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Greenhouse Gas Control Technologies

P Riemer
.

B. Eliasson and A. Wokaun, editors

1999 Elsevier Science Ltd All rights reserved

385

PRODUCTION OF SYNTHESIS GAS

THROUGH PLASMA-ASSISTED REFORMING OF GREENHOUSE GASES

U. Kogclschatz, L. M. Zhou , B. Xue and B. Eliasson ABB Corporate Research Ltd, 5405 Baden, Switzerland
*

On leave from Xi,an Jiaotong University, Xi,an, P.R. China

ABSTRACT

Low temperature conversion of the two major greenhouse gases C02 and CH4 to synthesis gas (a mixture of H2 and CO) is investigated theoretically and experimentally in a high power dielectric-barrier discharge (DBD). Utilising this nonequilibrium discharge technique high conversion rates can be achieved in this special gas mixture. A pronounced synergetic effect caused by free radical reactions was observed using these two gases simultaneously. This way C02 separated from flue gases could be combined with methane to produce syngas which then can be processed to yield liquid fuels like e.g. methanol or dimethyl ether. Parameters studied are CH4/CO2 mixing ratio (0 - 100% of C02), electric power (100 - 800 W), flow rate (0.1 - 4 Nl/min), gas pressure (0.35 - 2 bar) and reactor wall temperature (80 C 250C). This technique of plasma reforming of methane with carbon dioxide can produce syngas with different H2/CO ratios depending mainly on the C1VC02 mixing ratio. The amount of syngas produced rises almost linearly with increasing discharge power. Up to 66 moles of syngas with a H2/CO ratio of 3.7 were obtained from 100 moles of feed gas in a single pass through the DBD reactor of 31 cm active length. The minimum required specific energy was 40 eV/molecule for the production of syngas (II2 plus CO) and the highest energy efficiency (electric energy converted to chemical energy in the syngas) reached so far was about 7 %.

INTRODUCTION

Continued excessive anthropogenic emissions of the greenhouse gases carbon dioxide and methane to the atmosphere may lead to an increase of the average global temperature. Therefore disposal or reuse of these gases has become a major issue. The hydrogenation of C02 to methanol has been investigated with copper-based catalysts at elevated pressure and temperature or, in combination with electrical discharges, at less demanding operating conditions. At about
220C and moderate pressures of less than 30 bar, a methanol yield of 5 - 10% per single pass was obtained in a

catalytic packed-bed reactor [1,2]. This methanol yield is already close to the equilibrium value. A methanol selectivity of about 40% was reached. When a catalyst was inserted into a dielectric-barrier discharge (DBD) gap the simultaneous presence of the discharge shifted the temperature region of maximum catalyst activity from 220 C to 100C [3, 4]. In

this temperature range, the theoretical equilibrium yield of methanol is 34% at 8 bar, roughly ten times higher than that at 220 C So, in principle, there is more room to increase methanol yield at this low temperature. Obviously, hydrogenation of C02 will only be attractive if the required hydrogen is produced in a cheap way and without causing additional C02 emissions [5]. The partial oxidation of methane to methanol with oxygen or air was investigated experimentally and theoretically in DBDs [6, 7]. The highest methanol yield of 3% and the highest methanol selectivity of about 30% were achieved in CHi/02 mixtures. In CHVair mixtures, up to 2% methanol yield was obtained. The partial oxidation of methane is always accompanied by the undesired by-products COx and H20, which were theoretically shown to be the main substances limiting methanol yield. Based on these experimental results our efforts are now directed to plasma reforming of C02 and CH4 to synthesis gas an important intermediate for chemical synthesis. Syngas can then be turned into methanol and other valuable oxygenated components in a second process step. Today steam reforming of methane (CH4 + H20 - CO + 3H2, 229.7 kJ/mol) is the major industrial process for syngas production. The disadvantages are high cost, about 60 - 70% of the total investment cost of the methanol plant, and a resulting H2/CO molar ratio > 3 which is too high for methanol synthesis and for many other synthesis processes. Carbon dioxide reforming of methane, or dry reforming of methane to syngas is considered an attractive reaction with economic and environmental benefits [8]. This highly endothermic reaction (C02 + CH4 -> 2CO + 2 H2, 247 kJ/mol) can be utilised to transfer and store energy (e.g. solar energy or electricity) in the form of CO and H2. Although the conversion of C02 and CH4 to syngas has potential applications in industry it has not yet been practically commercialised. A major problem is the deactivation of the catalyst due to carbon deposition. Recently, the utilisation of plasma techniques for syngas or hydrogen production has attracted considerable attention. With short high voltage pulses DBD processing of C02/CH4 mixtures led to the formation of syngas [9]. In a special GlidArc discharge [10] syngas production from C02/CH4 mixtures was reported with high efficiencies at

