Methods of production 0f Under Water Plasma

BY

Ejaz Nazir

M.Sc. PHYSICS

2016-ag-3352

SUPERVISOR

Mrs. Ramiza

REPORT FOR THE DEGREE OF

MASTER OF SCIENCE

IN

PHYSICS

DEPARTMENT OF PHYSICS

UNIVERSITY OF AGRICULTURE, FAISALABAD

1
2
 TO,

The Controller of Examinations,

University of Agriculture,

Faisalabad.

We the supervisory committee, Certify that the contents and form of Report
Submitted by Ejaz Nazir 2016-AG-3352 have been found satisfactory and
recommend that it be processed for evaluation, by the External Examiner(s) for the
award of degree.

Supervisor,

----------------------------------

Mrs. Ramiza
Lecturer,
Department of Physics

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 ACKNOWLEDGEMENT

All praise belong to Almighty Allah, enables me to complete this thesis. It is one of
infinite blessing of Allah that bestowed me with the potential and ability to complete the present
research program in time and make a material contribution towards the deep ocean of knowledge
already existing. I also offer my humble praise to the Holy Prophet Hazrat Muhammad
(PBUH), who is forever a torch of guidance and knowledge for humanity as a whole.

I feel great honor to express my deep sense of gratitude & appreciation to my

venerable supervisor, Mrs. Ramiza Associate professor, Department of Physics, University of
Agriculture, Faisalabad, under whose skillful guidance, encouragement, valuable suggestions
and kind supervision, this research work was planned executed & completed.

I also feel greatest pleasure in expressing my humble feelings of obligation and gratitude
to Dr. Abdul Ghafaar, Chairman, Department of Physics, university of Agriculture Faisalabad
for his valuable suggestion and sympathetic attitude. Words are lacking to express my humble
obligation to my parents, whose hands always rise in pray for my success and because of whole
moral support. As my entire to this stage is the result of their efforts, prayers and inspiring
sentiments.

I am highly grateful to my all teachers for their cooperation and patience. I am also
thankful to my family members for their, help and moral support.

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 Table of Contents…

Chapter 1 Introduction.......................................................................................................7

Cooling Water Management............................................................................................ 7

Water Sterilization............................................................................................................ 9

Previous Studies on the Plasma Water Treatment.............................................10

Process of Conventional Electrical Breakdown in Water..................................11

Chapter 2 Underwater Plasma Sources..................................................................14

Direct Discharges in Liquid..............................................................................14

Bubble Discharges in Liquid.............................................................................15

Chapter 3 Literature Review.................................................................................18

Chapter 4 Materials and methodology...................................................................25

Main chemical reactions...................................................................................26

Evaluation of conversion performance..............................................................27

Thermodynamic equilibrium calculations.........................................................28

Chapter 5 Results and discussion..........................................................................29

Glycerol conversion..........................................................................................29

Wood conversion..............................................................................................32

Comparison of the conversion process..............................................................35

Conclusions...........................................................................................................38

List of References.................................................................................................39

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 ABSTRACT

Plasma plays an important role in a wide variety of industrial applications,

including material processing, semiconductor manufacturing, light sources, propulsion
and many more. In recent years, there were increasing interests in the plasma discharges
in liquids because of its potential applications for various biological, environmental, and
medical technologies. For example, electric breakdown was developed as a non-chemical
method for bio-fouling removal and contaminant abatement in water, with a potential for
extension into a wide range of other water treatment applications. Comparing with other
conventional water treatment technologies, plasma methods effectively combine the
contributions of UV radiation, active chemicals, and high electric fields which leads to
higher treatment efficiency. However, the fundamental knowledge of the electric
breakdown in water had not kept pace with these increasing interests, mostly due to the
complexity of the phenomenon related to the plasma breakdown process. In most cases,
the electric breakdown of liquids is initiated by the application of high electric field on
the electrode, followed by rapid propagation and branching of plasma channels. The first
part of the report tried to answer the question whether it is possible to ionize the liquid
without cracking and bubble formation. Fast optical diagnostic platform was constructed
with 500 ps time-resolution. It was demonstrated for the first time that the possibility of
formation of non-equilibrium plasma in the liquid phase without bubble formation under
nanosecond and sub nanosecond high voltage excitation. The dynamics of excitation and
quenching of non-equilibrium plasma in liquid water were investigated and it was
observed that under some circumstances the plasma in liquid water possesses certain
similarities as gas phase discharge.

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Chapter 1

INTRODUCTION

Water is used as a cooling medium in large centralized air-conditioning

systems as well as in thermoelectric power plants. In both cases, the cooling water plays an
essential role in removing heat from condensers. Since the evaporation of pure water is the basic
means to remove heat from the condensers, the concentration of mineral ions in circulating
cooling water increases with time, resulting in hard water within a week even if soft water is
used as makeup water. Hence, a part of the circulating water is periodically or continuously
discharged in order to maintain the proper concentration of the mineral ions in circulating
cooling water in the form of blow down (Feeley et al., 2008).

Thermoelectric power plants produced about half of nation’s electricity. According to the
US Geological Survey’s (USGS) water use survey data thermoelectric generation accounted for
39% (136 billion gallons per day [BGD]) of all fresh water withdrawals in the nation in 2000,
second only to irrigation. Furthermore, the average daily national freshwater consumption for
thermoelectric power generation is predicted to increase from the current 4 BGD for the
production of approximately 720 GW electricity to 8 BGD for 840 GW in 2030.

In the cooling water management, it is important to distinguish between water withdrawal

and water consumption. Water withdrawal represents the total water take from the source, while
water consumption represents the amount of water withdrawal that is not returned to the source.
Freshwater consumption for the year 1995 (the most recent year for which these data are
available) is presented. Freshwater consumption for thermoelectric uses appears low (only 3%)
when compared with other use categories (irrigation was responsible for 81% of water
consumed). However, even at 3% consumption, thermoelectric power plants consumed more
than 4 BGD.

One of the critical issues in the cooling water management is the condenser tube fouling
by mineral ions such as calcium and magnesium. Since calcium carbonate CaCO 3 problem is
most common in cooling water, one can use the word “calcium scale” to refer all scales caused
by mineral ions. In order to prevent or minimize the condenser tube fouling, the COC

7
(Cycloolefin Copolymer) in wet recirculation cooling systems is often kept at 3.5. Since
increasing the cycles of concentration can reduce the amount of makeup water, the water
consumption can be reduced with the increased COC. For example, if one can increase the COC
to 8, the freshwater consumption can be reduced by approximately 25%, meaning that the
makeup water can be reduced by 2.5 million gallons a day in a 1000-MW thermoelectric power
plant (Zhang et al., 2006).

Since the amounts of mineral ions in circulating cooling water primarily depend on the
COC, the condenser tube fouling also depends on the COC. Hence, the issue in the cooling
water management is to increase the COC without the condenser fouling problem. The present
review deals with an innovative water treatment technology utilizing plasma discharges in water,
with which one can increase the COC without the fouling problem in condenser tubes. The key
issue is how to precipitate and remove mineral ions such as calcium and magnesium from
circulating cooling water so that the calcium carbonate scales can be prevented at the condenser
tubes and at the same time the COC can be increased.

