rapid hydrogenation.
Table 2 shows that up to 91 % waste glycerol was converted in nitrogen plasma at 50 W and the yield of
acetol was high at all tested powers. The glycerol content in waste glycerol was mainly converted into
acetol at 50 W in nitrogen plasma. A 22 % reduction in acetol yield (decreased from 44.91 wt% to 34.92
wt%) when increasing power from 10 W to 30 W could be due to the instability of this compound20,
which decomposed further to form formic acid (5.67 wt% at 30 W), methane and CO. At 50 W, no formic
acid was observed but a significant amount of CO2 was formed. This can be explained due to formic acid
decomposing further to CO2 at high powers. It can be also concluded that the rate of acetol formation is
faster than its decomposition at high plasma powers. It is also observed that in a nitrogen environment,
hydrogen production increased with increasing power. This could be explained due to the coupling
effect of small hydrocarbons i.e. C1-C2 into C3-C4.
A significant amount of CO and hydrocarbons (mainly C2) were formed in helium plasma (Table 2).
Acetol yield decreased with plasma power from 25 wt% at 10 W to 6 wt% at 50 W. The lower yield of
acetol than that in the nitrogen environment could be because the high energy level of excited helium
cleaves strong chemical bonds. Acetol decomposition generates CO, resulting in at least 145 % more CO
produced than the other carrier gases under any conditions. However, a low conversion of glycerol
molecules was observed because only a small fraction of excited helium is formed due to the
distribution of electron energy35.
In contrast, in a hydrogen environment, the conversion was mainly from the decomposition of FFA in
raw waste glycerol to form mainly hydrocarbons and oxygenated compounds of which more than 60 %
of the gaseous products were C1-C2. This can be explained by the low energy level of excited hydrogen
and abundant hydrogen radicals in the system. A high amount yield of formic acid obtained at 50 W (21
wt%) could be the results of stabilising COOH radicals derived from FFA decomposition. No CO2 and only
a small amount of CO (4.7 wt%) observed at 50 W was due to the decomposition of acetol. 4,48
Table 2: Yields and properties of products obtained from liquid waste glycerol decomposition in the
presence of cold plasma at atmospheric temperature and pressure without catalysts under different
types of carrier gas with a residence time of 16 seconds
Power, W 10 20 30 50
Carrier gas H2 N2 He N2 H2 N2 He H2 N2 He

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Conversion, % 28.91 65.91 54.62 65.12 29.77 67.91 50.37 35.04 91.11 52.74
±2.3 ±4.6 ±3.2 ±4.5 ±2.7 ±4.4 ±4.1 ±3.1 ±4.4 ±4.7
Total gas yield, wt% 22.9 21.1 30.0 24.4 26.3 25.5 38.2 12.8 38.2 46.7
±1.0 ±0.81 ±0.97 ±0.93 ±1.31 ±0.91 ±1.71 ±0.62 ±1.01 ±2.29
CO2 - - - 1.87 - 3.46 - - 10.79 -
H2 - 0.91 - 0.96 - 1.01 - - 2.72 0.46
CH4 9.33 7.14 1.60 5.19 8.17 3.25 2.75 1.63 4.44 1.37
CO - 2.14 15.01 6.81 - 8.56 17.32 4.70 9.90 23.51
C2 13.57 10.91 12.54 9.37 7.32 7.82 16.50 2.80 6.36 19.28
C3 - - 0.52 0.21 5.73 0.88 1.17 1.86 2.40 1.25

C4 0.03
- - 0.33 5.05 0.56 0.46 1.84 1.58 0.83

Liquid products yield, 6.01 43.91 24.63 42.38 3.5 40.59 12.16 22.21 52.2 6.3
wt% ±1.39 ±3.84 ±2.19 ±3.52 ±1.46 ±3.61 ±2.44 ±2.55 ±3.45 ±2.42
Formic acid - - - 1.17 3.13 5.67 - 21.48 - -
Propenal 0.59 - - - - - - 0.73 - -
Acetol 5.42 44.91 24.63 41.21 0.37 34.92 12.16 - 52.20 6.30
Unreacted feedstock, wt% Figure 2
Glycerol 62.01 14.00 42.82 22.86 62.70 23.19 48.68
shows59.70 2.00 46.80
FFA 7.59 7.54 1.18 6.89 5.71 5.46 0.05 4.96 3.81 0.02
Glycerides 1.49 3.55 1.39 3.43 1.82 3.44 that OH
0.90 0.29 3.08 0.44
groups
in the liquid phase were mostly converted to ketones instead of to water as reflected by the trend of
water content presented in Figure 3. This can be seen from the significant changes in the O-H, C-H and
C=O peaks at 3300cm-1, 2900 cm-1 and 1700 cm-1 respectively. A slight increase in the C-H peak (Figure
2a) could be a result of the hydrogenation. The hydrogenation of glycerol would require the
replacement of a hydroxyl radical with hydrogen or hydrogenation of C=C bonds formed from removal
of alcohol groups to other oxygenated groups. All the peaks in the range 700-1500 cm-1 decreased after
plasma treatment, which is an indicator of shorter chain hydrocarbons in the products. This is supported
by the formation of hydrocarbons in the gas phase. The same behaviour was observed in nitrogen and
helium plasma as shown in Figures 2b & 2c.
1.4
C-OH
(a)
1.2
10 W
30 W
1.0 O-H 50 W
Raw Waste glycerol
0.8
Intensity
C-H COOH
0.6
C=O
0.4 C=C
0.2
0.0
4000 3000 2000 1000
-1
Wavelength (cm )