Present address: Chemical Engineering Department, The University of Oklahoma Norman. OK 73019, U. S. A.
,

386

atmospheric pressure. Also plasma reforming of methane to hydrogen in thermal plasmas [ 111 has been investigated
recently.

In this study, we used a high power dielectric-barrier discharge to producc synthesis gas with pre-selected arbitrary H2/CO ratios from the two major greenhouse gases C02 and CII4. The discharge is used to establish nonequilibrium plasma conditions in which the major fraction of the electrical energy is transferred to electrons, typically in the energy range of 1 - 10 eV. In dielectric-barrier discharges at about atmospheric pressure the discharge consists of a large number of short-lived microdischarges. The plasma conditions in these microdischarges resemble those of transient high pressure glow discharges and can be optimised for specific plasmachemical reactions [12]. This has, for example, been demonstrated in industrial ozone production in which large-scale DBD configurations are used [13, 14]. The electrons in the microdischarges are heated to high temperatures while the actual gas temperature remains near ambient. Through electron-impact ionisation, dissociation and excitation of the source gas active radicals, ionic and excited atomic and molecular species are generated which in turn initiate the plasmachemical reactions. As a result, considerable amounts of H2 and CO are produced from CII4 and C02 even at ambient temperature and low pressure.
EXPERIMENTAL SET-UP

The experimental set-up was already described in detail [4, 7]. The discharge is maintained in an annular discharge gap of 1 mm radial width and 310 mm length, formed by an outer steel cylinder and an inserted cylindrical quartz tube. The outer steel cylinder serves as the ground electrode and an alternating sinusoidal high voltage of up to 20 kVpp amplitude and about 30 kHz frequency is applied to the centre electrode which is connected to a metal brush pressing a metal foil against the inner surface of the quartz tube.

uartz Tube

Discharge Gap

Ground Electrode

Insulation

Temperature Control

BP
High Voltage Electrode
Fig. 1: Diagram of dielectric-barrier discharge reactor showing the high-voltage feedthrough to the centre electrode on
the left side and a cross section on the right side.

The power supply (Arcotec corona generator CG 20) can feed between 50 W and 1000 W into the discharge reactor. CH4 and C02 are introduced into the reactor from high pressure bottles via mass flow controllers, admitting a total gas flow of 0.1 to 4.0 Nl/min. A back pressure valve and a vacuum pump at the exit are used to adjust the gas pressure in the reactor between 0.1 bar and 10 bar. The pre-selected temperature of the steel ground electrode can be maintained by a closed loop of re-circulating oil from a thermostat between room temperature and 400 C A MTI (Microsensor Technology Inc., M200H) dual-module micro gas chromatograph with a TCD (thermal conductivity detector) is used to analyse most of the gaseous products. A second gas chromatograph (HP 5890A) is connected to detect Hj by a TCD and

to monitor high hydrocarbon products on-line by a FID (flame ionisation detector). As a reference gas a controlled flow of nitrogen is added to the product stream at the exit of the reactor to detect changes of the volume flow due to chemical
reactions in the discharge. This way the mass balances for H, C and O could be established.