The availability of clean water is an issue that has paralleled the continual increase in
water consumption due to both global population growth and the economic development in a
number of developing countries. From a global perspective, an estimated 1.1 billion people are
unable to acquire clean safe water. As estimated by the Environmental Protection Agency (EPA),
nearly 35% of all deaths in developing countries are directly related to contaminated water. The
need for improved water treatment exists on both political and humanitarian dimensions.
Contaminated water can be attributed to a number of factors, including chemical fouling,
inadequate treatment, deficient or failing water treatment, and poor distribution system. An
additional cause of contamination is the presence of untreated bacteria and viruses within the
water. Even in the United States, the increased presence of Escherichia coli (E. coli), along with
various other bacteria has been a cause for concern (Sakiyama et al., 2009).

In an effort to inactivate bacteria, there are several commercially available methods such
as chemical treatments, ultraviolet radiation and ozone injection technologies. The experimental
success and commercialization of these water treatment methods are not, however, without
deficiencies. With regard to human consumption, chemical treatments such as chlorination could
render potable water toxic. Although both ultraviolet radiation and ozone injection have been

8
proven to be practical methods for the decontamination of water, the effectiveness of such
methods largely depends upon adherence to regimented maintenance schedules. It is because of
these deficiencies that the importance of research and development of new and improved water
treatment methods continues to grow.

In recent years, there is an increasing interest in the study of pulsed electric breakdown in
water and other liquids as it finds more applications in both industry and academic researches. A
large number of papers and conference contributions were published during the last few years.
High-voltage electrical discharges in water have been shown to be able to induce various
reactions including the degradation of organic compounds the destruction of bacteria and viruses
the oxidation of inorganic ions and the synthesis of nanomaterials and polymers. The reactions
are usually thought to be initiated by various reactive species, UV radiation, shockwaves, high
electric field or intense heat produced by pulsed electric discharge. The concentration of the
reactive species and the intensity of the physical effects largely depend on the discharge type and
solution properties (Vankov A. and Palanker D. 2007).

Locke published a comprehensive review on the application of strong electric fields in

water and organic liquids with 410 references in 2006. They explained in detail the types of
discharges used for water treatment, physics of the discharge and chemical reactions involved in
the discharge in water. More recently, Bruggeman and Leys published another review paper on
non-thermal plasma in contact with water. They discussed three different types of plasmas: direct
liquid discharges, discharges in gas phase with a liquid electrode, and discharges in bubbles in
liquids. A different excitation method for each type was discussed individually. In addition,
plasma characteristics of the different types of plasma in liquids were discussed. Currently
several research groups around the world actively study plasma discharges for water treatment,
which will be briefly discussed next.

Schoenbach and his colleagues at Old Dominion University have studied the electrical
breakdown in water with submillimeter gaps between pin and plane electrodes by using optical
and electrical diagnostics with a temporal resolution on the order of one nanosecond. By using a
Mach–Zehnder interferometer, the electric field distribution in the pre breakdown phase was
determined by means of the Kerr effect, which indicates a change in the refractive index of a
material. Values of electric fields in excess of computed electric fields, which reached over 4

9
MV/cm for applied electrical pulses of 20 ns duration, were recorded at the tip of the pin
electrode. The results of this research have found bioelectric applications in the construction of
compact pulse power generators.

Graves and his colleagues at the University of California, Berkeley presented a unique
method to inactivate microorganisms in 0.9% NaCl solution (i.e., normal saline solution) by
means of micro plasmas. They employed E. coli bacteria to investigate the disinfection
efficiency of the device. The device consisted of a thin titanium wire covered by a glass tube for
insulation except for the tip of the wire and ground electrode. Microbubbles could be formed at
both electrodes from the application of an asymmetric high-frequency, high voltage. . Repetitive
light emission was observed in the vicinity of the powered electrode. More than 99.5% of E. coli
was deactivated in 180 s.

Sato and his colleagues at Gunma University, Japan studied the environmental and
biotechnological applications of high-voltage pulsed discharges in water. A pulsed discharge was
formed in water by applying a high-voltage pulse in point-to-plane electrode systems. They
found that bubbling through a hollow needle electrode made it possible to raise the energy
efficiency in the decomposition of organic materials by reducing the initial voltage of the
discharge. Oxygen gas bubbling was found to be effective for the decomposition because of the
forming of active species originating from oxygen gas (Sato et al., 2006).

Sunka and other researchers from the Institute of Plasma Physics, Academy of Sciences
of the Czech Republic developed a pulsed corona discharge generator in water using porous
ceramic-coated rod electrodes. They studied the properties of the ceramic layer and its
interaction with the electrolyte, and reported that surface chemistry at the electrolyte/ceramic
surface interface was an important factor in generating electrical discharges in water using
porous ceramic-coated electrodes. Initiation of the discharge in water using these types of
electrodes depended on the surface charge of the ceramic layer in addition to the permittivity and
porosity of the ceramic layer. The surface charge could be determined by the polarity of applied
voltage, and pH and the chemical composition of aqueous solution. By applying bipolar high
voltage pulses to eliminate possible buildup of an electrical charge on the ceramic surface, a
large-volume plasma could be produced in water in the range of kilowatts.

10
 Recently, Yang and his colleagues from Drexel Plasma Institute, Drexel University
reported the formation of liquid-phase non-equilibrium plasma in water. Since plasmas were
only considered to exist through the ionization of gases, people had believed that plasmas in
liquids must have been generated inside gas-phase bubbles produced through intense local
heating or via cavitation and could be sustained within those bubbles. For the generation of a
non-equilibrium plasma in liquids, a pulsed power system was often used with 32 – 112 kV pulse
amplitude, 0.5 – 12 ns pulse duration, 150 ps rise time. The measurements were performed with
a 4Picos ICCD camera with a minimum gate time of 200 ps. It was found that discharge in liquid
water formed in a picosecond time scale, and the propagation velocity of the streamers was about
5000 km/s. The reduced electric field E/n0 at the tip of the streamer was about 200 Td. Both the
propagation velocity and the reduced electric field in the test were similar to the streamer
propagation in gas phase, indicating that the plasma could be formed in liquid phase without
phase change. The details of the experiment will be discussed later.

Although a large number of studies were conducted on electric discharges in gases,

studies on the electric breakdown in liquids have been limited by the high density of liquids and
a short mean free path of electrons, therefore requiring a very high electric field E/n0. The
critical breakdown condition for gas can be described by the Paschen curve, from which one can
calculate the breakdown voltage. A value of 30 kV/cm is a well-accepted breakdown voltage of
air at 1 atm. When one attempts to produce direct plasma discharge in water, a much higher
breakdown voltage on the order of 30 MV/cm is needed based on the Paschen curve due to the
density difference between air and water. A large number of experimental data on the breakdown
voltage in water showed, however, that the breakdown voltage in water was of the same
magnitude as for gases. In other words, the breakdown of liquids can be performed not at the
extremely high electric fields required by the Paschen curve but at those that only slightly exceed
the breakdown electric fields in atmospheric-pressure molecular gases. This interesting and
practically important effect can be explained by taking into account the fast formation of gas
channels in the body of water under the influence of an applied high voltage. When formed, the
gas channels give the space necessary for the gas breakdown inside water, explaining why the
voltage required for the breakdown in water is of the same magnitude as that in gases.

