DRAFT Hydrogen Manufacturing Using Plasma Reformers C.O’Brien ** DR. Cohn* L. Bromberg* S. Hochgreb** A. Rabinovich » ce a en fida 3 sain tn op AE Bt amen oe so oul emp ese ands 6 oe = Riera you Asda ou pan oe) say 2 PD aa a Ae oy top samr 0 wots mn 20) CHE soe to oan me sn me n> a Sets Su mn rs Pm ZN, HR 2 7 A erg prods om J sce ve psa 8 HL! SAL waWIVDSIC c B wn <= 5 £8 we = 3 5e gs saa Bae | ges 23 Es ges ang 3 ges 223 5 238 Shy 3 eas 25 3 Aue aus 3 3 ga = Fae a 3 3 fas = le \ ‘TE, DISTRIBUTION OF THIS DOCUMENT IS UNLE.‘TABLE OF CONTENTS 1. INTRODUCTION... 1.1. MOTIVATION. 1.2. PREVIOUS WORK 2.1, HYDROCARBON PYROLYSIS IN THERMAL PLASMAS... 2.1.1. Equilibrium. 1.3. Quenching ise wenn 2.1.4, Laboratory experiments 2.1.5, Large-scale experimen 2.1.6, Production of carbon black and hydroger 2.2, OXIDATION OF HYDROCARBONS IN PLASMA.. ‘Thermodynamics of C ~ H -O system. Kinetics of hydrocarbon oxidation in plasma. Experimental investigations of hydrocarbons oxidation in plasma. 2.3. REFERENCES 3, DESIGN OF PLASMATRON AND REACTOR... 4,1, RESEARCH PLASMATRON CHARACTERISTICS 4,2, CONVERSION RESULTS. ‘5, MODELING: EQUILIBRIUM. 5.1, INTRODUCTION ‘5.2, FUEL REFORMING AS PART OF THE ENERYG CYCLE, 5.3. AVAILABLE ENERGY AND REFORMING EFFICIENCY. 5.4, ANALYSIS OF THE INITIAL PARAMETER SPACE. 5.5. THERMODYNAMICS EFFICIENCY OF THE REFO! 5.6. REFERENCES, 6. MODELING: CHEMICAL KINETICS. 6.1. INTRODUCTIO? 62. PLUG FLOW REACTION PROGRESS CALCULATIONS 633, PERFECTLY STIRRED REACTOR MODEL OF THE PL 64, COMPARISON WITH EXPERIMENTAL RESULTS 64.1. Plug flow reactor calculations. 64.2. Perfectly stirred reactor calculations. 6.5. REFERENCES.7. ENERGY ANALYSIS. 7,1. FUEL CELL APPLICATION 7.1.1. Plasma Reformer-Fuel Cell Systems. 7.1.2. Partial Oxidation without heat recovery. 7.1.3. Partial Oxidation with heat recovery. 7.1.4. Comparison Between Reforming Technologies 7.1.5. Conclusions. 17.2. REFERENCES. 8, FUTURE DIRECTIONS... 83. MODELLING.. 84, SYSTEM ANALYSIS 85. SCHEDULE.1. Introduction 1.1. MOTIVATION ‘Manufacturing of hydrogen from hydrocarbon fuels is needed for a variety of applications. These applications include fuel cells used in stationary electric power production and in vehicular propulsion. Hydrogen can also be used for various combustion engine systems. ‘There is a wide range of requirements on the capacity of the hydrogen manufacturing system, the purity of the hydrogen fuel, and capability for rapid response. The overall objectives of a hydrogen manufacturing facility are to operate with high availability at the lowest possible cost and to have minimal adverse environmental impact. Plasma technology has potential to significantly alleviate shortcomings of conventional means of manufacturing hydrogen. These shortcomings include cost and deterioration of catalysts; limitations on hydrogen production from heavy hydrocarbons; limitations on rapid response; and size and weight requirements. In addition, use of plasma technology could provide for a greater variety of operating modes in particular the possibility of virtual elimination of CO; production by pyrolytic operation, ‘This mode of hydrogen production may be of increasing importance due to recent additional evidence of global warming. 1.2, PREVIOUS WORK Research on plasma production of hydrogen-rich gas has been carried out by Rabinovich and co-workers in the former Soviet Union using both steam reforming and partial oxidation [1,2] and by Kaske using steam reforming [3]. Scoping level studies have been performed for steam reforming, partial oxidation, and pyrolytic plasma reformer-fuel cell systems [4]. There is also industrial work on large-scale plasma manufacturing fromnatural gas in Sweden [5]. However, studies of factors affecting plasma power requirements, a key aspect of economic attractiveness, have not been discussed in the scientific literature. Hydrogen gas purity levels and pollutant generation (such as NOx production) have also not been discussed. 1.3. EFFORT IN FIRST YEAR In the first year of the program supported by the Advanced Utility Concepts Division, Office of Renewable Energy, Department of Energy, we have advanced the state of knowledge in the following areas: Plasma reformer design concepts (including both arc plasma and microwave plasma. technology for a range of applications). ‘© Chemical equilibrium and kinetics calculations for different modes of plasma reformer operation, ‘© Construction of experimental plasma reformer devices. ‘© Initial tests of experimental plasma reformer devices. «Energy system analysis of methane plasma reforming, with partial oxidation, steam reforming and pyrolysis. his report describes progress in these four areas and discusses directions for future work. The work has concentrated during this first year to the study of methane. Itis important to look at methane because it is relatively simple to model, easy to test (since it is gaseous) and easy to identify in the analytical instrumentation. We can obtain a great deal of insight by studying methane. Furthermore, the present level of understanding of pyrolysis of heavier hydrocarbons is that the plasma decomposes very rapidly the heavy hydrocarbons into lighter ones. The conversion of the lighter hydrocarbons are the rate limiting processes.1.4, REFERENCES [1] Rudjak, E. M., Rabinovich, A., and Tul, N. A. (1979), USSR Patent 700935, "Water Plasmatron,” Aug. {2].Shabalina, R. 1, Rabinovich, A., and Panfilov, S. A. (1989), "Slag Cleaning by Use of Plasma Heating," Proceedings of Symposium on Extraction Metallurgy, London, U.K, p. 89, July. [3]-Kaske, G. L., Kerke, L., and Muller, R. (1986), "Hydrogen Production in the Huls Plasma-Reforming Process," Hydrogen Energy Progress VI, 1. [4] Bromberg, L., Cohn, D. R., and Rabinovich, A., "Plasma Reformer/ Fuel Cell Systems for Decentralized Power Applications," to be published in Int. Journal of Hydrogen Energy. [5].Bromberg, L., Trip Report, July 1995.2. Review of Previous Work In this section the results of previous investigations of hydrocarbon processing in thermal plasmas are discussed. The literature of three types of plasma processing of hydrocarbons are reviewed: pyrolysis (nothing added to the fuel), partial oxidation (with air) and steam reforming (with water). Early studies were begun in the early 60s , peaking in the mid 70s. At that time the scientific and technical fundamentals of hydrocarbon processing in thermal plasmas were established. Pilot scale and semi commercial plants were been constructed. In succeeding years, interest in plasma hydrocarbon processing eroded and few large scale commercial applications exist now. A substantial amount of the work in the literature originated in the former USSR. In the ‘West, the work was carried out by industry, and little of it is in the open literature, We thank Dr. N. Alexeev, from Institute of Metallurgy (Russian Academy of Science) for providing an account of previous work in the USSR. During the first year of the program the experiment and modeling has been limited to partial oxidation of methane. The use of heavier hydrocarbons in the experiment will take place during second year of the program. There are several reasons to study the conversion of hydrogen, even if other techniques exist for its reformation. First the process is relatively easy to model, the experiments are easily carried out since methane is ‘gaseous (the difficulty of vaporizing the liquids are avoided), and the instrumentation is easily prepared ( both GC and FTIR), The study of methane will therefore provide a great deal of insight into the hydrogen manufacturing process. ‘Because equilibrium calculations are easily performed, it is important to determine under what conditions they are applicable, Discussions for the relevance of equilibrium andKinetic calculations to pyrolysis and partial oxidation of hydrocarbon fuels are described in this section. 2.1. HYDROCARBON PYROLYSIS IN THERMAL PLASMAS A large amount of work has been done on the plasma pyrolysis (thermal decomposition) of hydrocarbons. The main application of hydrocarbon plasma processing in the recent past has been indeed for the manufacture of acetylene from natural gas. However, even though in this program we are not interested in acetylene manufacture, this work is relevant for the pyrolysis of hydrocarbons for the production of hydrogen. One of the ‘main difference is the need of quenching for acetylene manufactured. We will start pyrolysis experiments with methane and heavier hydrocarbons towards the end of the second year of this program. In this section, a summary of previous work in this area is presented. Research in this area was driven by industrial production of acetylene and carbon black (similar to the pyrolytic production of hydrogen, but with an emphasis on the production of high quality carbon black). 2.4.4. Equilibrium Calculations of equilibrium and quasi-equilibrium (in the absence of solid carbon) compositions of C-H system make possible to obtain the theoretical characteristic of the following plasma processes: * production of acetylene, ethylene and hydrogen from hydrocarbons; * production of acetylene from carbon and hydrogen; production of methane and other hydrocarbon gases from coal © production of carbon and hydrogen from hydrocarbons.AA large amount of the investigation of hydrocarbon processing in thermal plasmas has been for the production of acetylene (C;Hz). Acetylene production is maximized in the temperature range 2000-3000K.[1]. Work in the USSR and in the West concentrated in the minimization of the energy consumption of the procéss.{2}. Iti difficult to model the plasma process. Equilibrium composition depends on the assumed compounds that are present. In reality, because some of these require reaction times that are longer than the residence time in the reactor and special processes after reaction (such as quenching), itis possible to prevent the formation of several final products. For example, soot formation requires nucleation, particle growth and agglomeration steps that have long time constants. In C-H systems, hydrogen and acetylene are the predominant components system calculated without including condensed carbon and aromatic hydrocarbons [1]. This fact is in good agreement with experimental results of hydrocarbon pyrolysis in the plasma reactors with quenching devices. Methane and aromatics (benzene, and higher aromatics) are the basic hydrocarbons in the 4uasi-equilibrium composition of C-H system at the temperature up to 1600 K if condensed carbon is eliminated from the list of components [3]. At higher temperatures acetylene dominates. ‘The temperature of maximum conversion into acetylene and ethylene peaks has been reported as 2000 K. In addition to the hydrogen present in the products, the acetylene from the system is diluted by other light hydrocarbons (ethylene, propylene). Increasing the C/H ratio leads to a rise in conversion to acetylene,‘The energy consumption for acetylene depends on the starting hydrocarbon, as well as on the hydrogen/carbon ratio. It has been determined that the energy expenditure decreases with increasing hydrocarbon weight and with increasing C/H ratio [1]. Calculations of pyrolysis of dirty fuels (commercial grade oils containing sulfur) in thermal plasmas with quasi-equilibrium modeling has been carried out in reference [6]. 