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ht. J. HJ’&o~I Ener,yy. Vol. 23, No. 6, PP.

419425, 1998
Published by Elsevier Science Ltd on behalf of the
lnternatmnal Assocration for Hydrogen Energy
Pergamon Printed in Great Britain
PII: SO360-3199(97)00092-X 0360-3199/98 $19.00+0.00


Department of Advanced Technology, Brookhaven National Laboratory. Upton. NY. 11973-5000. USA

Abstract-The thermal decomposition of natural gas forms the basis for the production of hydrogen with reduced
CO2 emission. The hydrogen can be used to reduce CO, from coal-fired power plants to produce methanol which can
be used as an efficient automotive fuel. The kinetics of methane decomposition is studied in a one inch diameter
tubular reactor at temperatures between 700 and 900°C and at pressures between 28 and 56atm. The Arrhenius
activation energy is found to be 31.3 kcal/mol of CH+ The rate increases with higher pressures and appears to be
catalyzed by the presence of carbon particles formed. The conversion increases with temperature and is equilibrium
limited. A thermodynamic study indicates that hydrogen produced by methane decomposition while sequestering the
carbon produced requires the least amount of process energy with zero CO, emission. Application to methanol
synthesis by reacting the hydrogen with CO2 recovered from coal burning power plant stack gases can significantly
reduce CO1 from both the utility and transportation sectors. Published by Elsevier Science Ltd on behalf of the
lntermational Association for Hydrogen Energy

The production of hydrogen by the thermal decompo- where pp is the partial pressure of each component.
sition of methane (natural gas) eliminates the emission of
CO?. The carbon is either sequestered or used as
a materials commodity. The hydrogen can be used in 100
several processes [l. 21 for- methanol production for I
reduced CO, emission.

Since the methane decomposition is endothermic, the
methane concentration decreases with increasing tem-
perature. Due to the increase of volume during methane
decomposition, the decomposition of methane is favored
by decreasing pressure.
CH4=C+2Hz- 17.9 kcal/mol. (1)
Figure 1 shows the equilibrium data for methane
decomposition at temperatures from 600 to 1200°C and
at pressures of 25, 30, 40 and 50atm. These data are
calculated from the Gibbs Free Energy and equilibrium
dG= - RTln Kx (2)
Kx = X&/XCH4 (3) I I I
600-’ 900 1000 1100 I200
where X is the mole fraction of each gaseous component Temperature (“C)
and Fig. 1. Equilibrium data of methane decomposition.