11
 To generate electrical discharges in water, usually one needs to have a pulsed high
voltage power supply. Water is a polar liquid with a relative permittivity of εr =80. The electrical
conductivity of water ranges from about 1 µS/cm for distilled water to several thousand µS/cm
for cooling water, depending on the amount of dissolved ions in water. Given that a specific
water is exposed to an electric pulse with a duration of Δt, when Δt>>εr ε0/σ, where ε0 is
vacuum permittivity and σ is the conductivity of water, the aqueous solution can be considered
as a resistive medium. For such a long electric pulse, the electrolysis of water takes place with
the production of hydrogen and oxygen. For the case of a much shorter pulse duration, i.e. when
Δt<<εr ε0/σ, water behaves as a dielectric medium and a high applied voltage will lead to the
breakdown of the solution.

High electric field strength can usually be achieved by using needle electrodes with sharp
tips, from which electric discharges in water usually start. If the discharge does not reach the
second electrode, it is called a partial discharge (also called pulsed corona discharge, in analogy
with the discharges in gases), and branches of such a discharge are called streamers. However,
the nature of the discharges in liquids and the mechanism of streamer formation are much less
understood, and maybe completely different from those for discharges in gases. If a streamer
reaches the opposite electrode, it makes a conductive channel between the two electrodes.
Furthermore, if the current through the discharge is very high (above 1 kA), it is usually called
an arc discharge. While an arc discharge is usually continuous, the transient phase of the arc
discharge is referred to as a pulsed spark discharge.

The characteristics of pulsed corona and pulsed arc are summarized in Table 1. In the
partial discharge the current is transferred by slow ions, producing corona-like non-thermal
discharges. In case of water with a high electrical conductivity, a large discharge current flows,
resulting in a shortening of the streamer length due to the faster compensation of the space
charge electric fields on the head of streamers. Subsequently, a higher power density, i.e., a
higher plasma density, in the channel can be obtained, resulting in a higher plasma temperature, a
higher UV radiation, and the generation of acoustic waves.

In the arc or spark discharges, the current is transferred by electrons. The high current
heats a small volume of plasma in the gap between two electrodes, generating quasi-thermal
plasma, where the temperatures of electrons and heavy particles are almost equal. When a high-

12
voltage, high-current discharge takes place between two submerged electrodes, a large part of the
energy is consumed in the formation of a thermal plasma channel. This channel emits UV
radiation, and its expansion against the surrounding water generates intense shockwaves. The
shockwave can directly interact with the microorganisms in water. Of note is that the pressure
waves can scatter microorganism colonies within the liquid, thus increasing their exposure to
inactivation factors. For the corona discharge in water, the shockwaves are weak or moderate,
whereas for the pulsed arc or spark the shockwaves are generally very strong. When the plasma
discharge is initiated between two electrodes, the medium between the two electrodes is ionized
creating a plasma channel. The plasma discharge generates ultraviolet radiation and converts
surrounding water molecules into active radical species due to the high energy level produced by
the discharge. The microorganisms could be effectively inactivated, while the organic
contaminants could be oxidized through contact with active radicals. The chemical kinetics of
these reactions remains an area of significant research. Various active species can be considered
as the byproducts of plasma discharge in water. The production of these species by plasma
discharge is affected by a number of parameters such as applied voltage, rise time, pulse
duration, total energy, polarity, the electric conductivity of water, etc. Among the active species,
hydroxyl radical, atomic oxygen, ozone and hydrogen peroxide are the most important ones for
the sterilization and removal of unwanted organic compounds in water. Table 2 summarizes the
oxidation potentials of various active species produced by plasma in water, which ranges from
1.78 V (hydrogen peroxide) to 2.8 V (hydroxyl radical). Note that fluorine has the highest
oxidation potential of 3.03 V, whereas chlorine, which is one of the most commonly used
chemicals for water decontamination, has an oxidation potential of only 1.36 V.

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Chapter 2
Underwater Plasma Sources

Direct Discharges in Liquid

Various electrode geometries have been studied for the generation of plasma discharges
in liquid. Figure 5 shows some of the typical electrode configurations. Note that only the cases
where both the high voltage electrode and ground electrode are placed in liquid are shown here.
Among them, the point-to-plane geometry has been the most commonly used configuration
(shown in Fig. 5a). Also a point-to-plane geometry with multiple points was used to generate a
large volume corona discharge in water (Fig. 5b). For pulsed arc discharges, a point-to-point
electrode geometry was often used (Joshi et al., 2009).

As mentioned in the previous section, one of the concerns in the use of a sharp needle as
the HV electrode is the tip erosion due to the intense local heating at the tip. To overcome the
limitation of the needle-plate configuration, ‘‘pinhole’’ electrodes (also called a diaphragm
discharge, as shown in Fig. 5d) with large surface areas were developed, where the high voltage
and ground electrodes are separated by a dielectric sheet with a small hole. When high voltage is
applied on the electrodes, an intense electric field could be formed around the pinhole.
Subsequently, a pre discharge current could be concentrated in the small hole, leading to strong
thermal effects, resulting in the formation of bubbles. Pulsed corona discharge occurs inside the
bubbles at the pinhole because of the high electric field. The length of the streamers generated is
decided by the parameters such as water conductivity, the size of the pinhole, flow velocity
through the pinhole, and voltage polarity. Similar to the corona discharge in the point-to-plane
geometry, a pulsed arc discharge could be formed once the streamer bridges the two electrodes.
Figure 6 shows (a) pulsed corona and (b) arc discharges through a pinhole produced at Drexel
Plasma Institute.

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 Fig. 5. Schematics of electrode geometries used for plasma discharges in liquid:
(a) single point-to-plane:(b) multiple point-to-plane;(c) point-to-point; (d) pinhole; (e)
wire-to-cylinder; (f) disk electrode; (g) composite with electrode with porous ceramic
layer.

15
 Bubble Discharges in Liquid

In engineering applications of plasma discharges in liquids, high voltage, high power

discharges are often needed for the generation of breakdown in liquids as well as for desired
processing. For example, high electrical current and/or high liquid temperature can sterilize
water. In this case, the high energy supplied by a power source is first used to evaporate the
liquid adjacent to the HV electrode, generating gas bubbles that are subsequently ionized by
large electric fields caused by the high voltage. Liquid temperatures in such applications are
usually high, at least locally near the breakdown locations, due to the excess power dissipated in
the liquid. However, in some circumstances high temperature is not desired. For such
applications, a non-thermal plasma system that can generate gas-phase plasmas in contact with
liquids is often used. Since the gas-phase plasma can only interact with the liquid through the
gas-liquid interface, a maximization of the interface area is usually desired, which can be
achieved by using bubble plasmas, i.e. plasmas generated in small bubbles suspended in liquid.
Note that the ratio of the area of gas liquid interface to the total gas volume is inversely
proportional to the radius of the gas bubbles. Many different configurations have been used as
shown in Figs. 10a-10e.