2.1.2. Macrokineties ‘There has been substantial experimental work devoted to the investigations of mechanisms and kinetics of thermal hydrocarbons pyrolysis at the temperature below 1000 K (of interest for combustion). However, the problems of high temperature kinetics have not been adequately studied. But some experimental and theoretical investigations make possible to estimate time-variation of product composition under plasma pyrolysis of hydrocarbons. The thermal decomposition of hydrocarbons at temperatures higher than 1000 K can be considered as a sequence of reactions [7]. Unsaturated hydrocarbons are intermediate products, carbon and hydrogen are end-products. As-the temperature increases, the contribution of chain reactions decreases, with radical and molecular reactions becoming predominant. ‘Modeling the kinetics of heavy hydrocarbons has been simplified substantially with the assumption that the heavy hydrocarbons are rapidly decomposed to a mixture of CH, CaH,, CoH, and Hy. The initial phase of hydrocarbons decomposition (alkanes higher than ‘methane, unsaturated series, aromatic series) has only a small effect on pyrolysis kinetics at the plasma temperature because the decomposition time of initial hydrocarbons is less than the time of CHs, C2H and C,H, conversion. Then reactions occur through the mechanism of L-Kassel [8]: 10© CHy->CHztHh, © CH:+CH,->CoHs, © CHe->CoHy+He, © CHy->CoHe+He, © CHy->2C(s)+Hb. ‘The ratio of the intermediate products CHy:C,Hy:C,Hi:He must be calculated properly, for each hydrocarbon [7]. Calculations of kinetics of CH, and C;Hg pyrolysis in plasma have been carried out in [1,2,7,9-14]. Kinetic calculations of gas-condensate and gasoline under plasma pyrolysis, have been carried out in [7,13,14]. Instant reagents heating and mixing were assumed, heat transfer in the reactor and in the quenching device were taken into account, ‘The heat transfer in plasma reactors markedly affects pyrolysis kinetics. Typical heat transfer rates in plasma reactors may be as large as 1 x 10°- 1 x 10” K/s. Such high heat transfer rates can be used for effectively quenching the plasmatron exhaust for acetylene production. 2.1.3. Quenching issues ‘The models predict the composition of the reformate at the reformation temperature. Since the gases will be used at lower temperatures, itis necessary to address the possible conversion of the products during the cool-down process. For some processes, it is necessary to rapidly decrease the temperature, accomplished by quenching. In practice, the quenching is usually accomplished by use of a coolant injected into the hot gas. The quenching coolant could be a hydrocarbon, and the quenching process happens with additional conversion of the quenching hydrocarbon, in a two-step process. nThe kinetics simulation of plasma hydrocarbon pyrolysis has shown that quenching with a rate of 5 10° K/s is required for acetylene production. The quenching "turn on" time is, about 1 10% at the process temperature of 1800 K. Pyrolysis of supplementary injected hydrocarbons may be carried out at this temperature. The authors in reference [10,11] have calculated the kinetics of these two-step pyrolysis, process. The time of additional hydrocarbon injection, amount of additional hydrocarbon and its composition was parametrized. It was presumed that the mixing and decomposition of the additionally injected hydrocarbon occurred instantly as well as an instant adiabatic decrease in the gas temperature as a consequence of injecting the cooler hydrocarbons. This results in higher yields and lower energy consumptions as compared with a single step process. 2.1.4, Laboratory experiments A wide range of experimental investigations of hydrocarbon pyrolysis in plasma have been carried out mainly in the former USSR and in the West during the 70's. ‘The following hydrocarbons were used as raw materials: © methane (1,12,16,17,24]; © natural gas [24]; propane [1]; © propane-butane mixture [4]; * mheptane [4]; ‘© gas-condensate [13,14]; © gasoline [4,6,18-21]; © gascil [6,15]; © oil [6,15,21-23}. © coal (55]Raw materials were injected into the plasma jet, which operated mostly in hydrogen [10, 25-28]. Hydrogen is the most useful plasma forming gas for hydrocarbon pyrolysis. It has ahigh enthalpy, hydrogen is one of the reactions products, and the addition of hydrogen inhibits carbon formation. The authors in reference [2] obtained experimental data on reactor length dependence of composition of the final products of gas-condensate pyrolysis in plasma. A heat exchanger was used for quenching the final products. Quenching rate was estimated to be 1-5 x 10°K/s. There was a good agreement between experimental and calculated data for methane plasma pyrolysis as well as a reasonable agreement for gas-condensate pyrolysis. Experimental data showed relationship between conversion into acetylene and the following process parameters: ‘© initial plasma temperature (enthalpy); ‘reaction time; ‘© raw materials composition and feed rate; quenching techniques. Under these conditions conversion into acetylene and ethylene was high (~ 80%). The total energy consumption was determined for both methane and liquid hydrocarbons (oil and gasoline). ‘The energy consumption for the liquid hydrocarbons was about half that of methane, Oil pyrolysis in hydrogen was investigated by authors in reference [23]. The effect of operating pressure was also investigated. Increasing the process pressure diminishes acetylene production under plasma pyrolysis [13,16,17]. 2B‘The temperature dependence of the concentration in the final product of unsaturated hydrocarbons (methyl-, vinyl-, diacetylene, butadiene, propadien and butylene) was investigated in reference [29]. These components are undesirable impurities in the production of acetylene. Concentrations of these compounds varied in the range of 0.1 - 14%, Plasma pyrolysis of highly viscous waste was carried out with the use of submersible type plasma reactor equipped with 15 KW hydrogen plasma generator. Conversion of organic compounds were close to 100%. Pyrolysis processing of heavy tars produced in ethylene manufacture using a 30 kW plasma unit as been investigated [47]. Finally, processing of cotton waste was reported in reference [50]. Initial heating of the raw material improves process characteristics. According to reference [16}, initial natural gas heating to 500 C makes possible to increase conversion into C>H2 and to decrease energy consumption to 25% under natural gas pyrolysis in Hy and CH, plasma, 2.1.5. Large-scale experiments ‘The results of large-scale research and development of hydrocarbon pyrolysis in plasma are discussed in this section. The experiments were carried out in 1000 KW plasmas (20,24). Various designs of plasma generators and plasmochemical reactors were tested. ‘The following DC arc plasma generators were used: plasma generators with the hollow copper electrodes for heating of hydrogen and hydrogen-methane mixtures; plasma generators were designed as single-jet and two-jet devices; «plasma generators with tungsten cathode; - plasma generators with consumable graphite electrodes. 4Plasma reactors with both jet and whirling mixing devices were used. The best results ‘were obtained with the use of plasma generators with tungsten cathode and whirling mixing. To avoid carbon deposition on the reactor wall, liquid film protection was tested (22). ‘The basic results of acetylene production from natural gas in a hydrogen plasma are shown in Table 2.1. Table 2.1. Inlaboratony] Large-scale Plasma power ew 20-30 930 (Current IA 200-300 | 450-700 " [Plasma generator efficiency _[% 70-80_| 85-80 [Conversion to acetylene _[% 70-80_| 65-85 [Gas content| ie vol ‘acetylene TE5-165 | 120-145 methane 3 20-120 hydrogen: 750-600 | 70.0-62.0 [Energy consumption IKWhikg C2H2|_9.0-10.0 | 100-105 [Natural gas Consumption —_[maikg C2H2 | _ 2.1 24-23 Results of large-scale gasoline pyrolysis in hydrogen plasma are given in references [18- 20]. A 1500 kW plasma reactor was used. Equipment for acetylene production consisted of the plasma unit followed with gas treatment systems. Gasolines with boiling temperature from 35C to as high as 165 C were used as raw material. Hydrogen and hydrogen-methane mixtures were used as the plasma gas. The process characteristics are shown in Table 2.2 Table 22 [C2F2 concentration (vou.%) 3-17 [C2H4 concentration (vol) 9-12 raw material conversion (2) 26-98 [conversion into C2H2+C2H4 __|(%) 755 lenergy consumption (kWhiikg C2HO2H4) 69 18‘After clean up, the gas product met the requirements for chlorine-organic compounds synthesis. Plasma reforming of light hydrocarbons (methane and natural gas) has been used in the Huls process [53] for the manufacturing of acetylene, ‘These systems are intended for industrial manufacturing of acetylene and were large, heavy, and not transportable. The Huls plasma processing has been investigated for the manufacturing of Hz by the steam- reforming of methane [52]. Large systems have been built (initial pilot experiments with a 50-5S0OKW system), with the goal of larger ones. Their reformate gas mixture, optimized for acetylene production (by operating at high gas temperatures), contains more than 60% hydrogen, 17% acetylene, and 7% ethylene. Due to the manufacturing of acetylene and the high temperatures, the process is strongly endothermic and requires large heat input. Higher hydrogen yields can be achieved by operating at lower temperatures (resulting in less acetylene and ethylene). The temperature of the reactor can be controlled by adjusting the plasma power, the gas throughput and the operating pressure, among others. ‘Moreover, by increasing the hydrogen concentration in the starting reagents (by, for example, recirculating excess hydrogen from the fuel cell), significant narrowing of the temperature range where condensed carbon and acetylene exists can be obtained. A further method of control is through the use of two step reactors, as described above. In the first step the plasma produces a high enthalpy gas that is used. to process a fluid introduced in a second step. ‘The plasmatron may, for example, operate with water, with the hydrocarbons