6~01%.~ldt=k.2.Gx491 -1/K<.5 10.= -dCc. 2. controlled regulator located next to the methane supply At both 700” and 800°C and at 56. Gas is sampled before and Generally.3 and 69.C+2H1 (5) gas is controlled in the range between 10 and 150 l/min by a flow valve located after the reactor. the con- cylinders which keeps the pressure approximately con. Methane flows through a preheater and enters conditions.Cc.. centration of methane decreases less with residence time stant at selected pressure of 28. The flow rate of exit CH. a gas-chromatograph and gas the inlet gas velocity. The total length of the conditions.3 ~01%. Methane concentrations vs residence time.1 ~01%. The rate of methane decomposition at the two effluent gas flows through the carbon trap connected at lower temperatures appears to be smaller than that at the the bottom of the reactor.1 atm in the than that at 900°C and 56.0 9..420 M.8 or 56. The imental temperatures of 700”.5 80 100 120 1 /T x 1Om4 Arrehenius plot Residence time (set) Fig. through the gas meter where the flow rate is measured and and k.1 atm... a carbon trap.0 8. 3.1 atm . 41. is the rate constant of methane decomposition. Rate constant of methane decomposition vs reciprocal Fig.1 atm.C~l Details of the experimental data are given in [3]. The exit gas flows where k. the concentration of methane decreases dra- the reactor which consists of a 1 inch inside diameter matically with residence time and approaches equilibrium 1 ‘4inch wall Inconel 617 tube.1 atm are 54. x C~21G~I) (6) Equilibrium data at 700°C and 56. time of 103sec was 48. Methane is decomposed into 800°C and at 56. librium concentration of the methane is 39. where the carbon generated higher temperature of 900°C. STEINBERG EXPERIMENTAL Figure 3 shows the relationship between the methane concentrations in the exit gas and residence time in the Figure 2 shows the schematic flow sheet of the exper.0 10. the equi- nally heated and selectively maintained at constant exper.:--.. The rate equation for this reversible reaction can be written as follows: EXPERIMENTAL RESULT AND DISCUSSION -rCH. CO and COP in the gas are measured. A summary of the calculated data is given below. the equation for the rate of decomposition after the reactor through sampling lines on an on-line of methane is derived as follows: gas-chromatograph and the concentrations of CH4. The concentration of methane at a residence reactor tube is 11 feet of which the first 8 feet are exter. The concentration of the methane meter.* Equilibrium data l~_~~:!~!~ 10-41 I I I I I 8. In this case. is the rate constant of methane formation.5 9. the gas is finally vented to the atmosphere. The residence imental equipment which mainly consists of a tubular time of the methane gas in the reactor is obtained by reactor. reactor under the conditions indicated. =k. by the reactor is separated.~--k. Under the latter system.1 atm). Methane enters the system through a remotely decreases with increasing temperature and residence time. 800” and 900°C by equilibrium data at the lower temperatures of 700 and clamshell electric heaters. temperature (at 56. respec- carbon and hydrogen in the heated reactor and the tively. .

AND CH.40r exit methane con. and quartz.. time t at the three different pressures investigated at The activation energy appears to indicate a diffusion 900 C the rate constant k. for experiments appears to be influenced by a heterogeneous inlet methane concentration C. some of the centration CH40.E. Rate constants at 56.O66E-2 l/s 700 ‘C 5. From the limited methane and H?. in the decreasing order of iron oxide. alumina.3 kcal/mol the rate constant of methane decomposition was inves- (8) tigated.753E-4 I/s 56. effect of surfaces. Schematic flowsheet of tubular reactor for methane decomposition. gives the materials increase the rate of the methane decomposition calculated k. 30 kcal/mol as opposed to a chemical reaction controlled The rate constant appears to be approximately constant process which has much higher activation energies rang- Table 2. During our experiments. I’ regulator Gas chromatograph l-l \ ’ lie cylinder Cl14 cylinder Carbon trap Fig. lo] clearly indicate that different Applying the experimental data. By plotting the value of k. value 28. k.1 atm Pressure k. = 5. the homo- The above differential equation for methane decompo. it was found that the carbon plugged the tube to the extent that it restricted the gas flow.306E-3 l/s 900°C 9. can be determined from the controlled process which usually has values up to about slopes of the lines. [9. The data gathered in these of CH. values are listed in Table 2. rate constants at the three temperatures. PRODUCTION OF H.4 x 10’exp (. ing above 50 kcal/mol. The following rate equation in terms of the the walls of the Inconel high alloy steel of the tubular residence time has been derived: reactor. respectively.3066-4 l/s ~ Average rate constant = 1.2 atm l. x t versus the residence k. decomposition data in the literature [4-g].O = 0 (initial concentration of hydrogen is 0). geneous activation energy for methane decomposition sition in the tubular reactor is solved for the condition is found to be 65 kcaljmol.. and equilibrium concentration of meth. are calculated to results in a lower activation energy for decomposition be as follows: The influence of the total pressure in this system on E= 3 1.8atm 1.12E. value Temperature k. In fact. . where CCH. Rate constants at 900’ Table 1. carbon formed from methane decomposition adhered to ane C. Thus.. the rate constants.657E-4 l/s 41. graphite In Fig. and CH2 are the molar concentrations of CH. The k. 4. 4. Table 1. for methane decompo. In the tubular reactor the small submicron sition are plotted versus reciprocal temperature. 421 . at the end of several extended runs. From particle size of the carbon formed presents a very large this Arrhenius plot an activation energy for methane surface area on which methane can decompose and thus decomposition and the rate constant k.I_ Gas vent Methane feed Gas ?L-tJ meter Press.380E-2 I/s 800 ‘C 1.E/RT)l/sec. the fine submicron carbon particles tend to catalyze the thermal decompo- sition of the methane.1 atm 9.-2 1 is.