Similar to direct discharges in water, the most commonly used configuration is the point-
to-plane configuration, where the point electrode was made of a small diameter hollow tube to
inject gas into water. Different types of gas were used depending on applications. For example,
oxygen gas was often used to promote the formation of oxygen radicals.

Alternatively, gas was bubbled between two metal electrodes (Fig. 10b). The discharge
occurred between the electrodes by applying the HV voltage, producing OH radical that was
detected by a spectroscopic technique.

Another interesting discharge in liquid was to use a gas channel, inside which two metal
electrodes were placed to generate plasma discharge (Fig. 10c). The gas is continuously supplied
through the hollow tube, flowing around the electrodes from both sides and exiting from the
open ends at the middle of the reactor (see Fig. 10c). The gases coming from the top and bottom
merge into one where two point electrodes were closely positioned, forming a stable gas channel

16
between the two metal electrodes. Subsequently, the generated discharge was an arc discharge
which was cooled and stabilized by the surrounding water (Schoenbach et al., 2007).

Aoki and his coworker studied RF-excited discharges in argon bubbles ina dielectric
covered metal rod and wire reactor (Fig. 10d). First, bubbles were formed in front of the slot
antenna (see black area in the figure) by microwave heating of water where water in an
evacuated vessel at a vapor pressure of 5 kPa was evaporated by a slight increase in the
temperature above the boiling point (room temperature). In the second step, microwave
breakdown took place inside bubbles filled with water vapor. In the third step, the bubbles
containing the plasma moved up due to the upward force by buoyancy. After that, new water
filled the vacant space in front of the slot antenna. These steps successively repeated forming a
large number of bubble plasmas. Microwave-excited plasma in water with or without externally
introduced bubbles was studied by Ishijama (Fig. 10e) and Nomura.

17
 Fig. 10. Schematics of electrode geometries for bubble discharge: (a) point-to-
plane; (b) parallel plate (c) gas channel with liquid walls; (d) RF bubble discharge (e)
microwave bubble discharge

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 Chapter 3

REVIEW OF LITERATURE

Tatiana et al., (2008) explained Mercury was a toxic element that could be found in
different chemical forms in the environment. It could be present in crude oil and contaminate the
water employed in the oil extraction and production. Sample treatment required for most
spectrometric techniques could lead to errors in the Hg determination, mainly by volatilization.
Vapor generation was the most recommended technique for sample introduction, but was too
time consuming. In this work, electro thermal vaporization was the chosen alternative for sample
introduction in inductively coupled plasma mass spectrometry to allow the accurate
determination of Hg in production water. Samples were analyzed by analyst addition in one
sample with low Hg content. In order to avoid Hg loss, low temperatures were employed in the
ETV program, pyrolysis at 200 °C and vaporization at 1000 °C, and gold was used as modifier.
Limit of detection of 0.12 μgL−1 and limit of quantification of 0.41 μgL−1 were obtained.
Accuracy was checked using recovery test, by adding a urine certified sample to a production
water sample and an average recovery of 106% was obtained. Among the 10 samples analyzed,
one presented Hg concentration over the limit for effluents, established by Brazilian legislation.
The proposed method presented better accuracy when compared to the analysis by ICP-MS with
direct introduction by means of a nebulizer specific for saline samples.

Volenik et al., (2009) explained an experimental plasma-chemical reactor equipped with

a novel hybrid gas–water stabilized torch was available at IPP Prague for the innovative and
environmentally friendly plasma treatment of waste streams with a view to their sustainable
energetic and chemical valorization and to a reduction of the emission of greenhouse gases.
Gasification/pyrolysis of biomass was experimentally studied using crushed wood as a model
substance. The experimental results demonstrate homogeneous heating of the reactor volume and
proper mixing of plasma with treated material in spite of the low plasma mass flow rate and
constricted plasma jet. The conditions within the reactor ensure complete destruction of the
tested substance. The economic viability, environmental performance and safety of
biofuels/hydrogen produced from syngas resulting from the plasma-thermochemical gasification

19
of a very broad range of second generation biomass feedstock will be investigated. The
performance of several types of plasma torches and of possible combinations of torches will be
compared. The final biofuels will be tested in the existing Internal Combustion Engine (ICE) test
stands.

Kim et al., (2010) extremely hot thermal plasma was used for the gasification of biomass
(spruce sawdust, wood pellets) and waste (waste plastics, pyrolysis oil). The plasma was
produced by a plasma torch with DC electric arc using unique hybrid stabilization. The torch
input power of 100–110 kW and the mass flow rate of the gasified materials of tens kg/h was set
up during experiments. Produced synthetic gas featured very high content of hydrogen and
carbon monoxide (together approximately 90%) that was in a good agreement with theory. High
quality of the produced gas was given by extreme parameters of used plasma – composition, very
high temperature and low mass flow rate.

Krcma et al., (2010) the objectives of the present study were to test a new plasma-based
method for bicarbonate removal in water produced from hydraulic fracturing for shale gas and to
verify bicarbonate removal as a mechanism for mineral fouling prevention. The study employed
dual hypotheses: (1) gliding arc plasma could reduce bicarbonate concentration of produced
water to negligible levels, and (2) water without bicarbonate content was unable to cause mineral
fouling in the form of calcium carbonate scale even in the presence of extremely high
concentrations of calcium ions as was often found in produced water. The plasma treatment of
produced water reduced the concentration of bicarbonate ions from a range of 684–778 ppm to
zero. Subsequently, heat transfer fouling tests were conducted with water samples, where the
concentration of bicarbonate ions varied from 0 to 500 ppm with a fixed concentration of
calcium ions of 5000 ppm. The weight of mineral scale that accumulated on a heating element
over time was determined. The present test results showed that no fouling was formed over 30 h
on the heating element in the water without bicarbonate ions. This proof-of-concept study
demonstrated that plasma treatment is capable of reducing the concentration of bicarbonate ions
in produced water to a level where CaCO 3 fouling could be prevented on a heat transfer surface.
The plasma gliding arc may represent a new non-chemical fouling prevention method for the
treatment of produced water.

20
 Arena et al., (2012) in this study, an experimental plasma-chemical reactor
equipped with an arc discharge water steam plasma torch was used for biomass conversion to
hydrogen-rich synthesis fuels. Glycerol and crushed wood were used as biomass sources. The
effects of different conversion parameters including the water steam flow rate, treated material
flow rate, and plasma torch power were studied. The experimentally obtained results were
compared with the model based on the thermodynamic equilibrium. Additionally, the
quantification of the plasma conversion system in terms of energy efficiency and specific energy
requirement was performed. It has been found that the synthesis gas could be effectively
produced from the biomass using water steam plasma.