injected downstream. Hydrogen yields (65% He, 35% CO) larger than those from the Huls process have been demonstrated by the work of Rudiak [54]. In the United States, AVCO has developed a process for converting coal to acetylene using an electric arc. A 1 MW prototype production reactor has been built. The system. include an active hydrocarbon quench to improve the overall process efficiency. The specific energy consumption using a propane quench was 6 kWhr/kg CsH+C;Hs ‘The coal feed rate was about 0.25 ton/hr. 162.1.6. Production of carbon black and hydrogen. Carbon black and hydrogen are formed under hydrocarbons pyrolysis in plasma in the absence of quenching. Carbon black produced in plasma is of excellent quality. Kinetics of carbon black formation from methane in an argon plasma jet was simulated by the authors of reference (30). The results were compared with an experiment. It was assumed that carbon black formation involved the following phases: thermal decomposition of hydrocarbon molecules to carbon vapor and hydrocarbon radicals; nucleation; particles growth from vapor and coagulation. [31] Kvaerner (Norway) is performing development work on the pyrolysis of natural gas and on the production of carbon black from aromatics using DC arc plasma technology. In collaboration with a company in Sweden (ScanArc, previously SKF), they were able to go directly to this scale size. ScanAre is well known in the plasma thermal processing industry. Kvaerner, at ScanArc's site in Hofors, has built a3 MW system for the manufacturing of hydrogen [56]. They utilize graphite electrodes in a nontransferred are configuration. They claim to have manufactured 99.5% hydrogen gas (the rest being a combination of hydrocarbons) when using natural gas. Since there is no natural gas in Sweden, their feedstock for the pilot plant is imported and stored in large tanks in the plant. They have been secretive about their process and did not release a schematic diagram of the plasma device or of the flows. However, they have assembled a complete system, with bag-houses for the removal of the dust and with systems for the purification of the hydrogen gas. Their process produces hydrogen with high enthalpy, utilizing 2 kWhr/m3. This number is comparable to the hydrogen heating value and therefore would be an inefficient manner of producing hydrogen to be used as fuel. This high enthalpy would be useful in application Wwhere a reducing gas with high enthalpy is needed, such as steel making (ore or dust. processing). Experiments will be carried during the second year of this program to investigate the pyrolysis of hydrocarbon fuels in a thermal plasma, and of methods for increasing the purity and decrease the energy consumption. 2.2. OXIDATION OF HYDROCARBONS IN PLASMA 2.2.1. Thermodynamics of C - H- O system. Calculations of equilibrium compositions of hydrocarbon conversion (CH, CaHls, CsHs and CnHzn) by water vapor and carbon dioxide were carried out at the temperature in the range of 400-6000 K and at the pressure of 0.1-3 MPa [39]. The C/O ratio was varied from 1 to 0.67. ‘The calculated equilibrium compositions of liquid fuel conversion by air, water vapor and carbon dioxide at the temperature of 500-5000 K, at pressures of 0.1-100 MPa under various fuel/oxidizer ratios were investigated in reference [42]. 2.2.2. Kinetics of hydrocarbon oxidation in plasma. A chain radical mechanism was suggested in reference [39] to describe the reaction of methane and water vapor or carbon dioxide in a plasma reactor. Oxidation of unsaturated ‘compounds was not included into the mechanism. Methane conversion in dissociated carbon dioxide under adiabatic conditions occurred in about 1 x 10* s at carbon dioxide temperature of 3500 K. 18‘The reaction times of liquid fuel droplets in the plasma jet of oxidizer were estimated in [42]. The following effects were include: © distribution of fuel droplets in the plasma jet, * droplets evaporation, mixing of vapors with oxidizer. The chemical mechanism included: ‘* Decomposition of initial hydrocarbons, ‘* formation and decomposition of formaldehyde and acetylene, ‘© carbon black formation and its gasification, It was determined that methane conversion to acetylene and carbon black gasification were the rate-determining phases of the process at 1500 K. At 3000 K mixing and carbon ‘gasification were the rate-limiting processes. To prevent carbon black formation it was suggested to provide fuel decomposition up to 1300 K in the outer regions of the plasma jet. Decomposition of fuel at such temperatures occurs without formation of fully oxidized compounds. The kinetics of the formaldehyde formation from methane and oxygen mixtures in plasma reactors was simulated in [40]. 2.2.3, Experimental investigations of hydrocarbons oxidation in plasma, There are only a few references that cover the conversion of methane or natural gas in an air plasma, It is not necessary to use air as the source of oxygen in the experiments. Other commonly used sources of oxygen are CO and H:0. 19Conversion of methane and propane-butane mixtures in COz and HO plasma jets was investigated in reference [39,41]. Hydrogen and carbon monoxide were the predominant ‘components in the reaction products at the temperature of the plasma jet (2400-3600 K), with smaller amounts of Czlf:. We propose to investigate the reforming of hydrocarbons using a steam plasma, (steam reforming). Higher hydrogen yields are obtained in this manner pre unit fuel (as compared to partial oxidation and pyrolysis) although at higher energy consumptions. Complete conversion of natural gas into Hz and CO mixture was achieved with high enthalpy CO; plasmas [39]. They also tested a water vapor plasma, and found that the energy consumption rose slightly. The effect of using different hydrocarbons as the feed ‘material (propane and butane) was also investigated. They concluded that the energy consumption decreased by 5-10% as compared to natural gas. Conversion of diesel fuel with overall element composition C2,1Fls9s by air-water vapor mixture was investigated in reference [42]. The temperature of the plasma jet was in the range from 2400 K to 3500 K. The fuel was atomized into the plasma jet by a atomizer. Benzene pyrolysis in the system Ar-Ny-CHg-H,O was investigated in reference [51]. A 10 KW DC plasma generator was used, Benzene was injected into the plasma as droplets, water was fed as a vapor. Feed rates of raw materials were in the range of: 2-6 g/min CoHis, 3-12 g/min H,O, 10-13 g/min Ar, 1-3 g/min Np. ‘The reaction of methane with oxygen for the purpose of formaldehyde production were investigated in an argon plasma jet [40]. The temperature dependence of the product composition was determined.2.3. REFERENCES 1, Suris A.L. “Plasmochemical processes and apparatuses”, M., Khimiya, 1989 384 p. (in rus.) 2. Polak L.S., Ovsyannikov A.A., Slovetski D.L, Vursel FB. "Theoretical and applied plasmochemistry” M., Nauka, 1975, 304 p. (in rus.) 3. Slin'ko L.E., Vursel F.B., Valibekov Yu.V., Gutman B-E. Dokladi AN TadgSSR, 12, 1973. (in rus.) 4, Vursel F.B., Polak L.S. "Acetylene and olefins production from some hydrocarbons and gasoline" Sb. Kinetika i termodinamika khiicheskih reaktsii v nizkotemperaturnoi plasme. M., Nauka, 1965, p.100-117. (in rus.) 5. Nursultanov O.S., Polak L.S., Popov V.T. "Generalization of characteristics for hydrocarbon pyrolysis in plasma," Khiiya visokih energii, v.8, 5, 1974, p.401-40S. (in rus.) 6. Volodin N.L., Vursel F.B., Polak L.S., Endyuskin P.N. "Gasoline pyrolysis in plasma," Sb. Nekotorie voprosi neftekhimicheskogo sinteza, Ufa, 1970, p.11.; Fizika i primenenie nizkotemperatumnoi plasmi. Alma-Ata, 1970, p.576-578. (in rus.) 7, Valibekov Yu.V., Volodin N.L., Vursel F.B. "Macrokinetics of hydrocarbons and chlorohydrocarbons pyrolysis in plasma," Khimiya visokih energii, v.9, 1, 1975, p.55-62. (in ms.) 8. L. S, Kassel. J.Amer.Chem.Soc., 54, 3949, 1932, 9. Suris A.L., Shorin S.N. Tezisi doklada na Vsesoyuznoi konferentsii "Poluchenie atsetilena iz. prirodnogo gasa", Severodonetsk, 1968. (in rus.) 10. Gershuni $.Sh., Suris A.L., Shorin S.N., Alexeev N.V. "Investigation of acetylene production from natural gas in plasma under quenching by heavy hydrocarbons," Khimiya visokih energi, v.9, 1, 1975, p.63-69. (in rus.) 11. Vursel FB., Polak L.S., Epstein LA. "Kinetics of hydrocarbon pyrolysis in plasma,” Khimiya visokih energii, v.9, 2, 1975. (in rus.) 12, Kobzev YuN., Kozlov GL, Hudyakov GN. "Processing of natural gas into acetylene, hydrogen and carbon black," Preprint IPM AN SSSR i ENIN im. Krgiganovski, M. 1974, N 48. (in rus.) 13. Vursel F.B., Valibekov Yu.V., Gutman B.E., Polak L.S. Khimiya visokih energii, v.7, 3, 1973. (in rus.) 214, Priimak A.D., Valibekov Yu.V., Pathomenko V.D., Polak L.S. "Characteristics of reaction of gas condensate with nitrogen at high temperature," Tez. dokladov Vtorogo soveshaniya po plasmokhimicheskoi tehnologii i apparatostroeniyu, M., v.1, p.213- 214, 1977. (in rus.) 15, Volodin N.L., Vursel FB., Dyatlov V-T., Polak L.S., Shmikov Yu.l. "Gas oil pyrolysis in plasma," Khimiya visokih energii,v.5, 3, 1971, p.280-282, (in rus.) 16, Kobzev YuN., Hudyakov GIN. "Influence of natural gas preheating on acetylene production in plasma jets," Plazmokhimiya - 71, M., INHS AN SSSR, 1971, p.155. (in mus.) 17. Kozlov G.L, Hudyakov GN., Kobzev Yu. "Investigation of acetylene production from methane in hydrogen plasma jet at normal and high pressure," Neftekhimiya, v.7, 2, 1967, p.224-231. (in rus.) 18, Tuhvatullin A.M., Volodin N.L., Rudzit RR., Shmikov Yu.L, Zubairov RR. "Development of process for acetylene and ethylene manufacture by gasoline pyrolysis plasma with the use of pilot plant 1.5 MW in power," Tez. dokladov Vtorogo soveshaniya po plasokhimicheskoi tehnologii i apparatostroeniyu, M., v.1, p.237-240, 1977. (in tus.) 19, Shmikov Yu.L, Shorin $.N., Suris A.L., Volodin NL., Izenger Yu.V., Rudzit RR. “Investigation of acetylene and ethylene production from gasoline on plasma setup 1.5 MW in power," Tez. dokladov Vtorogo soveshaniya po plasokhimicheskoi tehnologii i apparatostroeniyu, M., v.1, p.241-243, 1977. (in rus.) 20. Onis'kova 0.V., Chislovski V.V., Martsevoi E.P., Karp IN. "Reactors for acetylene production in plasma," Tez. dokladov Vtorogo soveshaniya po plasokhimicheskoi tehnologii i apparatostroeniyu, M., v.1, p.241-243, 1977. (in rus.) 21. Polak L.S. "Production of acetylene and olefins for chemical industry," 8th Oil Congress. Discussion Symposium 18. M., 1971, p.40.(in rus.) 22. Mosse A.L., Zabrodin V.K., Krilova I.A. "Investigation of oil pyrolysis in methane- hydrogen plasma jet," Fizika, tehnika i primenenie nizkotemperatumoi plasmi, Ala- Ata, 1970, p.578-580: Inzhenemo-fizicheski zhumal, v.20,p.3,1971; Knimiya visokih energii, v.7, p.491, 1973. 