Gasification of Biomass in Water-Stabilized DC Arc Plasma

M. Hrabovsky1, V. Kopecky1, M. Konrad1, M. Hlina1, T. Kavka1, G. van Oost2, E. Beeckman3, J. Verstraeten3, J. Ledecky4, E. Balabanova5
2

Institute of Plasma Physics, ASCR, Za Slovankou 3, Prague 8, Czech Republic Department of Applied Physics, Ghent University, Rozier 44, B-9000 Gent, Belgium 3 EnviTech S.A., Belgium, 4 Ateko a.s., Hradec Kralove, Czech Republic 5 Institute of Electronics, Bulgarien Academy of Science, Sofia, Bulgary

Abstract Pyrolysis of biomass in thermal plasma was experimentally studied in reactor with dc arc plasma torch stabilized by combination of gas flow with water vortex. Crushed wood was used as a model substance for treatment of organic waste materials. Temperature distribution within the reactor, power balances of the process and composition of produced gas were measured. Synthetic gas with high content of hydrogen and CO was produced. Key words: plasma pyrolysis, biomass, dc arc gas/water plasma 1. Introduction The gasification of biomass to produce synthesis gas (syngas) offers an alternative to fossil fuels. Since syngas contains hydrogen and carbon monoxide, it has the potential to be used as a re-burning fuel to reduce NOx emissions. Common biomass gasification technologies are based on the reaction between a heated carbon source with limited amounts of oxygen and steam. Thermal plasma offers possibility of decomposition of biomass by pure pyrolysis in the absence of oxygen. In the process all energy needed for gasification comes from plasma, no energy for decomposition is produced by combustion. The process acts also as energy storage electrical energy is transferred to plasma energy and then stored in produced syngas. The main advantage is better control of composition of produced gas, higher heat capacity of the gas and reduction of unwanted contaminants like tar, CO2 and higher hydrocarbons. Most of the experiments with plasma pyrolysis have been performed with arc plasma torches with relatively high flow rates of plasma gas. Production of syngas from wood in plasma generated in ac air plasma torches is discussed in [1]. Coal gasification in hydrogen, air and steam plasma was studied in [2, 3]. In [4] wood was gasified in steam plasma. The mean enthalpy of plasma, given by ratio of net arc power to gas flow rate, was usually not higher then 10 MJ/kg [1 - 4]. The high flow rate of plasma ensures good mixing of plasma with treated material. However, produced synthetic gas contains components of plasma gas, usually nitrogen and oxygen if air or nitrogen are used as plasma gases [1, 3]. The usage of mixtures of inert gas with hydrogen [5, 6] eliminates this disadvantage but it increases cost of the technology. Therefore steam was used as plasma gas in [2, 4]. In this paper a dc plasma torch with gas/water stabilized arc, usually applied for plasma spraying, is used [7]. Plasma gas is mixture of steam with small amount of argon. Due to principle of arc stabilization by water vortex the flow rate of plasma gas is very low and plasma enthalpy is more than 200 MJ/kg and mean plasma temperature more than 15 000 K [7, 8]. This is the main difference from gas plasma torches with steam used as plasma gas [2, 4] where temperatures are lower then 4 000 K. The utilization of high enthalpy, high temperature plasma offers advantages in possibility of adjusting high reaction temperature. As low amount of plasma carries high energy, the power needed for heating of plasma to reaction temperature is very low and the efficiency of utilization of plasma power for waste destruction is extremely high. The paper describes first series of experiments in the plasma reactor with high enthalpy gas/water plasma torch designed for destruction of solid waste materials and gasification of biomass. 2. Experimental system The experimental plasma-chemical reactor (Fig. 1) with water-cooling system has been designed to operate at a wall temperature up to 1700 C. The inner lining of the reactor was made from special

refractory ceramics. Ceramic insulation wall with the thickness of 400 mm reduces power loss to the walls. All parts of reactor chamber were water-cooled and calorimetric measurements on cooling circuits were made. The material container was equipped with a continuous material supply system with controlled flow rate. The pressure in the supply conveyer was automatically kept higher then the

Fig. 1. Schematics of experimental reactor for plasma pyrolysis pressure inside the reactor by controlled nitrogen flow to prevent reactor gases flow into the material supply system. Crushed wood was supplied to the reactor and was injected into plasma jet in the position about 30 cm downstream of the input plasma entrance nozzle at the reactor top. It was partially gasified during its flight within the jet, the non-gasified part of the wood falls onto the bottom of the reactor where it was gasified in the hot gas flow. The exit tube for exhaust gas was in the upper part of the reactor, so as the produced gases passed through the zone of high temperature within plasma jet or close to it. Inputs for additional gases for control of reactor atmosphere are at three positions in the upper part of the reactor. Table 1. Experimental parameters Run 1 Arc current [A] 350 Arc power [kW] 95 Steam plasma flow rate [g/s] 0.2 Argon plasma flow rate [slm] 12 Torch efficiency [%] 58 Argon flow rate in anode chamber [slm] 20 Nitrogen flow rate [slm] 4 CO2 flow rate [slm] 23 Power loss to the reactor [kW] 16 Power available for material treatment [kW] 39 Material (wood) mass flow rate [kg/hour] 20 Humidity of treated wood [%] 7