Lee et al., (2014) Coal remains integral to the supply of energy in many parts of
the world despite the associated negative effects on the environment. Plasma arc reforming had
the potential of making coal to liquids processes cleaner by reducing its greenhouse gas
footprint. However, the chances of adoption without a clear understanding of how the process
modification could affect economic performance are slim. In this study, financial models were
built using an existing commercial coal to liquids process as a reference case. Economic analyses
were done to evaluate the impact of deploying a plasma arc reformer on financial performance of
a coal to liquids process. In building the financial models, the possibility of the introduction of a
carbon tax was taken into consideration. The results show that deploying plasma arc reforming
reduces the oil price required for break-even from $89/bbl. to $82/bbl., achieves a positive
project NPV and exceeds the hurdle rate for similar projects. In the process, it reduces
vulnerability to the introduction of a carbon tax. The requirement for extra low carbon electricity
could be a hurdle to implementation, however the alternative carbon tax related charges are less
desirable. Overall, it was concluded that the deployment of plasma arc reforming to coal to
liquids processes was value added. The project demonstrates that by implementing a cleaner
production initiative it was possible to reduce greenhouse gas emissions of coal to liquids
without significantly losing shareholder value.

Yang et al., (2015) accurate analysis of osmium was important in geochemistry and
geochronology. The current osmium analytical methods often suffer from low sensitivity, multi-
step extraction, high procedural blank, and severe memory effect. In this work, a highly sensitive
and simple method for the determination of osmium in natural waters was developed by coupling

21
inductively coupled plasma-mass spectrometry with photochemical vapor generation. The
procedural blank is low due to the needlessness of high concentration strong oxidant. What's
more, the memory effect was successfully solved by using 5.0% ammonium hydroxide elution
instead of using concentrated inorganic acid or oxidant reagent reported before. The influences of
the concentration of nitric acid, the flow rate of carrier gas, the photo irradiation time on osmium
detection were investigated. Under optimized conditions, the detection limit was 0.8 pg. mL−1.
A precision of 3.2% (RSD, n = 5) was achieved at a concentration of 1 mg mL−1. The accuracy
is successfully validated in several natural water samples with spike recoveries from 97% to
106%. The proposed method is sensitive, simple, low blank, and memory effect-free, which had
a great potential in relevant geochemistry and geochronology study.

Akiyama et al., (2016) a comprehensive review of the analytical literature revealed

substantial under-representation of trace element concentrations in fish blood, particularly for
marine species. We describe a simple dilution procedure to measure Li, Mg, K, Ca, Mn, Cu, Zn,
Se, Rb, Sr, Ba and Pb concentrations in low volumes of blood plasma of adult plaice
(Pleuronectes platessa) using high resolution-inductively coupled plasma- mass spectrometry
(HR-ICP-MS). Captive male and female plaice (n = 18) were serially sampled for one year and
samples collected outside of the spawning season (n = 157) used to estimate reference ranges for
this species. Method accuracy was deemed satisfactory, based on its application to the analysis of
a certified reference material. Precision was generally <3%, with the most conservative measure
of precision being≤10% for all elements except Pb (∼20%). This is the first study to analyses fish
blood plasma by ICP-MS and includes some of the first reference ranges for trace element
concentrations in fish blood.

Aoki et al.,(2016) Low-temperature plasma was used to control bacteria, endotoxins

and natural organic matter (NOM) in water by a dielectric barrier discharge (DBD)
device. Results indicate that DBD plasma had an obvious inactivation effect on various
bacteria in water. The degree of inactivation from difficult to easy is as follows: Bacillus
subtilis > Escherichia coli > Staphylococcus aureus. Activated ultrapure water treated
using DBD plasma exhibited a sustained sterilization effect, but this sterilization effect
decreased gradually after 1 h. The total-endotoxin (free-endotoxin and bound-endotoxin)
released by Escherichia coli during inactivation, as well as artificially simulated endotoxin

22
in a control solution, was significantly controlled by DBD plasma. Both the metabolites
that appeared after inactivation of microorganisms by plasma treatment, and the NOM in
filtration effluent of a water treatment plant were well removed by DBD plasma if the
treatment duration was sufficiently long. However, the acute toxicity increased
significantly, and persisted for at least 2 h, indicating that some long-life active
substances were generated during the DBD process. Therefore, the removal of bacteria,
endotoxins or NOM does not mean a safe water was produced. It was also important to
eliminate the toxicity and byproducts produced during water treatment for the continuous
promotion and industrial application of DBD plasma

Shin et al., (2016) in this work, an experimental plasma-chemical reactor equipped with a
water vapor plasma torch was used for catalyst-free thermal plasma reforming of propane to
produce a synthesis gas. Thermal arc discharge plasma (a mixture of water vapor and argon) was
generated at atmospheric pressure. The influences of the H2O vapor and C3H8 flow rates on the
syngas production, composition, and energy conversion efficiency as well as specific energy
requirements were investigated. The best results were obtained under the experimental
conditions of H2O vapor flow rate of 360 l/min, C3H8 flow rate of 47 l/min, and input plasma
torch power of 63 kW. The concentrations of the products were as follows: H2 68.9%, CO 21%,
CO2 5%, CH4 0.55%, and C2H2 0.9%. The C3H8 conversion ratio, H 2 yield, H2 selectivity, and
CO selectivity were 100%, 67%, 48.5%, 25.3%, respectively. The highest energy efficiency and
the lowest specific energy requirement were 65% and 32.7 kJ/mol, respectively, and the H 2/CO
ratio was 3.28. The modeling of chemical processes, based on the classical thermodynamic
equilibrium reactor, was also proposed. The calculated data fit quite well the experimental
results.

Ishijima et al.,(2016) This research involves two in-liquid plasma methods of methane
hydrate decomposition, one using radio frequency wave (RF) irradiation and the other
microwave radiation (MW). The ultimate goal of this research was to developed a practical
process for decomposition of methane hydrate directly at the subsea site for fuel gas production.
The mechanism for methane hydrate decomposition begins with the dissociation process of
methane hydrate formed by CH4 and water. The process continues with the simultaneously
occurring steam methane reforming process and methane cracking reaction, during which the

23
methane hydrate was decomposed releasing CH4 into H2, CO and other by-products. It was found
that methane hydrate can be decomposed with a faster rate of CH4 release using microwave
irradiation over that using radio frequency irradiation. However, the radio frequency plasma
method produces hydrogen with a purity of 63.1% and a CH conversion ratio of 99.1%, which is
higher than using micro- wave plasma method which produces hydrogen with a purity of 42.1%
and CH4 conversion ratio of 85.5%.