23, Valibekov Yu.V., Novikova G.A., Priimak A.D., Polak L.S. "Oil fractions pyrolysis in plasma," Tez. dokladov Vtorogo soveshaniya po plasokhimicheskoi tehnologii apparatostroeniyu, M., v.1, p.207-209, 1977. (in rus.) 224. Barkov A.P., Zubkova K.A., Kovinev V.P. "Process and process equipment 1 MW in power for acetylene production from natural gas," Tez. dokladov Vtorogo soveshaniya po plasokhimicheskoi tehnologii i apparatostroeniyu, M., v.1, p.231-233, 1977, (in rus.) 25. Volodin N.L., Suris A.L. "Investigation of plasma reactor for gasoline pyrolysis," Khimiya visokih energii, v.9, 5, p.423-426, 1975. (in rus.) 26. Gershuni S.Sh., Suris A.L., Shorin S.N. “Investigation of natural gas pyrolysis in plasma reactor with two-step quenching," Khimiya visokih energii, v.9, 6, p.528-534, 1975, (in rus.) 27. Shmikov Yu.L, Shorin S.N., Suris A.L. "Investigation of acetylene production from gasoline in hydrogen plasma jet on setup 1.5 MW in power," Khimiya visokih energii, val, 3, p.259-262, 1977. (in rus.) 28, Shmikov Yu, Shorin SN. Suris A.L. “Investigation of chlorohydrocarbons pyrolysis in plasma reactor," Khimiya visokih energii, v.9, , p.371-375, 1975. (in rus.) 29. Polak L.S., Enduskin P.N., Uglev V.N., Volodin N.A. "Production of acetylene and olefins under oil pyrolysis in hydrogen plasma jet," Khimiya visokih energii,v.3, 2, p.184-185, 1969. (in rus.) 30. Rikalin N.N., Tsvetkov Yu.V., Petrunichev V.A., Glushko LK. "The use of plasma for highly dispersed carbon black production," Fizika, tehnika i primenenic nizkotemperatumnoi plasmi, Ala-Ata, 1970, p.602-604, (in rus.) 31. Shoihedbrod S.P., Novikova G.A., Valibekov Yu. V. "Modeling of carbon black production in plasma," Tez. dokladov IV Vsesoyuznogo simpoziuma po plasmokhimii, Dnepropetrovsk, 1984, p.251-252. (in rus.) 32, Ganz S.N., Krasnokutskii YuJ. Tez. dokladov seminara "Primmenenie nizkotemperatumoi plasmi v tehnologii neorganicheskih materialov i _poroshkovoi metallurgii", Kiev, 1968, p.18; Khimicheskaya tehnologiya, 19, Kharkovski gos. universitet, vip.19, 1971, p.18. (in rus.) 33, Polak L.S., Pathomenko V.D., Mel'nikov B.L, Ganz $.N. Khimiya visokih energii, v.7, 4, p.303-308, 1973. (in rus.) 34, Parhomenko V.D., Zrazhevski V.L., Mel'nikov B.L. "Kinetics of liquid hydrocarbons in high temperature nitrogen jet,” Sb. "Issledovanie plazmennih protsessov i ustroistv", Minsk, 1978, p.71-74. (in rus.) 35. Ganz SN., Parhomenko V.D., Krasnokutski Yu.I. "Production of acetylene and cyanogen compounds in plasma," Kiev, Ukr. NIINTI, 1968.36. Volodin N.L., Vursel F.B., Polak L.S., Enduskin P.N, “Investigation of gas mixture for vinyl chloride synthesis by gasoline pyrolysis in plasma," Plazmokhimiya-71, M., INHS AN SSSR, 1971, p.157-159. (in rus.) 37. Volodin N.L., Vursel F.B., Polak L.S., Enduskin P.N. "Hydrocarbon pyrolysis in plasma," Fizika, tehnika i primenenie nizkotemperaturnoi plasmi, Ala-Ata, 1970, p.583- 586. (in rus.) 38, Shikov Yu.L, Shorin S.N., Suris AL, Volodin N.L., Izenger Yu.V. “Pyrolysis of chlorohydrocarbon waste in plasa reactor 200 kW in power," Tez. dokladov Vtorogo soveshaniya po plasokhimicheskoi tehnologii i apparatostroeniyu, M., v.1, p.247-249, 1977. Gn rus.) 39. Alexeev N.V., Sutis A.L., Shorin $.N. Thermodynamics of hydrocarbon oxidation at high temperature, Sb. "Teoriya i praktika szhiganiya gaza", L., Nedra, v.5, p.140-148, 1972; Sb. Plazmokhimiya-71, M., INHS AN SSSR, 1971, p.149-150; Fizika, tekhnika i primenenie nizkotemperaturnoi plasmi, Alma-Ata, 1970, p.589-592. 40. Ovsyannikov A.A., Polak L.S., Yudin V.I. "Experimental investigation of oxidation of methane at high temperatures," Khimiya visokih energii, v.2, 5, p.387-394, 1968, (in mus.) 41. Mikhailov V.V., Suleimenov A.B. "Conversion of methane by CO2 and H20 with the use of plasma generators for metallurgy," Sb. Plazmennie protsessi v metallurgii i tehnologii neorganicheskih materialov, M., Nauka, p.152-155, 1973. (in rus.) 42, Yakovlev E.A., Plastinin B.G., Polak L.S., Popov V-T. "Conversion of liquid hydrocarbons in water-vapor mixture at high temperature,” Khimiya visokih energii, v.16, 5, p.454-457, 1982. (in rus.) 43. Suris A.L., Artamonov A.G., Beskov A.G. "Conversion of organic compounds by oxygen at high temperature," Khimiya visokih energii, v.18, 4, p.342-346, 1984. (in rus.) 44, Beskov A.G., Suris A.L., Artamonov A.G. "High temperature processing of organic waste," Tez, dokladov IV Vsesoyuznogo simpoziuma po plasmokhimii, Dnepropetrovsk, 1984, p.228-229, (in rus.) 45, Frolov K.L, Nazarenko A.A., Yakovlev P.V. "Investigation of halogen-containing hydrocarbon waste pyrolysis in hydrogen,” Tez. dokladov IV Vsesoyuznogo simpoziuma po plasmokhimii, Dnepropetrovsk, 1984, p.242-243. (in rus.) 46. Tuhvatullin A.M., Shmikov Yu.L., Beresneva LV. "Utilization of pesticide production waste in plasma," Tez. dokladov IV Vsesoyuznogo simpoziuma po plasmokhimii, Dnepropetrovsk, 1984, p.230-231. (in rus.)47, Tubyatullin A.M., Beresneva LV., Hohlova L.N, "Utilization of pyrolysis tars in plasma," Tez. dokladov TV Vsesoyuznogo simpoziuma po plasmokhimii, Dnepropetrovsk, 1984, p.232-233. (in rus.) 48, Karp LN,, Tuhvatullin A.M., Chislovski V.V. "Simulation of chlorine-containing hydrocarbons waste pyrolysis in plasma," Tez. dokladov IV Vsesoyuznogo simpoziuma po plasmokhimii, Dnepropetrovsk, 1984, p.200-201. (in rus.) 49. Kostich G.G., Pavlovich P-B., Stefanovich PLL., Shikmanovich S. "Thermodynamics of chlorinated diphenyls decomposition in plasma,” Khimiya visokih energii, v.27, 6, 1993. Gin mus.) 50. Valibekov Yu.V, Shoihedbrod S.P., Mahkamov K.M. "Utilization of cotton-waste in plasma," Tez. dokladov IV Vsesoyuznogo simpoziuma po plasmokhimii, Dnepropetrovsk, 1984, p.244-245. (in rus.) 51. Gerasimov Yu.A., Idinov N.A., Polak L.S., Popov V. of benzene pyrolysis at high temperature," Tretii Vsesoyus! plazmokhimii, v.1, 1979, p.177-179. (in rus.) “Experimental investigation simposiumm po 52. Kaske, G., L. Kerke, and R. Muller, Hydrogen Production in the Huls Plasma- Reforming Process, Hydrogen Energy Progress VI, (1), (1986). 53. Muller, R., The Use of Hydrogen Plasma Processes in the Petrochemical and Iron- ‘Smelting Industries}, in: Hydrogen Energy Progress IV, {\bf 3} 885 (1982). 54, Rudiak, E.M., A. Rabinovich, and N.A. Tul, USSR Patent 700935, Aug. (1979). 55. AVCO Coal Pyrolysis, A.J. Patrick and RE. Gannon, A 1 MW Prototype Arc Reactor for Processing Coal to Chemicals, in “Radio Frequency Radiation and Plasma Processing,”, P.N. Cheremisinoff, eds, Technomic Publishing Co, NY (1982) 56. The Kvaemer/ScanAre work was orally communicated to Dr. Leslie Bromberg by Mr. S. Lynum (Kvaerner) and Dr. S. Santen (SKF) during a trip to Scandinavia in the summer of 1995,3. Design of plasmatron and reactor 3.1. OVERVIEW OF PLASMATRON DESIGN AND CONSTRUCTION After more than 30 years of research and development the plasmatrons have reached high degree of reliability{1-6].They have been designed for a wide spectrum of applications including chemical and material processing, nitrogen fixation, coal gasification, and ‘melting and refining of materials. They are successfully employed in extractive metallurgy, for welding, cutting, spraying, surfacing, spherodizing; they are also used in space-related applications, for example, reentry simulation and ablation studies. The power levels, at which plasmatrons are operated varies from a few kilowatts to several megawatts. In the case of arc furnaces, power levels in the order of 100 MW are of interest, The standard. commercial plasmatrons have thermal efficiency 80-90% and lifetime ~ more than 1000 hoursf1]. Based upon cathodes the plasmatrons could be divided into two major groups{2]: * Plasmatrons with hot cathodes, operating in thermionic emission mode. ‘¢ Plasmatrons with “cold” hollow cathode operated in field emission mode. In thermionic emission plasmatrons (Fig.3.1) the cathode surface must be heated to such a high temperature that sufficient numbers of thermally excited electrons can overcome the ‘work function (potential barrier at the surface) of the cathode material. For most metals, this temperature exceeds the melting temperature and only tungsten can be used. Adding thorium oxide or lanthanum oxide to tungsten lowers the work function, reducing the required temperature for thermionic emission. ‘The shape of hot cathodes is mainly determined by the range of arc currents for which the plasmatron is designed. “Rod” cathodes, with or without sharp or rounded tip, are useful 26for currents up to approximately 1,000 A. “Button” type cathodes may be adequate for currents up to around 5,000 A. Cathode erosion may become a severe problem if air, oxygen, or other reactive gas mixtures are used in the plasmatron. This type of plasmatron requires protective gases : pure Ar, Na, Hz without O2, This disadvantage could be minimized by using a cathode section with small amount of non-oxidizing protective gas and by injecting the main amount of reactive gases further downstream (Fig.3.2). This design is also applicable in case where the excess supply of Hs exist, for example, recirculating hydrogen from the fuel cells. Figure 3.1 Plasmatron with thermionic cathode. (a) Rod type (b) Button type‘The second type of plasmatrons operate with a “cold” hollow cathode operated in field emission mode (Fig.3.3). In this type of emission the electrons are leaving the cathode surface by means of the intense ion bombardment (secondary emission) and the radiation from the are. cathode anode diaphragm sections of injection of protective and working gases interelectrode section insulators solenoid aR oo to He me Figure 3.2 Plasmatron with cathode section (diaphragm).Cold cathodes are frequently made as hollow cathodes (tubes) or in the shape of wells, protected by highly effective cooling systems. Due to the high current densities at the cathode and the associated extremely high specific heat fluxes, even the most sophisticated cooling system cannot provide adequate protection if the cathode spot remains at the same location for any extended time period. For this reason the natural tendency of the cathode spot to move randomly over the cathode surface is enhanced by a gas vortex and/or by external magnetic fields. The resulting movement or rotation of the cathode spot distributes the heat load over a substantially larger surface area, reducing cathode erosion. For this reason the efficiency of the cold emission cathode plasmatrons (80-85%) is lower than for plasmatrons with thermionic emission cathodes. However the plasmatrons could utilize the broad range of reactive and nonreactive gases. Magnetic Replaceable field coils electrodes Plasma tail flame { Cooling Gas Gas water Figure 3.3 Westinghouse self-stabilizing plasmatron with copper tubular electrodes