387

EXPERIMENTAL RESULTS

Experiments were performed with varying mixing ratio CH4/C02 in the feed at a pressure of 1 bar. A specific electric energy (electric discharge power in [kW] divided by the flow rate measured in [Nm3/h]) of 16.7 kWh/m3 was used. The syngas production from 100 moles feed gas is shown together with the obtained H2/CO ratio as a function of C02

content in feed (Fig 2). The syngas amount reaches a pronounced maximum in gas mixtures containing between 70% and 80% C02. The molar ratio of H2/CO strongly depends on the feed gas composition, varying from about 3.5 to
almost zero.

The required specific energy for the production of syngas was calculated to determine the used electric energy per syngas molecule (H2 plus CO). The lowest energy requirement of slightly less than 40 eV/molecule of syngas was obtained close to the maximum at a C02 content in the range of 70 - 80%. In the product gas, the concentrations of all higher hydrocarbon products decrease with increasing C02 content in feed. In contrast, water production increases with rising C02. CO formation increases with the C02 content in the feed up to 80% and then drops sharply. 02 formation is hardly detected in mixtures containing up to 80% C02. At these operating conditions higher hydrocarbons (C3 - C6)
.

amount totally to less than 1% in the product gas.

20

40

60

80

100

10

15

20

25

30

35

40

45

CO, content In teed (/<J

Specific Input energy (kWh/Nm>)

Fig. 2: Syngas production from 100 moles feed versus C02 content (Power: 500 W; Flow rate: 0.5 Nl/min; Wall temperature: 80C; Pressure: 1 bar)

Fig. 3: Syngas production from 100 moles feed and obtained H2/CO ratio versus specific input energy (Flow rate: 0.2 Nl/min; Wall temperature: 80C;
Pressure: 1 bar; CHVC02 = 30/70)

In a mixture of CHVC02 = 30/70, a discharge power from 0.1 to 0.5 kW was applied resulting in the specific input , energies in the range of 8.3 - 41.7 kWh/Nm at a very low total gas flow of 0.2 Nl/min. In general, increasing the specific input energy leads to an increase in the conversion of CH4 and C02 and the production of syngas. The syngas amount increases almost linearly with the specific input energy (Fig. 3). The molar ratio of H2/CO around 0.5 is hardly dependent on the specific input energy in this parameter range. Other gas mixing ratios yielded other H2/CO ratios, again independent of applied power or flow rate. This way any desired II2/CO ratio between about 3.5 and practically 3 zero can be pre-selected. Very high conversion rates were obtained for high specific input energies. At 87 kWh/Nm 52 moles of H2 and 14 moles of CO were obtained from 100 moles feed CH4/C02 = 80/20 In this case CH4 conversion reached 64% and C02 conversion reached 54%. Under ihese extreme conditions the H2/CO molar ratio eventually increases slightly with specific input energy and carbon deposition and wax formation are observed The gas pressure is normally regarded as an important operating parameter for thermal chemical reactions and electrical discharges. The influence of operating pressure on syngas production is shown in Fig 4. Low pressure clearly favours the conversion of CH4 and C02 to syngas. The H2/CO ratio is practically not affected by changes of the operating pressure. The variation of operating pressure also leads to a change in the gas residence time Therefore, this effect was examined in a separate experiment by varying of total flow rate at a fixed pressure The results demonstrated
, ,
.
.

that the variation of the residence time had no obvious influence on syngas production. It therefore appears that the enhancement of the conversion of CH4 and C02 to syngas at lower gas pressures is due to more favourable discharge
conditions.

The temperature is the most important parameter in thermal reactions The equilibrium calculations demonstrate
.

that normal chemical reactions between CII4 and C02 cannot be expected at temperatures lower than 250C (Fig 5). In endothermal reactions normally high temperatures are required to add enthalpy In our DBD reactor, the conversion of
. .