Nomura et al.,(2016) Banana peduncle biomass was processed in thermal plasma

reactor to produce potassium (K) enriched biochar. The effect of different gases (argon
and oxygen) and plasma processing time (3, 5, 7 and 9 min) on enrichment of K in
biochar was evaluated. Potassium of banana peduncle enriched in biochar due to its
residualization and mineralization during the plasma processing. Proximate, elemental, FT
IR, BET surface area and SEM analysis revealed the dominant effect of processing time
on physicochemical and surface characteristics of biochar. K enrichment was found to be
relatively higher in case of Argon (Ar) gas and 7 min plasma processing time. The
available K content of banana peduncle (66.3 g/kg) increased to 86.2, 163.5 and 258.5
g/kg in biochar produced by argon plasma processing for 3, 5 and 7 min respectively.
XRD peaks confirmed the formation of K containing Kalicinite (KHCO 3) mineral in
biochar samples, which mainly contribute for water soluble K-fraction. The research
findings highlight the scope of K-enriched biochar production through plasma processing
of waste biomass for K replenishment in soil along with additional advantages of liming,
conditioning and carbon.

Yoon et al.,(2017) A pulsed electrical discharge plasma formed in a tubular reactor

with flowing argon carrier gas and a liquid water film was analyzed using methylene
blue as a liquid phase hydroxyl radical scavenger and simultaneous measurements of
hydrogen peroxide formation. The effects of liquid flow rate, liquid conductivity,
concentration of dye, and the addition of ferrous ion on dye decoloration and degradation
were determined. Higher liquid flow rates and concentrations of dye resulted in less
decoloration percentages and hydrogen peroxide formation due to initial liquid
conductivity effects and lower residence times in the reactor. The highest decoloration
energy yield of dye found in these studies was 5.2 g/kWh when using the higher liquid

24
flow rate and adding the catalyst. The non-homogeneous nature of the plasma discharge
favors the production of hydrogen peroxide in the plasma-liquid interface over the
chemical oxidation of the organic in the bulk liquid phase and post-plasma reactions with
the Fenton catalyst lead to complete utilization of the plasma-formed hydrogen peroxide.

Rutberg et al.,(2017) This study presents results of an experimental investigation on

the development of water vapor plasma technology and its applications in environment-
friendly processes. An experimental linear 55–69 kW DC plasma torch operating at
atmospheric pressure was developed, tested and employed to conduct an experimental
research on the production of hydrogen-rich gas. The average temperature of water vapor
plasma jet in the exhaust nozzle varied from 2000 to 3000 K, and the plasma jet
velocity was 210–350 m s−1. Propane gas conversion into syngas by water vapor plasma
technology was investigated; this process was found to proceed efficiently. Hydrogen and
carbon monoxide gases were produced as the main products, and additionally also small
amounts of CO2 and H2O and O2 were obtained. Propane conversion depends on the
plasma jet temperature, total gas flow rate and stable operating conditions of the plasma
torch. The obtained results will be useful in further investigations to improve the
construction of a plasma reactor for solid biomass and organic waste decomposition

25
 Chapter 4

MATERIALS AND METHODOLOGY

In this study, the conversion of glycerol and wood to synthesis gas was carried out using an
entrained bed plasma-chemical reactor (PCHR). The experimental system is shown in Fig. 1.
It consists of an atmospheric pressure DC arc plasma torch, a power supply
system, a steam generator, a super heater, a gas supply system, a chemical reactor, an organic
material supply, a condenser with silica gel (to remove moisture from the gas produced), and a
gas chromatograph. The entrained bed plasma-chemical reactor used in this study was 1 m long
with 0.4 m inner diameter. At the bottom of the reactor, there is a section for the removal of char
and condensed water, and in the middle an outlet chamber for the produced gaseous products is
installed. The residence time varied from 0.5 to 1 s, which depended on the flow rates of steam
and the treated organic material, and the size of the PCHR.
Pure glycerol (99.5%) was used as a substitute for crude glycerol, which is
considered a by-product of biodiesel production after the trans esterification process. Glycerol
was supplied to the chemical reactor at a constant rate of 2 g/s through the special spray nozzles.
The optimal operating pressure of a spray nozzle is 10 bar. Therefore, the pressure in the glycerol
feeding line was kept at 10 bar and regulated by nitrogen gas from a cylinder. To improve the
fluidity and spray stability of glycerol, it was preheated to 343 K with a heater before supplying
to the reactor. Wood was chosen as a solid organic material because of the known chemical
composition: C - 50.25%, H - 6.09%, O - 43.35%, N - 0.2%, and S e 0.1%. It was supplied to the
reactor by a special feeder at the flow rate of 1.2 g/s. An atmospheric pressure DC arc plasma
torch was used to generate active plasma radicals (O, H, and OH) from the water steam. The
power of the plasma torch depends on the current intensity, voltage, and the flow rate of the
plasma-forming gas. Argon was used as a shielding gas in order to protect the tungsten cathode
of the plasma torch from erosion. During the experiments, the plasma torch power was changed
from 48 kW to 56 kW (current 200 A, voltage 240e280 V, steam flow rate (at 500 K) 2.63e4.48
g/s). The mean temperature in the plasma-chemical reactor was simply calculated from the heat
balance equation corresponding to the plasma enthalpy. The methodology is concisely defined.

26
During the experiments, the mean jet temperature was 2800 K, with the maximal absolute error
in the range of ±6-8%.

The gas produced after the conversion was analyzed by means of an Agylent 7890A gas
chromatograph equipped with dual-channel thermal conductivity detectors (TCDs) and a valve
system. The flow rates of the formed products were calculated from the mass balance equation
using the known flow rates of the reactants and the product concentrations measured with a gas
chromatograph. Additionally, a flow meter was used after the condenser to measure the flow rate
of the outlet gas. Thus, it was easier to check whether the mass balance equation was valid for all
the products after the flow rate calculation.

Main chemical reactions

Generally, the biomass/waste conversion to synthesis gas involves complex chemical reactions.
The main chemical heterogeneous and homogenous reactions of pyrolysis and the gasification
taking place in the reactor are described in detail in arena states that the final composition of the

27
synthesis gas will be determined by the reaction rates and also by the effect of catalysts, which is
important for tar decomposition in the reactor, rather than by the thermodynamic equilibrium.
Nevertheless, the initiation of the chemical reactions in the reactor starts not only due to the high
temperatures but may also be affected by the arc discharge being used. Therefore, firstly, active
radicals such as O, H and OH are produced in the discharge chamber of the plasma torch under
the impact of energetic electrons or the thermochemical pyrolysis of steam (where M refers to
charge transfer):

H2O + M → OH + H* + M (1)
H2O + O * → OH* + OH* (2)
H2 + O * → OH + H* (3)
H2 + OH * → H2O + H* (4)

The produced active radicals can considerably accelerate the pyrolysis/gasification process in the
plasma chemical reactor where the heterogeneous and homogeneous reactions mentioned in take
place.