Since cold cathodes are usually protected by a cooling system, materials with high thermal conductivity are preferred as, for example, copper or copper alloys. In both designs the arc usually strikes in the shortest distance between two electrodes and then stretched by tangentially injected working gas. 29For thermionic cathode plasmatrons the cathode root of the arc is centered on tungsten rod or button (Fig.3.1), the anode root of the arc is rotated by gas vortex in order to prevent excessive erosion of the anode’s material. For cold cathode plasmatrons both roots of the arc are rotated on the electrodes surfaces with average speed of rotation more than 1000 rpm. In order to increase speed of rotation ‘one or both electrodes could be equipped by magnetic coils connected in series with the arc. Interaction of electric current with magnetic field creates JxB forces which increase speed of rotation. Mainly due to economical considerations the thermionic cathode plasmatrons are being used in welding applications, for ultra-fine powders production, for remelting scraps of titanium and nickel-base alloys, high-alloy steel, etc. The main suppliers of these plasmatrons are: Jonare, Blectro-Plasma, Plasmadyne, Plasma Technik and others. ‘The cold cathode plasmatrons are wide spreaded in plasma chemistry and plasma ‘metallurgy for hydrocarbons and coal reforming, waste treatment ete[3]. ‘The Huls, plasmatrons ranging in size from 2 MW to 8.5 MW are used in Germany since 1925 for acetylene, hydrogen and synthesis-gas production{4,5]. The plant uses methane, Cy- hydrocarbons, coal, crude and residual oils as a feedstocks. For acetylene production, 19 8.5 MW plasmatrons are installed (corresponding to a total power of 160 MW). Fig.3.4 shows a cross-section of the Huls plasma reactor. The plasma reactor mainly consist of ‘two water-jacketed tubular electrodes, the anode tube being at earth potential. The gaseous feedstock is injected tangentially by means of a whirl chamber and set in rotation. As a result, the arc is also forced to rotate. If the feed gas rate changes, the length of the are and hence the voltage drop across the are are varied. The power can be influenced in this way, with constant arc current. In the center of the arc, the temperatures are up to 20,000 K, i.e. a “plasma state” truly exists there. Because of the tangential flow of the gas the arc is surrounded by a steeply decreasing coaxial temperature field, and the gas ‘temperatures at the wall are only about 700 K. As a result, thermal losses can be limited toabout 10% of the electric power. The residence time of the gas in the plasma reactor is of the order of a few milliseconds, Within this time period the hydro-carbons are cracked into acetylene, ethylene, hydrogen and soot. At the end of the plasma reactor the gases are still at a temperature of about 1,800 K. The high enthalpy content of this gas can be exploited for additional acetylene production by means of a prequench with liquid hydrocarbons. This lowers the temperature to about 1,200 K. Since acetylene very rapidly decomposes into soot and hydrogen at these temperatures, the gases are immediately quenched with water to about 500 K. The furnace products, when operating with natural gas, contain about 60% of hydrogen, 17% of acetylene, 12% of methane and 7% of ethylene. Eleetrieot Insulator U7 ennaction Plaam Tongentiot oe aesiniets — Autiliary electrode Preumanie cylinder Figure 3.4 Huls 8 MW high voltage plasmatron for acetylene production. 31‘The Huls also carried out industrial testing of acetylene production from coal. Finely ‘ground coal is injected together with hydrogen into the hot plasma jet and then heated up in the course of milliseconds to temperatures of several thousand K. This high heating rate makes it possible to isolate very high proportions of volatile constituents from the coal, which are then cracked in the plasma jet to give acetylene. For the production of hydrogen from hydrocarbons, steam as an oxidizing agent is added to the feed, In the plasma reforming stage, the feed gas is converted to a crude gas which contains essentially H, and CO. The CO content in the crude gas is converted to Hy in a water shift reactor. After CO; scrubbing, pure hydrogen in the required purity can be produced from the gas in a pressure-swing adsorption unit. It was shown, that in contrast to catalytic steam-reforming processes, the steam/carbon ratio in plasma process is much lower, since the catalyst deactivation problems arising due to soot depositions no longer apply{4]. Also compared to catalytic reformer, the plasma reformer, because of the high temperatures and the resulting high space-time yield, can be relatively small. Since there is no catalytic reaction, a wide, flexible variety of raw materials, such as, for example, gas/oil or coal, can be employed. A second cold plasmatron has been developed by SKF Steel Engineering (Sweden). The plasmatron (Fig,3.5) has a segmented, fixed-length plasmatron with power rating 6-7 MUW(6]. The plasmatron has two equal-diameter water cooled copper electrodes. Two or more insulated segments are added between the electrodes to stretch the length of the arc in order to develop a higher arc voltage. Based on that plasmatron design the SKF has developed several plasma processes - PLASMARED, PLASMADUST and others- to recover valuable metals from iron ore, steel plant dusts etc. To make a reducing gas (Ez + CO) from coal or any other carbonaceous material SKF Stee! has developed a plasma gasifier (Fig.3.6). Introducing plasma energy into a gasification system permits operation independent of the oxygen potential and provides efficient heat transfer to the gasifying medium, 2Cathode ae = Magnetic. coil t 1 i] Aro 4 i | Plasma gas Figure 3.5 SKF 6 MW segmented wall plasmatron Boke Cokefilled shaft Oxyger/H,0 NS oo « ‘Slag Figure 3.6 2-step plasma gasifier‘The coal is injected into the reaction chamber where it is gasified with oxygen and steam. Complete gasification is obtained by maintaining the CO; + HO content in the exit gas at 10-15%.The exit gas at about 1600°C is then passed through a conditioning tower filled with coke or char for carburetion. In this concept, most of the energy required is supplied by the exothermic reactions with a minor part provided by the plasmatron to control the temperature in the reaction chamber and increase the gasification rate. The H2/CO ratio in the synthesis-gas can be varied by adjusting the amount of oxygen originating from steam. In 1963, the DuPont Company installed production facilities for manufacture of acetylene, using an are process, wherein hydrocarbons diluted with hydrogen are pyrolyzed in an continuous plasma produced by magnetic rotation of the arc (Fig.3.7). The plant was operated until May 1968 when it was shut down because of economic considerations [7]. Hydrocarbon feed ‘Cooling water outlet Post-arc hydrocarbon — Post-arc hydrocarbon inlet inlet Cooling water inlet: Product gas Quench water Source: U. S. Patent 3,168,592 Figure 3.7 DuPont 2-stage are fumace for acetylene manufacturing 34‘The DuPont process has been effectively demonstrated at the production rate of 50,000,000 Ibs/yr of acetylene scale at power 10 MW. The overall process includes the following major steps: 1. Vaporization of liquid hydrocarbon, Dilution with a recycle crude hydrogen stream. Pyrolysis in a direct-current magnetically rotated arc. Carbon scrubbing. Gas compression. Acetylene recovery and refining. a aAwayn Disposal of waste products in a steam generator. The best chemical yield, 75%, is achieved with butane as a feedstock. The process has demonstrated flexibility at pilot-plant scale with a methane feed, although the plant scale operation has been limited to liquified petroleum gas or liquid hydrocarbon distillates. The product gas analysis after water scrubbing to remove carbon: hydrogen-74.5 vol.%; methane- 4,7 vol.%; acetylene- 15.2 vol.%; ethylene- 3.0 vol.%. The carbon-water slurry from the scrubbing step is contacted with fuel oil and decanted to give a carbon-oil slurry suitable for combustion. The acetylene recovery system involves a dual solvent treatment using dimethylformamide and oil. The overall purity of the acetylene produced in this refining system is 99% with small quantities of various impurities. The waste gas from the recovery operation (hydrogen-89.5 vol.%; methane-5.7 vol.%; ethylene- 3.6 vol.%) could bbe used after additional refining for ammonia synthesis. twas also shown that the commercial large scale plasmatrons could be applied for ‘treatment of hydrocarbon and carbonaceous materials for different applications. In applications of plasma reformers for fuel ces, itis clear that both plasmatrons of group 1 (with tungsten cathode) and group 2 (with hollow cathode) could be used for hydrogen- rich gas production. But application of plasmatrons of group 1 is justified only when the 38price of protective gas -Ar, No, Ho- is not prohibitive or when the excess Hy is available, For all other cases the plasmatrons of group 2 should be used. ‘The hot hydrogen-rich gas produced in a plasma reformer from a variety of feedstocks could be used without major downstream treatment or additions in MCFC or SOFC fuel cells. These fuel cells can operate on synthesis-gas at 700°C and 1000°C respectively. ‘When it is necessary to produce pure hydrogen for PEMFC or PAFC, the plasma reformer could be equipped by conventional well developed water shift unit and preferential oxidation unit. The heat of hot hydrogen-rich gas could be utilized to preheat feedstocks (air and hydrocarbons) into the plasmatron by heat exchanger. For small power fuel cells, for example for transportation applications, the fuel cell could be equipped by compact plasma reformer with power range 1-3 kW. The design of research plasmatron which could be used as a prototype is described below. 3.2, EXPERIMENTAL PLASMATRON ‘The experimental plasma system (1-2 KW unit) has been developed using a commercially available Air Plasma Cutting System PAK MASTER 25. The power supply provides 20 A maximum current at an are voltage of 120-140 volts. The power supply consists of a AC- DC switching supply operating at 50 kHz, resulting in very small ripple. The standard system has been customized in order to control and measure the arc current and voltage by digital volt and current meters. It has also been modified in order to increase the ‘maximum operating voltage, and also to decrease the minimum current capability.