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1.4
(b) C-OH
1.2
10 W
30 W
1.0 O-H 50 W
Raw Waste glycerol
0.8
Intensity
C-H COOH
0.6

C=O
0.4 C=C
0.2
0.0
4000 3000 2000 1000
-1
Wavelength (cm )
1.4
10 W C-OH
1.2 30 W
(c) 50 W
Raw Waste glycerol
1.0
O-H
0.8
Intensity
COOH
0.6 C-H
0.4 C=C
C=O
0.2
0.0
4000 3000 2000 1000
-1
Wavelength (cm )
Figure 2: FTIR spectra of the liquid phase before (raw waste glycerol) and after (a) hydrogen; (b)
nitrogen and (c) helium purged plasma

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12
H2 plasma treated
10
N2 plasma treated
He plasma treated
Water Yield (wt%)
8

6
0
Raw 10 20 30 40 50
Plasma Power (W)
Figure 3: Water content of waste glycerol feedstock and liquid products obtained at various treatment
conditions without catalysts at atmospheric temperature and pressure with a 16 second residence time
To date, direct conversion of waste glycerol to high value added liquid products has not been reported.
However, conversion of waste glycerol into gases at high temperatures (650-800oC) has been
studied.49,50 Dehydration of pure glycerol under high temperature water and/or high pressure of CO2 via
catalytic reactive distillation was reported20, 51 with the yield of acetol varying from 26-60 wt%
depending on catalysts over >1 hour reaction time. By using cold plasma in this study, without a catalyst
and at ambient conditions, 52 wt% acetol from waste glycerol was obtained at around 16 second
residence time alongside 14.78 wt% hydrocarbon gas (C1-C4), 2.72 wt hydrogen and 9.90 wt% CO. Based
on the trend of acetol and gases (hydrocarbons and CO) with cold plasma power, it can be concluded
that the acetol formation pathway in cold plasma is similar to that obtained in thermal processing,
where glycerol dehydrates secondary OH to form acetol. Propenal is the product of the dehydration of
the primary OH group.52 Propenal could decompose to ethene and formate radicals19, 53, of which the
latter can dehydrogenate further to carbon monoxide.54, 55 In this study, propenal was not detected
except in the presence of hydrogen, which is due to the instability of aldehydes in cold plasma56. It was
also noted that the water content decreased in the presence of plasma, which suggests that OH radicals
are formed from the water and maintain an equilibrium.
Formic acid and hydrocarbons were the products of FFA decomposition.57 The formic acid is likely then
dehydrogenated to CO2, particularly in the absence of hydrogen radicals. However, from the
experimental data, no correlation between FFA content and CO2 formation suggests that CO2 formation
in nitrogen is dominated by another reaction. The OH radicals formed would react with carbon
monoxide, and in turn dehydrogenate to carbon dioxide. 57-60 57-60 This only occurs in nitrogen, which

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suggests that the energy required for this pathway is closest to the energy of nitrogen radicals. Formic
acid is generated under certain conditions at yields of up to 21 wt%. The proposed mechanism for cold
plasma assisted glycerol decomposition is shown in Figure 4 below.

