Jointly published by React.Kinet.Catal.Lett.

Akadémiai Kiadó, Budapest Vol. 74, No. 1, 71-77

and Kluwer Academic Publishers, Dordrecht (2001)

RKCL3917

ZEOLITE-ENHANCED PLASMA METHANE CONVERSION

DIRECTLY TO HIGHER HYDROCARBONS USING DIELECTRIC-
BARRIER DISCHARGES

Changjun Liua ,b*,Baldur Eliassonb,c, Bingzhang Xueb,c, Yang Lia,b and

Yaquan Wanga
a
State Key Laboratory of C1 Chemical Technologies
b
Tianjin University-ABB Plasma Greenhouse Gas Chemistry Laboratory
Tianjin University, Tianjin 300072, P.R.China
c
ABB Corporate Research Ltd., Baden, CH-5405, Switzerland

Received May 9, 2001

Accepted June 21, 2001

Abstract
A zeolite-enhanced plasma methane conversion with pure methane feed using
dielectric-barrier discharges (DBDs) at atmospheric pressure has been conducted.
This plasma methane conversion over NaX has led to a selective production of
light hydrocarbons.

Keywords: Methane conversion, dielectric-barrier discharge plasma, zeolite

INTRODUCTION

The significant potential benefit of economically converting methane, the

principal component of natural gas, to more valuable hydrocarbons has been
well established. An intense investigation has been conducted to convert
methane directly to higher hydrocarbons or oxygenated hydrocarbons
catalytically. However, there is still no proven technology for such direct
catalytic methane conversion. It is important to investigate continuously the
catalytic methane conversion, while to exploit some alternative technologies
simultaneously. The plasma is a promising alternative for methane conversion.

0133-1736/2001/US$ 12.00.
© Akadémiai Kiadó, Budapest.
All rights reserved.
72 CHANGJUN LIU et al.: METHANE CONVERSION

The methane conversion using plasmas can lead to a much higher methane
conversion (close to 100% in some cases) [1-10]. There are usually two ways
for plasma methane conversion, one is indirect plasma methane conversion via
syngas step [1,2], and the other is direct plasma methane conversion to more
valuable hydrocarbons [3-10]. The former one produces syngas first using
plasma and then produces more valuable hydrocarbons from syngas
catalytically. The pilot test of syngas production using plasmas has been
reported recently [11,12]. The direct way produces more valuable hydrocarbons
from methane using plasmas without through syngas step that attracts more
attentions recently. However, co-reactant or oxidant or dilution gas is needed to
sustain a stable operation of plasma methane conversion directly [3-10], which
leads to a reduction in the selectivity or yield of objective products. Especially,
there are few reports for the use of pure methane feed for plasma conversion (at
atmospheric pressure) to clean liquid fuels. In this paper, we present a zeolite-
enhanced methane conversion directly to higher hydrocarbon using dielectric-
barrier discharge (DBD) plasmas over NaX zeolite with pure methane feed.

EXPERIMENTAL

The DBD reactor applied here, as shown in Fig. 1, is similar to that used in
previous investigations on plasma methane conversion with carbon dioxide as
co-reactant using DBDs [3]. The gas flow is subjected to the action of DBD in
an annular gap (the radical width is 1 mm and its length is 300 mm) formed
between an outer steel cylinder maintained at constant temperature and an inner
quartz tube. A high voltage generator working at about 30 kHz applies the
power. When the amplitude of applied ac electric field reaches a critical value,
breakdown is initiated in the gas. Once breakdown is initiated at any location
within the discharge gap, charge accumulates on the dielectric resulting in an
opposite electric field. This opposite electric field locally reduces the external
electric field in the gap and interrupts the current flow within a few
nanoseconds. By this mechanism individual current filaments called micro-
discharges are formed. Their duration depends on the pressure, the properties of
gas involved, the dielectric and zeolite used. A large number of such micro-
discharges will be generated when a stable DBD operation is established, esp.
in the case that zeolite presents. The principal advantages of the DBD are that
non-equilibrium conditions can be easily established at atmospheric pressure
and that the entire electrode area is effectively used for discharge reactions.
The feed gas, methane, was introduced into the system flowing through the
reactor. Two MTI (Microsensor Technology Inc., M200H) dual-module micro
gas chromatograph containing a Poraplot Q column, an Al2O3 " S" column and
CHANGJUN LIU et al.: METHANE CONVERSION 73

a molecular sieve 5Å. Plot column with TCD detectors were used to detect
gaseous products. The liquid sample was analysed at the Laboratoire d'Analyse
at the Shell Raffinerie de Cressier/Switzerland with gas chromatographs. It
contains more than 200 branched higher hydrocarbon (HHC) components in the
range of C5 to C11 that represents a better fuel production. A HP6890 GC with
FID was also used to analyze the carbonaceous species adsorbed on the plasma-
used zeolite.
NaX zeolite was used here to inhibit the formation of carbon black and to
increase the yield of gasoline and/or light hydrocarbons. The zeolite was
obtained from Condea Augusta and applied as received. In each case about 9 g
zeolite powder was introduced into the discharge gap. The loading of zeolite
has also been described elsewhere [3].
The gas temperature was measured using two thermocouples: one has been
located in the gap between the dielectric and the grounded electrode, while the
other has been placed in the exit of active region of DBD plasmas. A TGA
study was performed for Temperature Programmed Oxidation (TPO)
characteristics of DBD plasma-used zeolite using a Shimadzu TGA-50 system
under an air stream (flow rate: 20 mL/min). 2.319 mg of DBD plasma-used
NaX zeolite sample was mounted in a platinum cell. The reaction temperature
with the TPO was raised from room temperature with a ramping rate of
10°C/min.