- ‘This, power supply characteristics are ideal for plasmatron operation. In addition, the unit has an igniter (high voltage, high frequency) that is useful for starting the plasmatron,The research plasmatron (Fig.3.8) has a steel cathode with zirconium button and water cooled copper tubular anode. The cathode is cooled by air injected through the tangential channels in the ceramic gas distributor-insulator. The length of the arc is stabilized by the ledge in the internal diameter of the anode. The hydrocarbons (methane) are injected radially after the anode root of the arc. Experiments were carried out without the ledge, with a uniform intemal diameter. The downstream gas injection occurred prior to the root of the are. As a consequence, as the gas flow was increased, the root of the arc moved, increasing the arc length and the are voltage. Since the power supply was operating near its voltage limits, relatively small gas injection were sufficient to extinguish the plasma. Furthermore, the experiment was complicated by the fact that the arc voltage (and consequently, the arc power) was increasing with downstream gas injection. The plasmatron shown in Fig. 3.8 solves this problem by moving the place of injection further downstream, and by increasing the diameter of the internal diameter. It should be noted that the modification was done in order to allow experimental flexibility, but the original design may result in more efficient plasmatrons. cathode insulator anode are sone Figure 3.8 Research plasmatron 7‘The effect of the location of the injection port will be studied in the larger plasmatrons, with the larger power supply. This type of plasmatron with zirconium cathode and copper anode has long lifetime at low power because zirconium could provide thermionic emission in air or nitrogen atmosphere at currents less than 100 amps. At higher currents, the cathode erosion increases significantly. 3.3, ANALYTICAL INSTRUMENTATION 33.4. Gas Chromatography Diagnostics Figure 3.9 indicates the arrangement of the gas chromatography diagnostic system for species concentrations. The gas chromatograph (GC) used (MTI model M200) consists, of asample loop, vacuum pump, and two columns, each with an injector valve and thermal conductivity detector (TCD). ‘The first column is a Molesular Sieve SA PLOT using argon (BOC, Grade 5.0) at 25 psi as the carrier gas, and is capable of separating Hz, O2, Nz, CO and CH. The second column, a PoraPLOT U, uses helium at 25 psi as the carrier gas (BOC, Grade 5.0) and can resolve composite air, CHs, CO», and some higher hydrocarbons, notably acetylene (C:H,), ethylene (CH) and propane (C3Hs), Gas samples are provided directly from the reactor by means of a water-cooled sampling probe, shown schematically in Figure 3.9. The probe consists of a 0.5 mm inner diameter fused nickel tube, one end of which is soldered into the side of a copper tube, Water flows through the outer tube counter to the flow direction in the nickel tube, so as to quench the sampled gas as quickly as possible. ‘The reactor section shown in Figure 3.9 is designed to provide a large number of GC sampling points. At each of four axial locations, spaced approximately 2.cm apart, the sampler may be inserted in either of two orientations at 90° to each other. The sampler inlet can be moved to any position along 38the diameter of the reactor. This arrangement allows the measurement of both axial and radial concentration variations, with the slight disadvantage that the sampler/reactor unit must be disassembled in order to change the axial sampling location. The GC system has been calibrated using a gas mixture of 20.2 volume percent Hz, 20.0 percent CHL, 10.0 percent CO, 10.0 percent CO>, and 39.8 percent No (Matheson Gas Products). EXHAUST ee a - FROM PLASMATRON Figure 3.9. Sampler and instrumentation for gas chromatography diagnostics 3.3.2, FT-IR Diagnostics A system is currently under development to measure both species concentrations and temperatures non-intrusively through in-situ Fourier transform infrared (FT-IR) spectroscopy. Similar diagnostic methods have been used previously in combustion systems [8]. Figure 3.10 shows a schematic of the prototype system. The apparatus is based on a Nicolet Magna-IR 550 spectrometer with DGTS-A and liquid nitrogen cooled MCT-A detectors. This unit has been modified so as to pass the source radiation throughan external reactor before it reaches the detector. A detailed view of the reactor section used for infrared access is included in Figure3.11. The cylindrical reactor is water-cooled to stabilize the wall temperature; an uncooled or heated reactor could be substituted to decrease heat losses, Calcium fluoride (CaF;) windows are used (Ealing Electro-Optics 36-1790, 50.8 mm diameter x 4 mm) which have a peak transmission in the infrared of greater than 90 percent over the wavelength range 0.3 -7 pm. A slight flow of nitrogen gas (BOC Gases, Grade 2.0) is passed over the inner window surfaces to prevent damage by water in the reacting mixture and to insulate from thermal shock when the plasma is ignited. The aperature allows optical access to a section of the cylindrical reactor 3.5 cm in length; the entire width of the reactor can be observed. The optics associated with this reactor allow the infrared beam to be located at any axial and radial position within the optically accessible area; the beam position can be moved at any time during an experiment, Spatial resolution is adjustable by means of an itis, at the expense of signal throughput. Initial results with the FT-IR diagnostics are promising; frequency resolution of 2 cm" has been achieved in experimental measurements. Portions of two experimental spectra are included in Figure 3.12, showing the v; absorption band of methane in cold flow and during plasma-driven reforming. Concentration measurements are obtained from the integrated area under bands such as this one, and temperature is obtained from the relative intensities of the lines contained in the band, which correspond to different rotational transitions of the molecule, Temperature resolutions of + 50 K have been acheived with related in-situ FT-IR systems, and the initial results suggest similar resolution for this apparatus [9].[Reference Laser (HeNe) FROM PLASMATRON,‘01g Feet TAS He BEGEs ee: ces om: \) 8: mmo ats 3100 sommes ama amo Figure 3.12. Spectra of the vs absorption band of CH, taken using the apparatus from Figures 4 and 5. Upper spectrum was taken during plasma-driven reforming (> 1000 K); lower spectrum shows cold flow for the same input flow rates (no plasma) a23.4, REFERENCES 1, Camacho, S.L. (1988) “Industrial -worthy plasma torches: State-of-the-art” in Pure & Appl. Chem., Vol. 60, No. 5, pp. 619-632. 2. Pfender, E. (1978) “ Electric Arcs and Arc Gas Heaters” in Gaseous Electronics, Vol. 1, pp. 291-398. 3, Fey, M.G. and Harvey, F.J. (1976) “Plasma Heating Devices in the Electric Energy Economy” in Metals Engineering Quaterly/May, pp. 27-30. 4, Kaske, G., Kerker, L. and Maller, R. (1986) “Hydrogen Production by the Huls Plasma-Reforming Process”, Hydrogen Energy Progress YI, Vol. 1, pp. 185-190. 5, Maller, R. (1988) “The Use of Hydrogen Plasma Processes in the Petrochemical and Iron-$melting Industries”, Hydrogen Energy Progress YII, Vol. 2, pp. 885-900. 6, Plasma Technology in Metallurgical Processing (1987), Warrendale, PA, Iron and Steel Society, 208 p. 7. JM. Holmes (1969) “ Evaluation of DUPONT Are Process for Acetylene and Vinyl Chloride Monomer Production”, US Department of Commerce/National Bureau of Standards, 30 p. 8. PR. Solomon, PE. Best, RM. Carangelo, J.R. Markham, PL. Chien, RJ. Santoro, and H.G. Semerjian, Twenty-First Symposium (International) on Combustion, The Combustion Institute, p. 1763 (1987). 9. PE. Best, P.L. Chien, R.M. Carangelo, P.R. Solomon, M. Danchak, and I. Hovici, Combustion and Flame 85 309 (1991).4. Experimental results and discussion 4.1. RESEARCH PLASMATRON CHARACTERISTICS In this section the characteristics of the research plasmatron are described. The research plasmatron has been tested in order to define the working characteristics and thermal efficiency. The electric power of plasmatron is calculated as follows:: Pu=IU wheré I is arc current and U is the are voltage. ‘The efficiency of the plasmatron was experimentally determined by measuring the electrical power in the plasmatron, and the heat losses to the plasmatron. The electrical input goes into heating the gas and heating the plasmatron. Heat that does not end in the plasmatron walls is carried out by the high enthalpy gas. In steady state, the power to the plasmatron walls equals the power to the cooling water in the plasmatron, The change in temperature in the cooling water was measured using a pair of calibrated thermocouples, and the water flow rate was determine with ball rotameter. The accuracy of the temperature measurement was 0.1 K, while the flow rate was determined within 5%, ‘The thermal losses with cooling water Phoss = Cp Mot (Text ~ Tin) where cp is the heat capacity of the water, my. is the cooling water flowrate, Tox is the temperature of cooling water out of plasmatron, T), and Ty, are the inlet and outlet, temperatures of the plasmatron cooling water.‘The thermal efficiency of the plasmatron is T= (Pat- Prss)/Pa- ‘The energy into the gas can be calculated from the difference between the electrical input power and the power into the plasmatron walls. The gas flowrate is measured with a calibrated ball rotameter. Therefore, the average mass enthalpy of plasma gas can be calculated. The average temperature of the plasma gas was determined from the enthalpy of plasma gas, once the gas enthalpy is known. This is done using the standard thermodynamic tables (JANAF). ‘The working gas during the tests was nitrogen. The experimental results are shown at Table.4.1 and Figures 4.1-4.4. ‘Table 4.1 Power(W) | deltaT | Efficiency (%) | _N2flow (m3) | ki/mol N2 | N2 final T (K) 1572, 33 2 088 56 1264 1589 35 1 076 7 1648 1485, 3 78 0.65 9, 2284 1526 39 7. 042 178 3310 1947 38 33 088 7 1520 1892, 42 80, 0.76 84 1859 1764 43 9 0.65, 105: 2601 1747 44 78 053 141 ‘3752 1737 45 7 0.42, 200 5879 2285 48 81 088 33 1736 2145 47 81 0.76 96 218 2106 49 80, 0.65, 126 3032, 2087 32 78 053 168 4417 2038 33 71 042 232 6688 As could be seen from the working drawing of the research plasmatron (Fig. 3.8) the length of the arc (and therefore the voltage) was stabilized by increased inner diameter ofthe anode, With a small diameter, the additional gas flowrate (injected after the discharge) affected the length of the are with the consequence that as the flowrate was changed, the electrical power into the plasmatron was also varying. By increasing the diameter of the are it was possible to adjust independently the power and the flowrare. For the experimental plasmatron, the arc voltage was relatively constant at 105-120 V as the range of nitrogen flowrates was varied between 0.42 and 0.86 m’/ir. Fig. 4.1 shows the dependence of the voltage on the nitrogen gas flowrate for arc currents of 13.5 A, 16.5 A. and 19.5 A. 10 us no g g 105 100 95 2» 2s 0 35 40 flow rate Fig.4.1 Dependence of arc voltage on nitrogen flowrate for several are currents ‘The power of the plasmatron was also relatively independent on nitrogen flowrate at the same level of current and was at range 1.5 - 2.3 kW (Fig.4.2). Therefore the plasmatron power depended exclusively on the arc current, Increasing the nitrogen flowrate has a positive influence on the plasmatron thermal efficiency, improving it from 77 to 83% (Fig.4.2). The reason for this improvement is that the thermal losses to water cooled copper anode become smaller (Fig.4.4) as bigger gasflowrate decrease the average gas enthalpy and the gas temperature, decreasing convection, conduction and radiation losses of the plasma to the plasmatron walls. 