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Figure 4: Proposed mechanism of cold plasma assisted waste glycerol decomposition
Effect of packing material and catalyst in the presence of cold plasma
Packing materials (e.g. BaTiO3) had a slight effect on the conversion but enhanced the decomposition of
acetol into gaseous products such as hydrocarbons and CO (Table 3). However, the degree of
decomposition was lower for Al2O3 than BaTiO3. This is because the packing materials and their
properties alter the electric field, consequently electron energy by varying the discharge gap (d) and/or
the gas density n (proportional to gas pressure).61-62 When introducing packing beads, the discharge gap
in the DBD reactor is the gap between the beads, which is much smaller than the gap without packing
materials (1.5 mm), thereby enhancing local electric fields. This occurs due to refraction of the electric
field as shown in Figure 5, making the local electric field non-uniform and stronger than the external
sources. Furthermore, the strength of electric field near the contact points between the beads can be
significantly higher than that in the void by a factor of 10–250 depending on the shape, porosity, and
permittivity of the beads.47 An increase in dielectric constant/permittivity of materials can result in a
further increase in electric field, particularly near the contacting points.62

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(a) (b)
Figure 5: Schematic discharge gap and discharge line (a) without packing and (b) with packing material

Figure 5: Schematic discharge gap and discharge lines (a) without packing and (b) with packing material
When the catalyst Ni/Al2O3 was embedded in the plasma zone, up to 99 % waste glycerol was converted
into gaseous products. Ni/Al2O3 is a common hydrodeoxygenation catalyst39 and therefore was used to
examine the ability of integrated hydrogen production from plasma and deoxygenation of the liquid at
near ambient conditions. When a catalyst is introduced to the plasma, chemical reactions in the plasma
occur in gas phase reactions and heterogeneous reactions on the catalyst surface.35 Therefore, a catalyst
may significantly influence the plasma chemistry. The interactions between DBD plasma and catalysts
are complex as the catalyst with its dielectric properties could modify the electric field and the electric
field may affect catalyst effectiveness, i.e. altering the surface properties of the catalyst to allow
operation at much lower temperatures and more effectively. These plasma-catalyst interactions have
been studied for CO2 decomposition.63,35 The conversion was slightly reduced when increasing power
to 50W due to the formation of plasma arcs.
Table 3: Effect of packing materials and catalyst on conversion and product distribution under a nitrogen
environment at 6 second residence time
Packing No BaTiO3 Ni/Al2O3 Al2O3

material packing
Plasma 50 10 30 50 10 30 50 10 30 50
power, W
Conversion, 56.98 26.85± 45.29±5.9 60.97±6.2 44.82±4.3 99.13±0.5 83.96±4.1 7.99±2.8 21.43±4.5 40.86±4.7
% ±2.03 4.7
Total gas 27.6 18.92 44.79 60.71 38.55 99.13 83.94 4.26 14.91 34.12
yield, wt% ±0.97 ±1.82 ±4.71 ±5.50 ±2.03 ±0.42 ±4.05 ±0.82 ±1.72 ±2.16
CO2 8.96 6.49 8.23 13.80 23.81 44.98 11.11 - 4.05 9.99
H2 3.35 0.24 1.50 2.45 1.22 7.02 4.94 0.06 0.41 1.31
CH4 3.66 - 0.44 0.87 0.38 3.46 2.77 0.99 1.18 2.27
CO 7.63 0.96 7.45 12.21 2.99 34.81 53.50 0.87 7.74 15.89
C2 2.46 4.43 11.44 14.72 8.07 5.36 6.31 1.50 1.00 3.83
C3 0.93 2.93 4.17 6.74 2.08 1.88 2.39 0.39 0.37 0.52
C4 0.61 3.87 6.03 7.59 - 1.61 2.30 0.45 0.17 0.31
C5 - - 5.52 2.32 - - 0.61 - - -
Liquid 29.29 7.55 0.50 0.26 7.08 0.20 0.02 3.73 6.52 6.74
products, ±1.67 ±2.88 ±1.19 ±0.70 ±2.28 ±0.08 ±0.05 ±1.96 ±2.81 ±2.53
wt%
Propenal - 0.23 0.05 0.04 0.81 0.01 0.02 0.02 0.05 0.13

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Acetol 29.29 7.32 0.45 0.22 6.27 0.19 - 3.71 6.47 6.61
Unreacted feedstock, wt%
Glycerol 34.52 64.06 47.60 35.19 52.81 0.81 15.24 58.26 46.22 31.47
Fatty acids 5.17 8.21 6.37 3.47 2.01 0.04 0.60 31.54 30.34 25.89
Glycerides 3.42 0.88 0.75 0.37 0.17 0.01 0.08 2.21 2.01 1.78
Figure 6 shows that the water content in the liquid was around 50 % lower than that in the feedstock
and remained almost constant at 4 wt% with increasing power in the case of BaTiO3 and Al2O3. This is
because the decomposition of H2O into OH radicals and generation of water via dehydration pathways