Evaluation of conversion performance

In order to compare different processes and to evaluate the performance of the conversion
system, it was quantified in terms of carbon conversion, H 2 and CO yield, H2/CO ratio, energy
efficiency and specific energy requirement. The criteria mentioned above are described in detail.
Carbon conversion writes:

where Xc(%) is the carbon conversion degree (%), XCO,CO ,CH ,C H ,OUT is the mass flow rate of the
2 4 2 2

carbon in the gas produced (kg/s), and X M,IN is the mass flow rate of the injected organic material
(kg/s).
The hydrogen yield is:

28
Where H2(Yield) is a hydrogen yield (%), XH ;syngas is the mass flow rate of hydrogen produced in
2

the syngas (kg/s), and XM,IN is the mass flow rate of the injected organic material (kg/s).
The carbon monoxide yield is:

Where CO (Yield) is a carbon monoxide yield (%), X CO,syngas is the mass flow rate of CO
produced in the syngas (kg/s), and XM,IN is the mass flow rate of the injected organic material
(kg/s).
The energy conversion efficiency is:

Where ƞeff is the energy conversion efficiency (%), (H 2+CO) is the mass flow rate of syngas
(kg/s), LHVM,IN is the lower heating value of the injected organic material (kJ/kg), and P plasma is
the power of the plasma torch (W).
The specific energy requirement (SER) is:

Where Pplasma is the plasma torch power (kJ) and (H2+CO) syngas is the molar flow rate of syngas
(mol).

Thermodynamic equilibrium calculations

The plasma-chemical processes occurring in the plasma-chemical reactor were simulated by

means of the Chemical Workbench (CWB) code [62] using a PT-type (constant pressure and
known temperature) thermodynamic equilibrium reactor (TER) model. The TER is designed for
calculating the chemical equilibrium of a multi-component heterogeneous system. A more
detailed explanation of the model is provided.

29
 Chapter 5

RESULTS AND DISCUSSION

The effects of the steam/treated material ratio and the plasma torch power on the biomass
conversion are discussed below. It should be noted that at a constant arc current intensity of 200
A, the increase of the steam (H 2O) flow rate from 2.63 to 4.48 g/s increases the power of the
plasma torch from 48 to 56 kW due to the raise in the voltage-drop in the arc discharge channel.
The concentrations of gas produced in each experimental case were measured three times, giving
a relative deviation below ±5%.

Glycerol conversion

Glycerol (C3H8O3) conversion in the ambient of water steam plasma was performed under the
following experimental conditions: glycerol flow rate 2 g/s, steam flow rate 2.63-4.48 g/s, and
the plasma torch power 48-56 kW. The H2O/C3H8O3 ratio changed from 1.3 to 2.2, Tf ¼ 2800 K.
The concentrations of gas produced after the conversion of glycerol are shown in
Fig. 2. As the H2O/C3H8O3 ratio increased from 1.3 to 2.2, the H2 and CO2 concentrations slightly
increased, whereas that of CO slightly decreased, and the concentration of intermediates (CH4
and C2H2) was below 5%. The experimentally obtained H 2 and CO concentrations differed from
those calculated at the thermodynamic equilibrium by 6% and 17%, respectively.
No traces of glycerol after the conversion were detected. It was fully decomposed
into gas, liquid and a little amount of char as indicated in Figs. 3 and 4. The highest carbon
conversion efficiency exceeded 88.9% at a water steam flow rate of 4.48 g/s and a plasma torch
power of 56 kW. As the H2O/C3H8O3 ratio and the plasma torch power increased, the yield of gas
produced in the total reaction product mass balance increased, while the yield of char decreased
significantly. The yield of liquid products, mostly condensed water, increased due to the excess
steam, methanation, and hydrogenolysis of glycerol. Nevertheless, the H2 yield was over 90%
and increased as the flow rate of steam increased (Fig. 5). However, the CO yield was lower and
increased only up to 55%, indicating that there was a potential to make the process of glycerol
conversion to synthesis gas more selective in terms of the CO yield. This could be done by trying
to minimize the content of intermediates such as CH 4 and C2H2 by using special catalysts and/or

30
by using the water-gas-shift reaction. The H2/CO ratio was close to stable (around 1.9), showing
the ability of the produced synthesis gas to be directly used for energy/ heat or chemical
production.

Fig. 2. Effect of the H2O/C3H8O3 ratio on the produced gas composition. The full line represents
the experimental results and the dashed red line represents the calculated results.

Fig. 3. Effect of the H2O/C3H8O3 ratio on the glycerol conversion degree and product yield.

31
Fig. 4. Effect of the plasma torch power on the glycerol conversion to gas and char.

Fig. 5. Effect of the H2O/C3H8O3 ratio on the H2 and CO gas yield and H2/CO ratio.

The best conversion process efficiency was obtained at an ƞ eff of 51% and SER of
59 kJ/mol (equal to 0.54 kWh/kg) when the flow rates of glycerol and steam were 2 g/s and 4.48
g/s, respectively, and the plasma torch power was 56 kW (Fig. 6). The results suggest that there
is a potential for the further increase of the flow rate of glycerol in order to achieve a better
reaction performance as well as the process efficiency. However, the char formation could be
minimized by improving the reactor design, i.e. installing the glycerol spray nozzles closer to the
plasma jet or by increasing the reaction temperature. Hence, glycerol could be converted even

32
much faster by a high-temperature steam plasma with a higher active radical concentration
inside.

Wood conversion

Wood conversion in the ambient of the water steam plasma was carried out under the following
experimental conditions: wood flow rate 1.2 g/s, steam flow rate 2.63-4.48 g/s, and the plasma
torch power 49 kWe56 kW. The H2O/wood ratio was in the range of 2e3.4, Tf ¼ 2800 K.
The concentrations of the gas produced after wood conversion are shown in Fig. 7. As the
H2O/wood ratio increased from 2 to 3.4, the H2 and CO concentrations slightly decreased,
whereas the CH4 content increased. The CO2 concentration decreased as the H2O/wood ratio
increased to 2.7 and began to increase above the H2O/wood ratio of 2.7. This could be affected
by the dominance of the exothermic water-gas-shift reaction. The experimentally obtained H2
and CO concentrations differ from those calculated at a thermodynamic equilibrium by more
than 40-50% and 25-50%, respectively. In this case, the CWB code was not suitable for the
modeling of the wood conversion process as it does not include the condensed solid phase
formation. Wood pyrolysis/gasification in the ambient of water steam plasma is complicated and
mostly based on the water-gas, Boudouard hydrogasification, water-gas-shift, and methanation
reactions.

Fig. 6. Effect of the H2O/C3H8O3 ratio on the energy expenditure

33
Fig. 7. Effect of the H2O/wood ratio on the produced gas composition. The full line represents
the experimental results, and the dashed red line represents the calculated data.
The wood was completely converted to gas, liquid and char, as it is shown in Figs.
8 and 9. At the plasma torch of 56 kW and the H 2O/wood ratio of 3.4, the residence time was
sufficient for the wood conversion to gas, liquid, and char. The yield of char in the total reaction
product mass balance decreased to 0.5%, while that of gas increased to 55%, giving a carbon
conversion efficiency of up to 97.5%. As wood consists of moisture (H 2O) and H2, the yield of
liquids, mostly condensed water, slightly increased due to the excess steam used in the process
and the wood methanation reaction. The H2 yield increased from 60% to 87%, while that of CO
increased only from 35% to 54%, as indicated in Fig. 10. If compared with the glycerol
conversion, wood consists of only ~5-7% of H 2 in the total mass, while the quantity of hydrogen
in glycerol is much higher. For this reason, the H2 yield is lower in the wood conversion case.
The formation of intermediates such as CH 4, C2H2 and the combustion product CO2 determines
the lower CO yield. This might be improved in the same way as described in the glycerol
conversion case. The H2/CO ratio slightly increased at a H2O/wood ratio of 3.4. It could be
explained by the dominance of the water-gas-shift, CO oxidation and methanation reactions. The
H2/CO ratio indicates that the produced synthesis gas was of high quality and could be used for
energy/heat or chemical production. The highest process efficiency of the wood conversion was
obtained at a ƞeff of 45.6% and SER of 69 kJ/mol (equal to 0.64 kWh/kg) when the flow rates of

34
wood and steam were 1.2 g/s and 4.48 g/s, respectively, and the plasma torch power was 56 kW
(Fig. 11).