200 2000 8 Flow rate (scale unl) Figure 4.2 Power and efficiency for several currents as a function of nitrogen flowrate. 2300 2200 2100 8 1900 . 8 ra g POWER (W) 1600 . 1500 8 00 1300 1200 2 13 “ 8 6 v7 8 ’ 2» ‘cuprent cay Figure 4.3. Plasmatron power as a function of the arc current for several flowrates. 4755 35 0 flow rato (at units) Figure 4.4. (Toy - Ti) a8 a function of nitrogen flowrate for several are currents. 4.2, CONVERSION RESULTS ‘The experiments of air conversion of methane were carried out by using the research plasmatron (Fig.3.8). Plasmatron was connected to water cooled copper tubular reactor equipped with the sampler. The sampler was used to take samples of plasma gas for gas chromatography (GC). ‘The results are preliminary. At the present time the instrumentation cannot determine water vapor concentration, although its concentration could be significant. Also the GC is not yet calibrated for acetylene and ethylene that also exist in large concentrations at conditions close to pyrolysis. 48Higher concentration of unreacted residual methane (up to 8%) and oxygen (~0.4%) at higher flowrates (Fig.4.7, 4.8) also indicate incomplete conversion of methane at those flowrates. Itis possible to improve completeness of conversion by increasing energy consumption (power of plasmatron spent on the treatment of initial methane) maintaining the same total flowrate. It could be seen from the Fig.4.9 that the residual methane concentration going down from 2.4% to 0 as the energy consumption increases from 14 to 27 Mikg-CH, Obviously, this method of increasing conversion of plasma reforming is not optimal, 180 14.0 pe . 120 ete S J Ba, re a a Lambda Figure 4.6 CO dependence on 2 at different flow rates20 70 CHa 10 0.9 a 0.00 0.05 o.10 0.5 020 0.25 0s oa os os 90s Boe oa os os 00 Total flowrate, o/s Figure 4.7 Residual CH, dependence on total flow rate at A= 0.2- 0.22 0.00 0.05 010 ots 0.20 0.25 Total flowrate, o/s Figure 4.8 Residual O, dependence on total flow rate at A= 0.2- 0.22 5125 18 cHa% 10 9 #4 _4—________,___] 00 5.0 100 15.0 200 25.0 30.0 Energy comsumption, M/kgCH4 Figure 4.9 Residual CH; dependence on specific energy consumption at A= 0.16-0.18 Injsion fier plasmaron Injection it plasmon 0 0.05 on 01s 02 025 Total flowrate, o/s Figure 4.10 Residual CH, dependence on total flow rate at A= 0.16-0.18 32os os : . oa icon serpin Hos 02 ot icon pumazon 09 ——— - 0.00 005 010 ons 020 025 Tota lowrate, o's Figure 4.11 Residual 0, dependence on total flow rate at A= 0.16- 0.18 ‘As shown in Fig.3.9, in these experiments the methane (or mixture methane with secondary air) has been introduced into the plasmatron channel at a single port downstream of the anode edge. At high flowrates it has been seen visually that the hot jet is distorted to one side by single port injection, indicating that mixing is not complete. In order to improve mixing, in a subsequent series of experiments the methane or mixture of ‘methane with air has been introduced at two radially opposite ports, right after the anode edge. As follows from the results presented at Fig.4.10 and 4.11, two-port injection is, also not optimal , since the unconverted methane and oxygen are still significantly higher than with injection into the plasmatron channel. This could be explained by the fact that the inner diameter of water cooled tubular reactor attached to plasmatron is 1.5 times bigger than the inner diameter of the plasmatron. ‘This difference in diameters creates an stagnation zone which, in combination with the cold wall, inhibits the partial oxidation reaction. 53.‘Work is currently underway to modify the research plasmatron in direction of distributed {20s injection into the plasmatron channel. Table 4.2 Experimental results (concentrations in vol%) RUNID totalflow Mufkg =, «HZ. «O2_-N2_CO CHS COZ CHa 16xI955.2 014 «27.8 O16 14.4 0.0 650 145 00 32 16xi966.2 0.15 «2580.20 190 00 896 165 02 21 1exi951 017 1990.12 97 00 725 117 01 48 16x92 0.19 157 018 137 00 686 124 1.0 35 16x94 0.20 140 018 18.0 01 644 130 23 34 16x96 0.21 129 0.20 187 02 614 124 59 27 t6xi957 0.22 116 028 155 04 586 119 80 25 16x98 0.23 108 025 151 06 564 112 103 23 16959 «0.13 «= 20S OT 152 00 651 143 03 30 16rxi9512 0.15 «= 180.18 17.1 0.0 61.9 145 1.1 25 16xi9514 0.16 «= 184021 182 00 586 138 29 22 169515 0.17 «= 142024 179 02 552 128 59 20 teri9516 0.18 «= 126 «(O27 184 08 529 120 99 18 169517 0.19114 029 17.9 04 505 11.1 128 17 2ixi9s02 0.18 82 044 150 08 447 x 215 14 21xi960s 0.18 84 040 172 04 473 115 188 15 21xI960S 0.14 98 085 178 03 498 121 142 17 21x9507 0.48 «14.9 O81 189 02 519 132 90 18 21xi9508 0.42 «= 18.20.27 191 OA 544 140 5.1 1.9 21xi9509 0.11 156 023 179 00 582 142 18 22 21xi9510 0.10 © 18:7 0.19 147 0.0 626 129 03 34 28x9501 0.12 «17.8 «(0.14 112 04 645 11.0 05 38 80x9501 0.15 144 017 129 01 663 106 40 39 30x9502 0.28 62 024 84 59 571 68 187 14 20x19503 0.20 85 028 14 19 605 96 115 24 20x9504 0.17 12.00.18 125 05 621 112 61 30 90xi9505 0.17 11.9 018 130 05 635 115 57 28 0xi9506 0.21 108 0.16 93 05 686 95 37 45 545. Thermodynamic Modeling 5.1 Introduction A major goal of this project is to produce hydrogen from hydrocarbon fuels. This process involves the transformation of one type of fuel molecule to others; itis of critical importance to retain as much of the fuel energy as possible. In order to design a system that will make the most efficient use of the input fuel energy, it is necessary first to consider the basic thermodynamics of the reforming process, which determine the possible final distributions of the initial energy. Daring this analysis, one should keep in mind both the benefits and the limitations of thermodynamic models. Thermodynamics can tell us the limiting behavior of the system, such as the maximum useful work that can be extracted from input and output fuels, the bounds on heat release during the reforming process, and the chemical composition of the output gas given infinite time, None of these are values that we are actually likely to see in a real reformer, in which residence times are finite, kinetic effects may outweigh equilibrium effects, and the useful work extracted from the reformed fuel may be significantly lower than the maximum theoretically possible amount. However, thermodynamics allows us to find these limits of system behavior through relatively simple analysis, hence giving us the ability to examine a large parameter space like the one in question here, where the variables include chemical compositions, temperatures, pressures, residence times, process details such as mixing, heating and expansion, and many others, and to find the most productive area or areas on which to focus a more detailed study. 5.2 Fuel reforming as part of the energy cycle ‘As a background for the following analysis itis important to consider how fuel reforming fits into the overall process of converting energy into useful work. The complete pathway proceeds from the delivery of energy by sunlight to the outputs of heat and work; the portion of 55this pathway that we need to consider, as shown in detail in Figure 5.1, starts with the energy contained in fuel molecules, and proceeds to the ultimate generation of useful work from that energy. Byproducts released along the way include heat and chemical emissions. HEAT WORK HEAT WORK OUT OUT ouT ouT Figure 5.1, Detailed energy consumption pathway with fuel reforming. ‘From the above diagrams, we can easily see some of the main issues that will concern us in the analysis to follow. Clearly, an important consideration is the ratio of the chemical and thermal energy contained in the output fuel to the energy in the input fuel. This ratio is essentially the minimum efficiency of the process, presuming that no work done by the system during reforming is captured as useful output work. In general, some parts of the heat release and work generated during reforming are recoverable, i.e they can still be converted to useful work either within or at the output of the energy pathway shown in Figure 5.1. The amount of recoverable energy determines the maximum efficiency; however, this maximum value is highly process dependent and hence will be affected strongly by small variations in system parameters. The analysis in this section will focus on the energy efficiency under the assumption of no heat or work recovery, ‘which represents a true thermodynamic limit to system performance, and is largely independent of the particular physical characteristics of a given reformer. ‘An additional issue that we can begin to understand using thermodymanics is the chemical composition of the output gas mixture. Although thermodynamic methods can only predict the 56equilibrium composition of a mixture, we will see later that in many situations, the output gas from the reformer will be very near to the equilibrium state. Hence, we can get a rough estimate of how the process parameters affect the output composition without a detailed kinetic analysis, which will be very helpful in focusing on a particular region of the initial parameter space. The thermodynamic efficiency and output composition are closely linked, so the efficiency calculation will necessarily involve constraints related to the desired chemical composition of the reformed gas. 5.3 Available energy and reforming efficiency In order to determine the energy efficiency of the reforming process, a more precise definition of “energy” is needed. We need to keep track not only of the chemical energy of the fuels, but of the energies involved in heating, expansion, performing work, and mixing, as well. We also need to determine what part of these energies can be converted into useful work output, and what partis lost during the reforming process. ‘Thermodynamic analysis concentrates on the energy interactions between a system and its, environment. Careful choice of the arbitrary division between system and environment can greatly simplify the analysis. In