Fig. 1. A schematically representative of DBD plasma reactor system

74 CHANGJUN LIU et al.: METHANE CONVERSION

RESULTS AND DISCUSSION

The effective active region for DBD plasma methane conversion is within
the gap between the dielectric (quartz) and the grounded electrode (the outer
stainless steel cylinder), as shown in Fig. 1. The following reactions would
occur at the initiation of DBD plasma CH4 conversion:

CH4 → CH3 + H (1)

CH2 + H (2)

CH + H (3)

C+H (4)

10
9
8
carbon atom select. (wt%)

7
6
5
4
3
2
1
0
2 3 4 5 6 7 8 9 10
carbon number

Fig. 2. The carbon atom selectivity via carbon number from the experiment of
pure methane feed with NaX (zeolite amount: 9.0 g, input power: 500 W, flow
rate: 150 mL/min, pressure: 1 bar, gas temperature: 150°C, frequency: around 30
kHz, methane conversion: 26.8%)
CHANGJUN LIU et al.: METHANE CONVERSION 75

In addition to carbon black, the radical chain reactions will start from CH3,
CH2 and CH to generate higher hydrocarbons. The experimental investigation,
however, shows the presence of zeolite within DBD plasmas can stop the
reaction at the step of reaction (3). The DBD plasma methane conversion has
therefore become sustainable with pure methane feed. The liquid sample
collected directly from the effluents of DBD reactor has a carbon number range
from C5 to C11, upon the results of GC analysis. Figure 2 presents carbon atom
selectivity with the increasing carbon number in the range from C2 to C11.
From Fig. 2, the most selective product of DBD plasma methane conversion is
C2 hydrocarbons. With increasing carbon number, the carbon atom selectivity
decreases at the beginning. To our surprise, the curve shows a jump in the
carbon atom selectivity at the carbon number from 5 to 8.
The oily carbonaceous species were also produced on the zeolite. Table 1
shows a GC analysis of the composition of oily carbonaceous species from the
DBD reactions using pure methane feed over NaX zeolite. Before this GC
analysis, the plasma-used zeolite was put into a pure CCl4 solution. The
carbonaceous species were thereby dissolved into the CCl4 solution to form a
mixture. Then the GC analysis was conducted to analyze the component of this
mixture. Table 1 also shows that a significant amount of branched
hydrocarbons have been produced that are characteristics of DBD plasma
reactions.

Table 1
Composition of carbonaceous species on DBD plasma-used NaX
(pure methane feed; flow rate: 150 mL/min; input power: 500W; gas temperature:
150°C; pressure: 1 bar; methane conversion: 26.8%; catalyst weight: 9.0 g )

Component Composition Component Composition

(mol%) (mol%)

≤ C15 5.47 C20 2.51

C15 14.00 C21 4.31
iC16+iC17 12.50 iC21+C22+iC23 8.99
C17 3.32 C23 1.64
iC18 1.48 iC24 9.62
C18 0.35 C24 5.58
iC19 3.76 iC25 3.60
C19 0.95 iC26 7.80
iC20 1.13 C26 10.77
>C26 2.21
76 CHANGJUN LIU et al.: METHANE CONVERSION

TPO characteristics of DBD plasma-used zeolite

Thermal analysis of DBD plasma-used zeolite shows a significant weight

loss of ca. 280°C, which can be attributed to the oxidation of carbonaceous
species (the components were shown in Table 1). A continuous weight loss is
shown in the TGA spectrum (Fig. 3) that suggests a wide range of
carbonaceous deposits. The TGA indicates an around 30% weight loss after the
TPO measurement. It is clear that a large amount of carbonaceous species have
been formed on the zeolite during the DBD plasma methane conversion.
Further investigation is being conducted to understand the mechanism of
interaction between zeolite and DBD plasmas.

Fig. 3. TGA spectrum of DBD plasma-used NaX zeolite from the experiment of
pure methane feed with NaX (zeolite amount: 9.0 g, input power: 500 W, flow
rate: 150 mL/min, frequency: around 30 kHz, pressure: 1 bar, gas temperature:
150°C, methane conversion: 26.8%)

CONCLUSION

The present investigation confirmed the effectiveness of DBD plasma in

converting pure methane directly into higher hydrocarbons in the presence of
zeolite without using co-reactant or dilution gas. The liquid hydrocarbons
produced are highly branched that represents a better fuel production.
CHANGJUN LIU et al.: METHANE CONVERSION 77

Acknowledgements. This investigation was supported in part by ABB

Corporate Research Ltd., Switzerland, Key Fundamental Research Project of
Ministry of Science and Technology of China (G1999022402) and National
Natural Science Foundation of China (29806011).

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