Fig. 8. Effect of the plasma torch power on the wood conversion to gas and char.

Fig. 9. Effect of the H2O/wood ratio on the product yield.

35
Fig. 10. Effect of the H2O/wood ratio on the H2 and CO gas yield and the H2/CO ratio

Fig. 11. Effect of the H2O/wood ratio on the energy expenditure.

Comparison of the conversion process

The comparison of glycerol and wood conversion to synthesis gas by means of the thermal steam
plasma is described in this section. The results of the conversion process under the best
experimental conditions are shown in Table 1.

36
Table 1
Comparison of the conversion processes.
Material H2(Yield%) CO(Yield%) H2/CO ƞeff (%) SER (kJ/mol)
C3H8O3 93 55 1.9 51 59
Wood 87 54 2.2 45.6 69

Due to the physical properties and size of wood, the process efficiency was lower and the
specific energy requirements were higher as compared with the glycerol conversion case.
Therefore, an additional energy was required to heat, boil up, evaporate and convert wood to gas.
Hence, wood required a higher energy to be converted to aseous compounds if compared with
liquid glycerol. According to the results in Table 1, the SER for converting wood to synthesis gas
was 10 kJ/mol higher than that in the case of glycerol, thus leading to a 5.4% lower process
efficiency. In the future, the process efficiency depending on the size of treated wood is planned
to be examined. It could be stated from the above table that in both cases the decisive parameter
for the effective material treatment was the steam flow rate which also influenced the power of
the plasma torch at a constant arc current. As the flow rate of steam increased from 2.63 to 4.48
g/s, the best conversion process efficiency was obtained. Moreover, the presence of active
radicals in the plasma stream and high plasma temperatures (reaching up to 2800 K) enabled to
treat materials with a high conversion efficiency at a short residence time (varying from 0.5 to 1
s). Therefore, the main components after the conversion of glycerol and wood are H2 and CO,
together representing around 55% in the total product mass balance. The concentrations of
intermediate gaseous products, such as CH4 and C2H2, even with a small content exceeding 5-7%
in the total mass balance should also be taken into account. This might help to increase the
process efficiency converting them to H2 and CO through the complex heterogeneous and
homogeneous reactions involving methanation, hydrogasification, water-gas, Boudouard and
water-gas-shift chemical reactions. During this experimental research, the concentrations of CH4
and C2H2 slightly increased as the steam/fuel ratio increased. In the case of glycerol reforming,
the content of CH4 and C2H2 increased from 4.5% to 5.3% and from 1% to 1.65%, respectively,
whereas in the case of wood conversion, only CH4 with concentrations in the range of 1%-4%
was observed. This suggests that there is potential to minimize the formation of these compounds
by improving the technological process.

37
 Another constituent in the mass balance is condensed incompletely reacted water which was
used as a plasma forming gas, the heat carrier and the main reactant. Due to its physical
properties, condensation is inevitable. Moreover, the flow rate of steam used to run the plasma
torch stably is optimal, and thus, there is no possibility to achieve it completely reacted.
Nevertheless, the increase of the flow rate of treated materials might help to increase the amount
of reacted steam and to minimize its quantity in the final reaction product mass balance.
Therefore, the optimal conversion process establishment is required.
The amount of char in the reaction products’ mass balance varies from 1 to 4%, showing the
great potential of the thermal plasma technology to be applied for the effective treatment of
organic materials. On the other hand, the low carbon monoxide yield requires making the
conversion process more selective. Therefore, special catalysts supported by Cu, CuO, Cr2O3, Ni,
NiO, ZrO2, Al2O3, and magnesium-containing materials might be used to reduce the content of
intermediates as reported. Furthermore, the increase of the plasma temperature up to 4000 K
would lead to a full steam decomposition into elemental substances such as H, O, OH, O2 and H2.
It will also help to increase the yields of H 2 and CO, because at a mean plasma temperature of
2800 K, reached during the experiments in the reaction zone, only 25% of steam was dissociated
according to the CWB calculations. However, the achievement of such a temperature is a
challenging technological issue.
The H 2/CO ratio was close to 2 in both cases. It implies that the produced synthesis gas is
suitable for the direct energy/heat or chemical production via the Fisher-Tropsh synthesis. It is
worth stating that no dangerous compounds after the glycerol/wood conversion have been
detected. Only condensed water, valuable synthesis gas (H 2+CO) and small amounts of solid
carbon were found. This implies that the thermochemical arc plasma technology, where the
overheated steam is used as a plasma-forming gas, the heat carrier and the reactant, can be an
effective and environmentally friendly biomass treatment method. Moreover, the method used in
this study is not limited to any kind of organic material (gaseous, liquid or solid) to be effectively
treated to valuable products. However, more detailed experimental investigations are required in
order to prove the economic feasibility of the technology used.

38
 Conclusions

In this report, a thermal DC arc discharge water steam plasma was used to convert
glycerol and wood to a synthesis gas. Additionally, chemical process modeling was used to
investigate the concentrations of products at the thermodynamic equilibrium. The TER model
showed quite a good agreement between the experimental and simulated data only for H 2 in the
case of glycerol conversion, but it was unsuitable in the case of wood conversion

The H2/CO ratio indicates that the produced synthesis gas is of high quality and, therefore,
may be further used for energy/heat or chemical production. The thermochemical DC arc
discharge water steam plasma technology could be an effective and competitive technology for
biomass conversion to synthesis gas because of the high plasma enthalpy (temperature), active
radicals, easy process control, and relatively high energy efficiency. The future studies will focus
on the process optimization. Furthermore, a detailed comparison with different plasma
technologies will be proposed.
A simple fast and cost effective hydrothermal plasma method has been
successfully applied for the fabrication of uniform distribution Ag/SiO 2 Nano fibers and
nanoparticles. The mechanism of the reaction is based on the reduction power due to the evolved
water vapor that results in formation of (CO and H 2) and complete decomposition of the silver
nitrate into metallic Ag at relatively short time (20 min). The high pressure in the autoclave
vessel facilitates fast Ag formation and promotes formation of nanostructures fibers and particles
based on the reaction temperature.
The thermal arc discharge water vapor plasma technology could be an efficient
and competitive technology for C3H8 reforming to synthesis gas because of its active radicals,
high enthalpy and temperature, large treatment capacity and relatively high energy efficiency.

39
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