when considering CO* emission. The . The rate of carbon formation from meth- ane on silicate substrates has been found to increase with pressure to the first-order up to 15 atm [4]. Table 4 compares the hydrogen basic energy require- ments for fossil with non-fossil energy processes. The Carnol Process consists of a methane decomposer and a conventional catalytic methanol synthesis reactor shown in the inset. emission. emissions from the coal-fired is practically reduced to zero. Thus. The energy required to recover CO. However. emissions.422 M. The rate equa- tion (6) modeled in this paper indicates that the rate constant should be constant and independent of pressure.0 kcal/mol) which includes the energy in the methane feedstocks. nuclear. METHANOL PRODUCTION The Carnol Process System is shown in Fig. When considering CO*. The system takes CO. STEINBERG with pressure. the rate is favored by higher pressure and appears to be catalyzed by the carbon particles formed by the reaction. when hydroelectric power is available it is very efficient to use it for the electrolysis of water. 5. recovered from a coal- fired power plant and reacts it with hydrogen from the methane decomposer. by a hindered amine solvent is provided by the exothermic heat of reaction in methanol synthesis. Methanol production by the Carnol Process is also practically reduced to zero. From an economic point of view at present. The methanol formed then is used as fuel in automotive IC engines. It can be seen that the process and total energy require- ments for electrical. The use of methanol in automotive IC engines is reported to be 30% more efficient than the use of gasoline [12]. However. Our data indicate that although the thermochemical equilibrium for methane decomposition is favored by lower pressures. This is in accord with other published results. that the rate of methane decomposition increases with the partial pressure of methane approximately to the first-order. methane decomposition and biomass process yields the least CO. solar and thermochemical water splitting processes are much higher than for fossil energy feedstock processes. Table 3 compares fossil fuel processes and includes biomass reforming. HYDROGEN PRODUCTION ENERGY REQUIREMENTS A comparison of the basic energy requirement for the production of hydrogen by various known processes is given in Tables 3 and 4. the cost of biomass energy cost is twice as high as that for natural gas [l 11. It is seen that the thermal decomposition process offers the least process energy requirements (11.3 kcal/mol) while the steam reforming uses the least total energy (71. the non- fossil systems provide zero CO. emission system. It is interesting to note that the combined cycle power generation pro- ducing electrical energy for use in the thermal decompo- sition of methane allows a low CO. the CO.

0%(t) CH.9 0. Table 4. + Hz0 2.=C+2H2 .1 0. 1.5 80%(e) 0.0 0. Hydropower.0 water 80%(e) (thermal wind and HZ0 = HZ + l/20: 64%(t) equiv.0%(t) U-235 Hz0 283. = C + 2H1 (A) 80%(t) 53.37 154. CH. CH. Hz0 106.1%(t) CH. Nuclear energy for electrolysis of water 30%(e) 24.9%(t) CH.3 126.0%(t) solar Hz0 725.67 11.0 0. Solar photovoltaics for electrolysis of water 10%(e) 8.2 0.5 154. 8 2.0%(t) Hz0 113.10 XO%(e~ CH.3 106.3%(t) H. Thermochemical cycle-coal fired heat for water splitting 60.6%(t) CH.12 Combined cycle power for electrical heating (D) 55%(e) 53. Hz0 1.00 (B) 80%(t) 58.F 60%(t) coal 0.81 11.34 i 3. Methane thermal decomposition CH.3 1.0 0.3 117. + 2H.O = CO* + 4H2 80%(t) 94. 4.0 w HZ0 = HZ + 1/202 &2 6.O=H*+ l/20> 44%(t) 4.9 0. Methane steam reforming CH. Natural gas combined cycle power for water electrolysis 55%(e) 44.0 io6.88 H.14 .68 11. 7. Process Feedstock Energy (kcal/mol H.3 0.3 126.3 283.) geothermal (thermal heat equiv. CH.8 71. Comparison of basic energy requirements and CO2 emission Energy efficiencv CO: .73 5 H./mol CH4 Process Total mol H.) emission Process Overall fuel Ratio mot mol Colt Process energy fuel H.05 (C) 80%(t) 64. Hydrogen production.00 11./coal KS 5. CH.) .%(t) waterfall.0 H>O=HZ+1/20.95 18. windpower and geothermal power for electrolysis of 80%(e) 64. 1.2%(t) C CfL 2. 1.0 725.3 113. 1.