this case, a useful choice of system is the reacting mixture; that is, the ‘chemical system that initially consists of separated fuel and air, which are mixed and react to form products during the reforming process. Thus, no matter ever crosses the border between system and environment, so all interactions between the two must consist of exchanges of heat and work. ‘The environment is everything that is not included in the system; in this case, the environment can be modeled as a reservoir with a constant temperature T,, and constant pressure p, that can also exchange volume with the system at no cost. Hence, the environment can receive heat from the system and the system can do work on the environment without changing T,, and the system may 37expand against the constant pressure p, by exchaging volume with the environment. In all cases below, T, = 298 kelvin and p, = 1 atmosphere. A more precise statement of the question we want to anwer is: starting from the initial resources of fuel and air, what is the maximum amount of useful work that can be output from the system per unit amount of fuel input, allowing arbitrary heat or work interactions with the environment? ‘The combination of the first and second laws of thermodynamics shows that the ‘maximum amount of work that can be extracted is obtained when all processes are reversible (i.e. there are no permanent effects of energy or entropy transfer to the environment) and the final products are in mechanical, thermal and chemical equilibrium with the surroundings. This ‘maximum work is termed the availability, ©. It depends only on the initial and final states and the constraints imposed on the system (e.g. whether progress toward mechanical, thermal or chemical equilibrium is allowed, so that pressure, temperature and chemical potentials are equalized, or whether there are specific constraints on volume, energy or chemical species transfer). The particular constraints that we will consider here are the following: the system is allowed in principle toreach pressure and thermal equilibrium with the environment (ie. the system reaches T, and Pg), and the chemical species within the system are allowed to evolve to chemical equilibrium at the final pressure and temperature conditions. In this case, we can define an availability function such that the availability between two states is given by the difference between the values of the availability function evaluated at the states: Oy =V,-Vy For the conditions described above, the availability function vy of a system state (denoted by s) is: v= Liny, = LH - TS) 2 7 in which n, is the number of moles of species j, H, the molar enthalpy of the species and S, the molar entropy of the species. 58Both H, and S, vary with temperature. To take these changes into account, each can be split into two parts; the first is an arbitrary reference value at a particular temperature, H? or $®, and the second gives the difference between the value of H, or S, at the specified temperature and the reference. In the standard definitions, the reference values are chosen so that H° is the enthalpy difference between the species and its component elements in their standard states (i. their most stable forms at 298 K), denoted AH®,, and S* is such that S, is zero for all species at zero Kelvin: H, = (H? + H(D), = (AH; +H), (S° + (7), = S(T), ‘The values of AH®,, H(T) and S(T) for a given species can be found in tables or calculated via polynomial approximations. The values of H, and S, at 298 kelvin are listed for species of interest in the reforming process in Table 5.1. ‘Molecule ‘AF, Gainol) ‘S@98 K) (Ki/mol.K) 'V;298 K) (elmo!) CH “433 0.186 -130.7 0; 0.053 (0205 “6151 H 0.056 0131 39.18 CO “1105 0198 “1699 CO, “3985 0214 “A577 HO) “383.51 0.189 “2984 Table 5.1. Thermodynamic properties of selected molecules at standard states ‘The maximum availability for the initial state of the reforming system (unmixed fuel and air at 298 K and 1 atm, indicated by the subscript i) will occur when the final state corresponds to thermal and pressure equilibrium with the environment (Le. T=298 K and p= 1 atmosphere), and chemical equilibrium within the system itself. At this equilibrium state, denoted by the subscript 0, the availability function y, of the system is minimized, given the constraints of thermal and 59pressure equilibrium and mixture composition. (Note that if T > 298 K or p > 1 atm, the system can still do work, so ® will not be minimized.) Hence, a final state at y, will give the maximum availability for any initial state of the specified system. ‘We can now quantify the energies involved in the energy consumption pathway of Figure 2. The energy of the input fuel corresponds to the availability of the transition between the initial (i) and equilibrium (0) states: Bo = Vi—Yo = Lr Hy ~ ToS) LPH — TS) i ‘o where the summation over j, indicates summation over all chemical species in the initial state, and jy indicates the equilibrium state species. The energy contained in the output fuel is the availability between the reformed state, given the subscript r, and the equilibrium state: Bio = VY, Yo = LM Hy ~ Tey) Lio Ho — ToS po) + ‘s Finally, the energy that could be recovered as work from the reforming itself is the availability of a process that takes the system from the initial state to the reformed state: ©, = YY, = (Hy TS) “Le Hy TS) a + Inthe current analysis, we assume that this energy is “lost” to the environment, To completely define the efficiency of reforming, we must also consider energy inputs to and losses from the system, Energy input during the reforming process (such as the electrical work input by a plasmatron, W,,) can be added to the initial availability; that is, the total energy input to the reformer is the sum of the availability of the fueV/air mixture and the energy added as electrical work during the process. Energy “losses” during the reforming correspond to heat or work: transfer to the environment; thus, the availabilities described above correspond to a situation with minimized losses. Using the above definitions, the thermodynamic efficiency € of the reforming process is given by 60Po oem, Hence, the problem of determining the efficiency of the system is reduced to determining the value of y for the initial and reformed states (which requires the pressure, temperature and chemical compositon of each state) and the minimam work or energy input required to move the system from the initial state to the reformed state. ‘The above energy relationships are shown diagrammatically in Figure 5.2. Several important points regarding the relationship between jy and ®jq may be noted here. The assumptions made above require that in the reformed stat, the system contains the same atoms as in the initial state (no mass crosses the border between system and environment) and the pressure is unchanged. The chemical species distribution and temperature of the reformed state will in general be different from those of the initial state, and these will determine the availabilty function of the reformed mixture. Since there may be an energy input during reforming, it is possible that ¥y, will be greater than Vy, ‘The preceding analysis applies to any set of inital, reformed and equilibrium states ofthe system as defined above, with transitions occuring at constant pressure. The variables that remain are the chemical compositions and temperatures of the intial, reformed and equilibrium states, the input energy, and the constraints placed on the path that takes the system from the initial tothe reformed state. In the following sections, the effects of changes of these variables on the efficiency and other system parameters are considered. 61Wit Wir- vo process coordinate Figure 5.2, Availability relationships forthe states of the reforming process 5.4 Analysis of the initial parameter space. Despite the assumptions and restrictions made above, the parameter space left to investigate is still extremely large. However, a few additional assumptions can be made in order to allow a useful analysis of this space without much further loss of generality. By specifying that the input mixture consists of a (gaseous) hydrocarbon fuel in air, we limit the chemical composition of the system. ‘The further assumption that nitrogen is unreactive allows the chemical composition (scaled by the amount of carbon in the system) to be characterized by the hydrogen to carbon and oxygen to carbon ratios. ‘Some restrictions on the initial, reformed and equilibrium states will complete the assumptions. A generalized reforming process can be a useful guide in deciding what limitations to place on the states. For a hydrocarbon fuel in air, the maximum availability is achieved through complete combustion; this is therefore the most common process used to release energy from hydrocarbon fuels. Hence, it is reasonable to define the initial state as separated fuel and air at the 62stoichiometric ratio for combustion, in thermal and presure equilibrium with the environment. Likewise, the equilibrium state can be defined as equilibrium combustion products (CO, and H,0), again in thermal and pressure equilibrium with the environment. ‘Thus, only the reformed state remains to be defined. To do this, we may model the reforming process as follows (see Figure 5.3 fora schematic representation of the states): the fuel and some portion of the air are injected into the reformer, where the energy input W,, is added to the resulting mixture, The heated gas then evolves to equilibrium adiabatically and at constant pressure (i.e. AH = 0). Although the equilibrium composition technically is only reached at infinite time, it will be shown in Chapter 4 that for most of the reactions under consideration, the major products concentrations are likely to be very close to equilibrium levels after only a short time (typically much less than a second under the conditions we will examine). ‘This defines the reformed state as consisting of two parts: the first is a mixture containing all of the fuel mass and some part of the air mass from the initial state, at a pressure of p, and at the “reformed temperature” T,, with a chemical composition corresponding to equilibrium at this temperature and pressure; the second part is.the remaining air ‘mass from the initial state composition, still at T and p. Try PR Ty, a O—-() LA reformed Ww PR Tre Pr TPR Try Pr inital state reformed state equilibrium stare Figure 5.3. States ofthe plasma fuel reforming system (horizontal line represents a physical separation of gases). Defining the three states as above reduces the variable system parameters to the H:C ratio of the input fuel, the O:C ratio of the portion of the gas that passes through the reformer (the overall 63