Run 2 450 138 0.25 12 59 33 4 0 18 63 20 7

The gas produced in the reactor flowed through the connecting tube to the quenching chamber, which was created by a cylinder with the length of 2 m. At the upper entrance of the cylinder the gas was quenched by a spray of water from the nozzle, positioned at the top of the cylinder. The water flow

rate was automatically controlled to keep the temperature of gas at the end of quenching chamber at 300 oC. The gas then flows into the combustion chamber where it is combusted in the flow of the air. Plasma was produced in the torch with dc arc stabilized by combination of gas flow and water vortex [7]. The torch generates an oxygen-hydrogen-argon plasma jet with extremely high plasma enthalpy and temperature. The torch is attached to the reactor at the reactor top. The anode of the torch is created by a rotating water-cooled disc, which is positioned outside the arc chamber downstream of the torch exit nozzle [7]. The anode of the torch was thus inside the reactor and it was separated from the reactor volume by a water-cooled wall. Additional argon was supplied into the anode chamber to protect anode from flow of reaction gases. Plasma enters the reactor volume through the nozzle with diameter of 40 mm in this wall.

Fig. 2. Temperatures of reactor wall in several positions (TIZA 101, 103, 104, 106, 107, 108) and temperature of produced syngas at position of gas sample collection (TIZA 105). Measuring system included monitoring of plasma torch operation parameters, temperatures in several positions inside the reactor and calorimetric measurements on cooling water loops. The temperature of inner wall of the reactor was measured in six positions by thermocouples. The flow rate of reaction gas was measured using a Pitot-static tube flow meter, gas temperature was measured at the input and output of quenching chamber. The composition of produced gas was measured at the output of reactor

before the gas enters the quenching chamber. The tube for collection of samples was cooled by the water spray at the input of the quenching chamber. The gas analysisys was made by a quadruple mass spectrometer Balzers QMS 200. As the gas can contain some amount of steam which could after condensation block or damage the inputs of the spectrometer, the freezing unit was connected into the gas sample circuit. 3. Results. Before the experiments the reactor was pre-heated by the gas burner to temperature about 900oC. The results of two runs are presented in this paper. At each run the torch was operated for about one hour. The basic experimental parameters are in Table 1. The flow rate of crushed wood was the same in the both runs, the water content in the wood was 7% of weight. CO2 was added into the reactor in the first run to increase the oxygen content and to reduce production of solid carbon deposits within the system. The temperatures of inner wall of the reactor in several positions during the both runs are shown in Fig. 2. The time of arc ignition corresponds to the sudden steep increase of temperatures at the time t = 1.5 min in the first run and the time t = 5 min in the second run. The time of start of supply of the wood was t = 20 min in the first run and t = 16 min in the second run. The temperature of gas measured at the output of the reactor, where samples for gas analysis were taken, is shown in Fig. 2 as well. The sudden changes of the temperature at the beginning of wood supply were caused by adjusting the thermometers into their measuring position in the center of the exhaust tube. The temperature of gas is somewhat lower then the reactor temperature as the gas was cooled down in the exhaust tube.

3.0E-10 plasma 2.5E-10 Ion current [A] 2.0E-10 1.5E-10 1.0E-10 5.0E-11 0.0E+00 0 10 20 30 Mass [amu] 40 5 wood + 23 slm CO2

Figure 3. Mass spectra of exhaust pyrolysis gas (red) compared with the gas spectrum without material feeding (blue). It can be seen that the differences of temperatures at different positions does not exceed 150oC despite of the fact that the reactor is heated by concentrated plasma jet with high velocity and temperature and low mass flow rate. Natural turbulence of generated plasma jet as well as disturbances of plasma flow caused by the interaction with solid evaporating material ensure strongly turbulent conditions within the reactor and thus sufficiently homogeneous heating of all parts of the reactor volume. After material is injected the temperatures fell down but were stable for the whole time of material feeding. Small differences in temperatures measured in different positions prove good mixing process in the reactor. The temperature increase at the end of the records correspond to reduction of flow rate of material.