OS/lb F0.) 0.2o2 = co2 2H20 + S. emtssion I t CLlrIl01 POWF methanol plant plant 1 and disuersed Coal + 02 = CO2 + H20 r 3/2CH4 = 3l2C + 3H2 bO”KCS CH30H + J Carbon CO2 + 3H2 = CH30H + H20 l. emissions. It is seen that the CO2 plants by the Carnol Process and using the methanol in emission can be reduced by 63-65% using the Carnol automotive engines could reduce the CO. (and CO. It should be pointed out that the ventional steam reforming of natural gas and biomass economics of the Carnol Process is enhanced when the with the Carnol methane decomposition process. compared for gasoline. Application to methanol synthesis by reacting gen plant to convert CO2 from the coal plant to methanol the hydrogen with CO.l4/GaI MeOH SO. (2) Carnol System and (3) biomass hydro. automotive engines. 1 Fig.P. . emission is. Production of hydrogen by methane decompo- line-fueled automotive engine with (1) methanol as a fuel sition requires the least process energy with the least CO. to the current emissions from coal-fired power plant and Table 5 compares methanol produced by the con.541 29 0 100 Steam gasification of biomass o. 4 Based on BNL process [14].76' 0 180 0 Carnol Process from CH. based on this study. 0. STEINBERG Natural gas methane $2. therefore.5 mol CH4 removes CO2 from or market I mol coal AND 1 mol CH4 rotnove~ CO2 from ( :arnol III process for producing methanol Ror n I mol CH4 natural gas and CO2 for . respectively. 2 Heating methane decomposition reactor with CH. based on this CO2 ermssmn. Carnol Process for methanol production to reduce CO. It is carbon produced can be sold on the market as a valuable seen that the CO. Methanol production and CO2 emission process comparison Process Production capacity CO> emission Moles % reduction % reduction MeOH/moles from from feedback conventional Ibs COJMMBTU conventional Conventional process steam reforming of CH. 900°C. emission from power plants and automotive engines. CO. emission can be reduced by 83-100% materials commodity. 40% less for methanol than Process and the biomass process.2liGal MeOH to dispose of CO2 to reduce CO2 r r. for IC engines. 3 Heating methane decomposition reactor with H. 5.21/Gal MeOH) For zero CO2 emission 1. by two-thirds Table 5.0O/MMBTU Pay carnal Pay carnal $O. The kinetics of methane decomposition indicate an Table 6 compares the CO? emission from the current autocatalyzed reaction which is rapid at temperatures of system consisting of a coal-fired power plant and gaso.504 35 0 100 ’ Based on thermal efficiency of 64% [I 31. Steam reforming of CONCLUSION biomass also produces less methanol per unit feedstock than the Carnol Process. recovered from coal-fired power for use in automotive engines.-$O.58’ 24 30 83 o. M. with a 24-29% reduction in production capacity per unit of feedstock using the Carnol Process compared to the conventional natural gas process.