were in equilibrium. With Ni/Al2O3, the water content remained similar to that in the raw material up to
25 W and then sharply decreased to zero at 30 W. This was due to the consumption of OH radicals by
hydrocarbons and ketones, followed by decomposition to form carbon oxides. An increase in the water
content at powers above 30 W was due to plasma arcing (heterogeneous environment).
12
10 BaTiO3
Ni/Al2O3
Al2O3
Water content (wt%)
0
Raw 5 10 20 25 28 30 40 50
Plasma Power (W)
Figure 6: Water content versus plasma power for packing materials and catalyst Ni/Al2O3 at 4 second
residence time
It was found that after 1 hour operating time, the conversion of waste glycerol in the presence of
Ni/Al2O3 significantly decreased, by approximately 50 %. This is due to fouling, which is in agreement
with previous studies.16 The same behaviour was observed for Al2O3 but not for BaTiO3. The spent and
fresh Ni/Al2O3 catalyst was then analysed using BET, SEM with EDX and XRD. For the fresh catalyst, SEM-
EDX analysis (Figure 7a) showed large particles of diameter of 0.5-1 mm with mainly Ni, Al and O
elements with a ratio of O/Al comparable to that reported in literature.64, 65 In contrast, SEM images of
the spent Ni/Al2O3 catalyst show rounded surfaces with very few pores and bubble like nodes
are visible on the material’s surface (Figure 7b). From XRD analysis (Figure 7d), the spent catalyst
had an additional peak at 21°, indicating a partial coverage of solid carbon on the surface66. A
very high degree of fouling which occurs within the 1 hour running time is carbon based, but

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contains significant potassium content (up to 15.5 wt%). The nodules form at the areas where
carbon accumulates. The resulting fouling on these points retains OH groups so more waste
glycerol adheres to it, building up into a nodule. The pores are largely clogged with waste
glycerol and some deposits could be formed internally. The sample was also regenerated
successfully and analysed, which showed no significant differences from the initial catalyst
(Figure 7c) as evidenced by the similar conversion and product distribution obtained over the
regenerated catalyst. When the spent catalyst was regenerated at 550oC in nitrogen, the
additional peak at 21o disappeared. It was found67, 68 that spent catalysts can be regenerated by

cold plasma at lower temperatures with shorter residence times than by conventional
regeneration methods. However, this is not in the scope of this study.
(a)
(b)
(c) 6000
5000
(d)
4000
Fouled
Intensity
3000
Fresh
2000
Regenerated
1000
0
0 20 40 60 80
Angle (2ϑ)
Figure 7: (a,b,c) SEM image of at x6500 magnification of (a) fresh, (b) spent and (c) regenerated catalysts
and (d) XRD of fresh, spent and regenerated Ni/Al2O3.

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DOI: 10.1039/C8GC01163J
Conclusions
In this study, the influence of plasma power, carrier gas, packing material and catalyst on waste glycerol
conversion was studied. The carrier gas was found to be a significant factor in the conversion and
product distribution. Hydrogen carrier gas favours the formation of hydrocarbon products and propenal,
and preferentially decomposes FFA molecules. Nitrogen carrier gas produces the highest yield of acetol
due to preferentially decomposing glycerol. Helium carrier gas favours carbon monoxide and
preferentially decomposes glycerides. The effect of reaction time was more pronounced than packing
materials. Approximately 99 % waste glycerol was converted into gaseous products at 30 W, of which 55

mol% (7.02 wt%) was hydrogen when using Ni/Al2O3. Ni/Al2O3 catalyst deactivated quickly within 1 hour
operating time due to the deposition of carbons and impurities from the waste glycerol feedstock i.e.
potassium. However, the catalyst can be regenerated easily in 550 °C oxygen free nitrogen. This study
reveals opportunities to convert waste into high added value products over a short period of time at
near ambient conditions with the products easily tuned according to demand.
Conflicts of interest
There are no conflicts to declare.
Acknowledgements
The authors wish to thank Newcastle University for funding this work through the EPSRC Doctoral
training allowance, grant number OSR/0530/DT14/HARR.
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Cold plasma catalysis as a novel approach for valorisation of untreated waste

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particularly for small and medium scaled plants. 7, 9

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Table 1: Waste glycerol composition

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and glycerides content was determined according to BS EN 14105-2011.

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The conversion of waste glycerol (X) is defined as:

The process yields are defined as:

Results and discussion

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C3 - - 0.52 0.21 5.73 0.88 1.17 1.86 2.40 1.25

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Plasma Power (W)

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Effect of packing material and catalyst in the presence of cold plasma

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Packing No BaTiO3 Ni/Al2O3 Al2O3

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Plasma Power (W)

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1. U.S-National-Biodiesel-Board, Biodiesel production, (http://biodiesel.org/what-is-biodiesel/biodiesel-basics), (accessed

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