CH4 and C02 to syngas is a non-equilibrium plasma process Radical reactions in the discharge play the major role in the syngas production. Therefore in this case syngas production proceeds already at low temperatures in the range of 80C. Again, the H2/CO molar ratio hardly depends on the temperature This is true only in C02-rich feed gas mixtures.
.

388

Experiments conducted in CH4-rich feed were hardly reproducible at high specific input energies and high operating temperatures. Wax and carbon production strongly interfered with discharge stability.

80

20
.

/Equilibrium Calculation:
60. 15
.

/ H,CO
4010
.

H,*CO
-

20-

Hyco

Simulation J

HVCO
_ _

05
.

00
.

1 0
.

1.5

200

400

600

800

1000

Pressure (bar)

Temperature ("C)

Fig. 4: Syngas production from 100 moles feed gas versus operating pressure
(Power: 200 W; Flow rate: 0.2 Nl/min;

Fig. 5: Comparison of theoretical and experimental data

(Power: 500 W; flow rate: 0.5 Nl/min; Pressure: 1
bar; CH CO;, = 20/80)

Wall temperature: 80C; CH4/C02 = 20/80)

NUMERICAL SIMULATION

The equilibrium calculations are based on the principle of Gibbs free energy minimisation. Five molecules C02, CH4, H2, CO and H20 are involved in the reactions in which C02 and CH4 arc chosen as the basic components and the rest as products. Equilibrium curves of H2+CO and H2/CO are also plotted in Fig. 5. These computations demonstrate that syngas production by ordinary chemical CH4/C02 reactions starts at temperatures above 250 C and that up to 80 moles of syngas can be obtained from 100 moles of feed gas if the temperature is above 700 C A simplified microdischarge model including 60 species and 353 reactions has been used to simulate the process of syngas production in the discharge. The microdischarges in DBDs are sources of electrons with mean energies high

.

enough to dissociate C02 and CH4 molecules.

e + CH4 -> CH3 + H + e
e + C02 - CO + O + e

(1)
(2)

In a next step the generated CO molecules and H2 molecules formed by recombination of H atoms can also be
dissociated by electron impact.
e + CO e + H, C + O + e 2H + e

(3)
(4)

By integrating the differential equations for the reactions (1) - (4) we get the number density of atoms generated in each
microdischarge:
[CHj] = [H] =
e [CH4| (5) (6) (7)

e [CH4I + a [H2]

[CO] = [C] [O] = =

3 [C02] - Y [CO]
Y [CO] P [C02] + y [CO]

(8) (9)

389

The coefficients e, (3, y and a, corresponding to reactions (1) to (3), and to reaction (4), respectively, are functions of the

electron density generated by one microdischarge and the field dependent rates of the dissociation reactions. In this simulation the microdischarge are simulated as a series of bursts of dissociation products [15, 16]. Fair agreement between experiment and simulation (Fig. 5) was achieved by using following values in the mixture of C02/CHi = 80/20:
a = 4.1 x 10
"

4
,

P = 1.3 x 10*", y = 1-4 x 10"< and e = 0.9 x 10"1. Both experiment and simulation show only a small

temperature influence in the range between 50C and 250C. This is typical for free radical reactions. The most important radicals for the formation of H2 and CO are H and CHO, respectively. The major reactions leading to H2 and
CO formation and destruction in this kinetic scheme and their reaction rates are discussed in more detail in a

forthcoming publication [17].