1989. A. BNL 47159. D. 1989..5 Carnol MeOH plant (methane decomp) with methanol fueled automotive IC engine’ 76 63 11’7 Coal-fired power plant 21. Kim&a Tcerdogo Top&a 11(l). Informal Report. and environmental effects of methanol as an automotive sition qf Methane in a Tubular Reactor. O. 116. Johansons rt al. ’ MeOH fueled IC automotive engine is 30% more efficient than gasoline driven IC engine. Upton. X66-923. United States Patent 3. Z. and Katofsky. In Transient Regime. 14. 22 August and methanol via biomass gasification. ’ Carnol plant for methanol is 90% efficient with respect to CO. An analysis of the economic 3. Renewable Energ?. Wyman. 1993. Pergamon Press. 90-Y 1.. emission from system of coal-fired power and liquid HC fueled automotive power.. and process hydrogen from hydrocarbons. Tenser. et al. P... 0730. fuel. Emission units in Ibs/MMBTU (HHV) (multiply by 0. 69. Industrial Pyrolysis. CO. decomposition on the carbon surface. Baku. Chemical Engin- 1. B. and Back. 4 Net CO? emission from biomass gasification to methonal is zero due to photosynthesis. A. angle Park. 1‘. ed. mochemical Biomass Ga.5 Biomass MeOH (gasification) plant with methanol fueled automotive IC engine‘ 71 65 106 Assumptions: ’ Oil refinery is 90% efficient for gasoline production-10% lost to CO>. NY. M. Brookhaven I 1. 113. PRODUCTION OF H2 AND CH. Island Press. 278-285. Kimiya Tverdo. obtained from coal-fired power plant. 2. er al. 4. and Jack. Elsevier Applied Science. DC. E. CO? emission emission from reduction Unit CO1 combined from System emission system conventional Coal-fired power plant 2I 5 Gasoline’ fueled automotive IC engine (conventional) 205 0 I96 Coal-fired power plant 21 5 Natural gas to methanol* by conventional reforming and with methonal fueled I69 18 automotive IC engine’ 139 Coal-fired power plant 21. 8 November 1966. 1993. In Renewable Energy.S.. Production of hydrogen 6. 1129. 1962. . 7. Kinetics of methane thermal London. K. Motor Vehicle Emissions Labora- BNL 60575. R. Biomass and Hydrocarb Technology . Biomass for energy supply prospects. Research Tri- Reaction of Methane. Institute of Petrochemical Processes. 15. 11996. SSR.. 7. Steinberg. B.. The Carnol Process for CO? mitigation from Vol. Larson. 1990.43 to convert to kg/GJ) % co. Ethanol and methanol from cellulosic 1135.for eering. Island Press. and Don&. How to produce hydrogen from fossil sectors. R. D. anol Production and Utilization with Reduced COP Emission. BNL 44410.. M. Washington. Method for hydrogen production by catalytic decomposition of a gaseous hydrocarbon REFERENCES stream.. The Thermal Decompo. Hedden. I. A.. ct al. 1977. 593-651. N. In National Laboratory. 1992. Muradov. Fourth Carbon Conference. U. 1992.R. 1994. Johansons et al. Arefeva. pp. M. pp. H. Back. Makarov. DC. Ann Arbor. Hall. K. 1969. NC 27711.161. M. 10. 425 Table 6.. and Pechic. F.. tory..~$cation. B. C. Pohlenz. EPA Report No. The Carnol Process for Meth. pp. Thermal Decomposition and as an EPA report NMRL RTP-015 USEPA.S. 1983. Kobayashi.qo Toplica 11(5). 12. 13. biomass. T. Removal of Atmospheric COZ. 1977.. To be published 8. fuels without CO2 emissions. Steinberg. E. M. Azerbaijan. In Adllances in Ther- 1961.284. ed. Michigan. F. A. E. from the current power generation and transportation 9. 5. V. and Steinberg. Steinberg. ’ Thermal efficiency is 64% for conversion of natural gas to MeOH-conventional steam reforming plant. power plants and the transportation sector... Oxford. Y . Washington.