Table 2. Composition of gases at the output from the reactor (in volume %) H2 No material fed Run 1 sample 1 Run 2 sample 1 Run 2 sample 2 Run 1 theory Run 2 theory 0.5 46.3 40.6 42.0 44.0 45.9 CO 45.2 43.4 44.3 47.8 45.1 CO2 0.5 1.9 5.3 3.4 0 0 O2 1.3 1.6 2.4 2.5 2.0 0.4 Ar 89.1 5.1 8.4 7.8 5.5 7.9 N2 8.6 0.7 0.7

The example of mass spectrum of exhaust gas compared with the mass spectrum of gas flowing from the reactor without material feeding is shown in Fig. 3. Results of analysis of gas samples are shown in Table 2. The first line gives the composition of exhaust gases in case when only plasma torch was operated. Equilibrium concentrations of reaction products, calculated for experimental flow rates of input substances under the assumption of complete decomposition of cellulose, water and CO2 into hydrogen and carbon monoxide, are shown for the both runs in the last two lines of Table 1. It can be seen that in the both cases almost complete decomposition of wood into mixture of hydrogen and carbon monoxide occurred, the concentration of CO2 was only several percent. Argon concentrations correspond to the flow rate of argon into the torch and the anode chamber, flow rate of nitrogen corresponds to amount of nitrogen in pressure control input of the material feed conveyer. The results show that all material was decomposed in the reactor and thus sufficient heat transfer takes place in the reactor between flowing plasma, solid injected material and produced gases.
5.00E-01 4.50E-01 4.00E-01 3.50E-01 Mole fraction 3.00E-01 2.50E-01 2.00E-01 1.50E-01 1.00E-01 5.00E-02 0.00E+00 300 800 1300 1800 Temperature, K 2300 2800
Ar H H2 H2O CO CO2 CH4 C-SOL

Fig. 4. Equilibrium composition of mixture of cellulose (1 mol) and water (1 mol) in dependence on temperature calculated using code ASTRA. For comparison, the temperature dependence of composition of mixture of 1 mol of cellulose with 1 mol of water, which approximately corresponds to the test conditions, calculated under the assumption of existence of thermodynamic equilibrium using the computer code ASTRA, is shown in Fig. 4. It can be seen that for temperatures above approximately 1000oC the reaction gas is composed mostly from mixture of hydrogen with CO with small percentage of CO2, steam and argon.

4. Conclusions. The plasma reactor for pyrolysis of waste was operated with wood used as a model substance. High enthalpy, low plasma flow rate plasma jet generated in hybrid gas/water torch was used as a source of plasma. The experiments prove that homogeneous heating of volume of plasma reactor and proper mixing of plasma with treated material were ensured despite of very low plasma mass flow rate. The conditions within the reactor ensure complete destruction of tested substance. Synthetic gas with high content of hydrogen and carbon monoxide and low concentration of carbon dioxide with high caloric value was produced. The concentration of hydrogen is higher than the maximum values reported for classical treatment of biomass. The main advantage of use of plasma torch with water-stabilized arc is in composition and low flow rate of plasma. The content of other gases commonly present in gas stabilized systems is very low. In further experiments the effect of experimental conditions on mass and energy balances of the process will be studied. Acknowledgement The authors gratefully acknowledge the support of this work by the Grant Agency of the Czech Republic under the project No. 202/05/0669. References [1] Rutberg P.G., Bratsev AN, Ufimtsev AA, Plasmochemical technologies for processing of hydrocarbonic raw material with syngas production, J. of High Temp. Mat. Process. 8 (2004), 3, 433-446. [2] Mikhailov B., Plasma gasification of coal, Thermal Plasma and new Materials Technology, ed. O.P. Solonenko, M.F. Zhukov, Vol. 2, Cambridge Interscience Publish., 1995, 345-369. [3] Zasypkin I.M., Nozdrenko G.V., Production of acetylene and synthesis gas from coal by plasma chemical methods, Thermal Plasma Torches and Technologies, Vol II., ed. O.P. Solonenko, Cambridge Interscience Publish., 2001, 234-243. [4] Kezelis R., Mecius V., Valinciute V., Valincius V., Waste and biomass treatment employing plasma technology, J. of High Temp. Mat. Process. 8 (2004), 2, 273-282. [5] Zhao ZL, Huang HT, Wu CZ, Li HB, Chen Y., Biomass pyrolysis in an argon/hydrogen plasma reactor, Chem. Engineering & Technology 24 (2001), 11, 197-199. [6] Zhao ZL, Plasma gasification of biomass in a downflow reactor, Abstract of Papers of the American Chemical Society 226: U536-U536 048-FUEL Part 1, SEP 2003. [7] V.Brezina, M.Hrabovsky, M.Konrad, V.Kopecky, V.Sember, Proc. 15th Int.Symp.on Plasma Chemistry, Orleans, 9-13 July 2001, Vol.III, p. 1021-1026.