DISCUSSION

In our DBD reactor, we can produce synthesis gas with an arbitrary, desired H2/CO ratio simply adjusting the mixing ratio of the two greenhouse gases C02 and CH4. Surprisingly enough, for a fixed CH4/C02 feed mixture the H2/CO molar ratio is practically independent of gas pressure and temperature in the reactor and the specific input energy up to a fairly high level. This advantage over catalytic reactions makes the DBD technique very convenient for producing syngas with a desired H2/CO molar ratio. In catalytic syngas production, operating temperatures must be higher than a certain limiting temperature to prevent carbon formation [8]. Plasma assisted conversion of CH4 and C02, on the contrary, takes place at low temperatures and without equilibrium limitation (Fig. 5). No carbon formation was observed in C02-rich feed and no 02 was detected in feed mixtures containing less than 80% C02. These results suggest that the presence of O atoms can avoid carbon deposition. Since the deposited carbon is an active species, it might react with chemically active oxygen atoms to form CO again (C + O -> CO). Strong carbon formation was observed in CH4-rich feed at high specific input energy and high temperatures. We believe that this is mainly due to CO decomposition and total decomposition of CH4. In CH4-rich feed gas mixtures the number of oxygen atoms generated may not be sufficient to fix all deposited carbon. The pronounced maximum in syngas production at a C02 content of 70 to 80% in the feed found in the measurements (Fig. 2 ) is a consequence of synergetic free radical conversion reactions in the C02/CH4 gas mixture. H atoms resulting initially from CH4 dissociation react with C02 molecules and O atoms originally stemming from C02 dissociation react with CII4 molecules to produce this pronounced synergetic effect in the gas mixture. Previous experiments investigating the decomposition products of pure C,H4 and pure C02 in our DBD reactor showed considerably smaller conversion rates [18]. The strong pressure effect exhibited in Fig. 4 is probably at least partly due to changes of the discharge conditions. For a given discharge gap the reduced elcctric field E/n required for electrical breakdown rises with decreasing gas density n. The electron energy, on the other hand, is a monotonously rising function of E/n [12], So we can expect more energetic electrons at lower operating pressure which apparently is beneficial for the dissociation
reactions.

The formation of syngas from a CHVCO2 mixture requires external energy. The highest amounts of H2 and CO

per single pass was obtained at the highest specific input energy used. The best result of required specific energy for syngas production is about 40 eV/molecule of syngas (H2 plus CO) at low specific input energy. As far as H2 production only is concerned, the present required specific energy level in the DBD reactor at this stage is 7 - 10 times higher than that of hydrogen produced by the electrolysis of water. Further improvements with this system to lower the required specific energy may lead to an economic process for the preparation of synthesis gas.
CONCLUSIONS

Conversion of the greenhouse gases CH4 and C02 to syngas was investigated in a high power dielectric-barrier discharge reactor at low temperature and pressure. Our experiments show that surprisingly high conversion rates of C02 and CHi can be obtained in a single pass through our small DBD reactor of 31 cm active length Kinetic simulations with a rather extended reaction scheme show that mainly free radical eactions are of importance Due to these radical reactions there is a strong synergetic effect when C02 and CILt are simultaneously present in the discharge plasma A simplified discharge model combined with the extensive chemical code including 60 species and 353 reactions has been used to simulate syngas production in the discharge. Fair agreement is achieved between experiment and simulation The results demonstrate that DBDs can be used for producing syngas of varying pre-selected H2/CO ratio. The desired
.
.

H2/CO molar ratio can lie between about 3 5 and close to zero. It is primarily determined by the CH4/C02 ratio in the
.

feed gas mixture. Specific input energy gas pressure and temperature hardly influence syngas composition in the absence of carbon formation. The amount of syngas produced however, depends strongly on the electric input energy. For a given discharge power the maximum amount of syngas with low H2/CO molar ratio is produced from a mixture
,
,

containing 70% - 80% C02. The minimum required specific energy was 40 eV/molecule for the production of syngas (H2 plus CO) and the highest energy efficiency (electric energy converted to chemical energy in the syngas) reached so
far was about 7%. Extremely high amounts of 52 moles H2 and 14 moles CO were obtained starting from 100 moles feed gas in a single pass through our DBD reactor in a 80/20 mixture of CH4/C02 at the highest used specific input

390

energy of 87 kWh/Nm In this case CH4 conversion reached 64% and C02 conversion was 54%. According to our experiments CCVrich mixtures prevent carbon and wax formation. Wax formation and carbon decomposition is observed only in CH4-rich feeding mixtures especially at high operating temperatures and high discharge powers. Low operating pressures favour syngas production.
.

