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PLASMA REFORMING OF HYDROCARBONS

IN PLASMA-LIQUID SYSTEMS WITH SECONDARY DISCHARGES
V.Ya. CHERNYAK
1
, V.V. NAUMOV
2
, V.V. YUKHYMENKO
1
, Yu.P. VEREMII
1
,
I.V. PRYASIAZHNEVYCH
1
, Yu.I. SLYUISARENKO
1

1
Radiophysical Faculty, Taras Shevchenko Kyiv National University,
Prospect Acad. Glushkova 2/5, Kiev 03121, Ukraine; e-mail: chern@univ.kiev.ua
2
Institute of Fundamental Problems for High Technology, Ukrainian Academy of Sciences,
Prospect Nauki 45, Kiev 03028, Ukraine; e-mail: naumov@ifpht.kiev.ua
Introduction
One of the basic features of chemical reactions in plasma is the participation of
particles in excited energy states (electronic, vibration, rotation). It ensures high reactivity of
plasma and potential efficiency of plasma-chemical processes, especially in non-thermal
conditions being far from equilibrium [1]. However, extremely broad spectrum of active
particles in multicomponent plasma leads to excessive multichanneling of chemical
transformations. This makes the chemical reaction control, i.e. selectivity by one of the most
actual problems of plasmachemistry. Complex kinetics in multi-reagent plasma-chemical
systems demands to consider not only chemical reactions, but also physical processes of
excitation and relaxation of energy states of reagents [2]. It complicates the description of
plasma chemistry but it shows the ways of solution of the selectivity problem in plasma-
chemical systems with high density of deposited energy. It can be the control of chemical
reactions by the specific energy distribution in the energy states of plasma-forming agents. In
electric discharges the electron impact is often the basic mechanism of excitation of internal
energy states of molecules [3]. It is necessary to take into account peculiarities of the electron
excitation function (EEF), i.e. dependence of the excitation cross-sections on the energy of
electrons. Judging from the EEF for vibrational states of most common molecules (H
2
, O
2
,
N
2
), the energy location of the EEF maxima changes very feebly with vibrational number ,
although the EEF value itself changes distinctly reducing with ascending of . It indicates
weak possibilities for control of vibrational population by changing of the average electron
energy. For electronic states of molecules the EEF behavior varies more strongly due to 1)
short distance between the energy threshold and the EEF maxima; and 2) large diversification
of electronic cross-sections in the energy spectrum [3]. Here one could expect essential
changes in the character of electronic population if the average electron energy will be much
higher than the ionization threshold.
The consideration of opportunities in conventional gas discharges (DC, RF, etc)
specifies that the drastic growth of the average electron energy in the plasma volume is hardly
achievable because of 1) low level of the electric field E in the positive column, and 2) small
range of the E change due to the exponential temperature dependence of the ionization rate
constant. The increase of the energy input in such discharges leads to the increasing of the
energy density in plasma and results not so much in the electron temperature T
e
as in the
increasing of electron concentration n
e
. Above-mentioned limitations inhered to gas discharge
plasma in a volume can be withdrawn in heterophase plasma-liquid or plasma-solid systems at
the medium interface. This approach is less common but according to our expertise it can be
very effective [410]. Principal features of such plasma systems are (a) direct input of plasma
particles in the work medium, (b) well-developed interface and large surface-to-volume ratio,
(c) long time of plasma-medium interaction for realization of deep chemical transformations,
(d) stable discharge operation due to intensive heat/mass exchange between plasma and
medium, and (e) high degree of plasma non-equilibrium which lead to high selectivity of
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plasma-chemical processing. Examples of technical realization of plasma-chemical processes
in heterophase plasma-liquid systems with secondary discharges exploited in our lab in Kiev
University are presented in this paper.