This process of plasma reforming of methane with carbon dioxide as an oxygen source offers several advantages over the classical steam reforming process like lower operating pressure and temperature and adjustable H2/CO ratio. So far the specific energy required for the conversion is too high to be of economic interest. It is expected that the use of pulsed discharges will provide the required free radicals at lower energy input.
ACKNOWLEDGEMENTS

Thanks are due to Eric Killer for help with the experiments and to Walter Egli for help with the computations. One of the authors (LMZ) would like to thank ABB Corporate Research Ltd for providing the opportunity to stay as a visiting scientist for 10 months during 1997.
REFERENCES

[1] Bill A, Eliasson B, Killer E, 11th World Hydrogen Energy Conf., Stuttgart, Germany, 1996, II, 1989-1995 [2] Bill A, Wokaun A., Eliasson B, Killer E, Kogelschatz U, Energy Convers. Mgmt., 1997, 38, S415-S422 [3] Eliasson B, Kogelschatz U, Xue B, Zhou L M, 13th Int. Symp. Plasma Chem., Beijing, China, 1997, IV, 1784-1789
[4] Eliasson B, Kogelschatz U, Xue B, Zhou L M, Ind. Eng. Chem. Res., 1998, 37, 3350-3357

[5] Eliasson B, CO2 Chemistry: An Option for CO2 Emission Control? in Carbon Dioxide Chemistry: Environmental Issues, Paul J, Pradier C M, Eds., The Royal Society of Chemistry, Cambridge, UK, 1994, 5-15 [6] Kogelschatz U, Eliasson B, Phys. Blatter, 1996, 52, 360-362 [7] Zhou L M, Xue B, Kogelschatz U, Eliasson B, Plasma Chem. Plasma Proc., 1998, 18, 375-393
[8] Wang S; Lu G Q, Millar G, J. Energy & Fuels, 1996, 10, 896-904

[9] Hibert C, Gaurand I, Motret O, Nikravech M, Pouvesle J M, 13th Int. Symp. Plasma Chem., Beijing, China, 1997,
II, 704-707

[10] Lesueur H, Czernichowski A, Chapelle J, Int. J. Hydrogen Energy, 1994, 19, 139-144 [11] Bromberg L, Cohn D R, Rabinovich A, O,Brien C, Hochgreb S, Energy & Fuels, 1998 12, 11-18 [12] Eliasson B, Kogelschatz U, IEEE Trans. Plasma Sci., 1991, 19, 309-322

[13] Kogelschatz U, Eliasson B, Ozone Generation and Applications in Handbook of Electrostatic Processes, Chang J S,
Kelly A J, Crowley J M, Eds., Marcel Dekker, New York , 1995, 581-605

[14] Kogelschatz U, Eliasson B, Egli W, J. Phys. IV, France, 1997, 7, C4-47-C4-66

[15) Eliasson B, Simon F G, Egli W, Hydrogenation of C02 in a Silent Discharge in Non-Thermal Plasma Techniques for Pollution Control, Penetrante B M, Schultheis S E, Eds., Springer, Berlin, 1993, NATO ASI Series G, 34 B,
321-337

[16] Eliasson B, Egli W, Kogelschatz U, Pure & Appl. Chem., 1994, 66, 1275-1286

[17] Zhou L M, Xue B, Kogelschatz U, Eliasson B, Energy & Fuels, 1998 (in print)

[18] Eliasson B, Kogelschatz U, Killer E, Bill A, 11th World Hydrogen Energy Conf., Stuttgart, Germany, 1996, III,
2449-2459