Characteristics of plasma-liquid systems with secondary discharges
Typical plasma-liquid systems are electrical discharges with one or two electrodes
immersed into the liquid. Here plasma is a source of active particles which inject through the
plasma-liquid interface and initiate plasma-chemical reactions in the aqueous solution. The
main feature of plasma-liquid systems is the intensive emission of molecules from the free
liquid surface into the discharge volume due to evaporation of the solution and formation of
gaseous products. Another feature is that plasma in such systems is generated at pressures
near the saturated vapor pressure at given temperature when the ionization instability could
occur. However, application of secondary discharges inhibits the development of the
ionization instability and provides the uniformity of parameters during the plasma-liquid
interaction. Physically, such plasma system can be considered, on the one hand, as an
auxiliary self-sustained discharge with a liquid electrode; on the other hand, a liquid electrode
can be considered as an immersion electrode in plasma of the auxiliary self-sustained
discharge similar to the electrical probe. This gives additional degrees of freedom and
controls for the efficient plasma chemical processing.
We realized two base schemes of supporting secondary discharges in plasma-liquid
systems: 1) DC discharge with one liquid electrode supported by the auxiliary gas-discharge
plasma flow [4]; and 2) DC discharge with a liquid electrode supported by the auxiliary
discharge in a gas channel with a liquid wall [10]. The first type of the secondary discharge is
distinguished by high stability of plasma-liquid interface and wide range of work pressures.
The second type is featured by large ratio of the plasma-liquid interface area in the plasma
volume. It is important that plasma generated in such gas-liquid discharges is very stable
against the overheated instabilities.
Typical current-voltage characteristics of secondary discharges in plasma-liquid
systems with one liquid electrode consist of several zones: positive exponential branch and
negative branch, which contains the linear range and the range corresponding to the abrupt
exponential current increase. Therefore, its behavior (existing of the exponential positive
branch and linear range of negative branch) is similar to I-V curves of Langmuir probe. In
case of the positive potential of the liquid against plasma the current is by two orders higher
than that in case of the negative potential.
Axial distributions of the floating potential in plasma-liquid systems with the
secondary discharge with a liquid electrode studied by the electric probe method for different
polarities of the liquid and for different currents of the discharge have shown an existence of a
jump of the electric field potential in the boundary layer between the liquid and plasma. Its
value (amplitude) depends on the polarity and voltage drop in the secondary discharge. This
makes possible the effective control of electro-radiolysis processes in aqueous solutions.
Properties of liquids after plasma-liquid treatment
The properties of aqueous solutions after plasma-liquid treatment were explored by
different diagnostic methods. The UV absorption spectroscopy was applied for analysis of the
organic and inorganic agents in water solutions and emulsions. The ion-metrical procedure
was used for measurements of pH factor. The flame-sorption spectrometry and chemical
titration were utilized for diagnostics of dissolved metal ions. Bio-tests of the residual toxicity
were conducted by the growth rate of the land and root systems of the lettuce plants and the
life-time of Daphnia magna micro-organisms in tested water solutions.
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Main results after the plasma treatment of water at low pressure are that 1) water
properties depend on the dissolved gases; 2) plasma treatment gives "acid" effect for non-
degassing and "alkaline" effect for degassing water; 3) basic oxidizing agents in plasma-
treated water are hydrogen dioxide and ozone. The water treatment at atmospheric pressure
gives only "acid" effect and basic oxidizing agents in plasma-treated water are hydrogen
dioxide and nitrous acids [5].
Plasma destruction of high-molecular toxic materials (phenol, surfactants, DDT and
pesticides) in plasma-liquid systems with secondary discharges have shown: 1) work solutions
are labile after plasma treatment and their stabilization can occur during days; 2) efficiency of
plasma treatment is much higher than conventional ozonization and grows linearly with
ascending of the solution concentration; 3) bio-toxicity of solutions after the complex plasma
+ boiling + reagent processing can be minor [6].
Besides plasma-liquid sterilization, we have demonstrated that plasma-liquid systems
allows to realize removal of ions of heavy metals (Cd, Cr, Co, Cu, Fe, Mn, Nb, Ni, Pb, Ta, Te,
Zn, Ur) from water [7] and dissolution of non-soluble metals (Cu, Ag, Au, Pt) in electrolytes
[8].
Our latest experiments related to applications of plasma-liquid systems for the
synthesis of nanopolymer carbon particles in toluene [9], gasification of plastic wastes
(polyethylene) [10], reforming of hydrocarbon fuels (ethanol) [10] are in progress.
Acknowledgements
The work was partially supported by the INTAS, by the Ukrainian Ministry of
Education and Science and by the Belarus-Ukraine Scientific Cooperation Program
20042006.
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