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

PRODUCTION OF HYDROGEN AND METHANOL FROM NATURAL GAS

WITH REDUCED CO, EMISSION

MEYER STEINBERG
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 900C 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

INTRODUCTION K, = (PPH,)~/PPCHJ (4)

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.

CHEMICAL EQUILIBRIUM
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 1200C and
at pressures of 25, 30, 40 and 50atm. These data are
calculated from the Gibbs Free Energy and equilibrium
constant
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.

419
420 M. STEINBERG

EXPERIMENTAL Figure 3 shows the relationship between the methane

Figure 2 shows the schematic flow sheet of the exper-
imental equipment which mainly consists of a tubular
reactor, a carbon trap, a gas-chromatograph and gas
meter. Methane enters the system through a remotely
controlled regulator located next to the methane supply
cylinders which keeps the pressure approximately con-
stant at selected pressure of 28.2, 41.8 or 56.1 atm in the
system. Methane flows through a preheater and enters
the reactor which consists of a 1 inch inside diameter
1 4inch wall Inconel 617 tube. The total length of the
reactor tube is 11 feet of which the first 8 feet are exter-
nally heated and selectively maintained at constant exper-
imental temperatures of 700, 800 and 900C by
clamshell electric heaters. Methane is decomposed into
carbon and hydrogen in the heated reactor and the
effluent gas flows through the carbon trap connected at
the bottom of the reactor, where the carbon generated
by the reactor is separated. Gas is sampled before and
after the reactor through sampling lines on an on-line
gas-chromatograph and the concentrations of CH4, CO
and COP in the gas are measured. The flow rate of exit
gas is controlled in the range between 10 and 150 l/min
by a flow valve located after the reactor. The exit gas flows
through the gas meter where the flow rate is measured and
the gas is finally vented to the atmosphere.
EXPERIMENTAL RESULT AND DISCUSSION
Details of the experimental data are given in [3]. A
summary of the calculated data is given below.
concentrations in the exit gas and residence time in the
reactor under the conditions indicated. The residence
time of the methane gas in the reactor is obtained by
the inlet gas velocity. The concentration of the methane
decreases with increasing temperature and residence time.
At both 700 and 800C and at 56.1 atm, the con-
centration of methane decreases less with residence time
than that at 900C and 56.1 atm. Under the latter
conditions, the concentration of methane decreases dra-
matically with residence time and approaches equilibrium
conditions. The concentration of methane at a residence
time of 103sec was 48.1 ~01%. In this case, the equi-
librium concentration of the methane is 39.6~01%. The
equilibrium data at the lower temperatures of 700 and
800C and at 56.1 atm are 54.3 and 69.3 ~01%. respec-
tively. The rate of methane decomposition at the two
lower temperatures appears to be smaller than that at the
higher temperature of 900C.
Generally, the equation for the rate of decomposition
of methane is derived as follows:
CH,;C+2H1 (5)
where k, is the rate constant of methane decomposition,
and k, is the rate constant of methane formation.
The rate equation for this reversible reaction can be
written as follows:
-rCH,= -dCc,,~ldt=k,Cc,~--k,C~l
=k,Gx491 -1/K<, x C~21G~I) (6)

Equilibrium data
at 700C and 56.1 atm

...:--..*

Equilibrium data

l~_~~:!~!~
10-41 I I I I I
8.0 8.5 9.0 9.5 10.0 10.5
80 100 120 1 /T x 1Om4 Arrehenius plot
Residence time (set) Fig. 3. Rate constant of methane decomposition vs reciprocal
Fig. 2. Methane concentrations vs residence time. temperature (at 56.1 atm).
 PRODUCTION OF H, AND CH, 421

;I_
Gas
vent
Methane
feed
Gas

?L-tJ
meter
Press. I
regulator
Gas
chromatograph
l-l

\ lie cylinder
Cl14 cylinder
Carbon
trap

Fig. 4. Schematic flowsheet of tubular reactor for methane decomposition.

where CCH, and CH2 are the molar concentrations of CH, ing above 50 kcal/mol. From the limited methane
and H?, respectively. decomposition data in the literature [4-g], the homo-
The above differential equation for methane decompo- geneous activation energy for methane decomposition
sition in the tubular reactor is solved for the condition is found to be 65 kcaljmol. The data gathered in these
of CH,O = 0 (initial concentration of hydrogen is 0), for experiments appears to be influenced by a heterogeneous
inlet methane concentration C,,40r exit methane con- effect of surfaces. During our experiments, some of the
centration CH40, and equilibrium concentration of meth- carbon formed from methane decomposition adhered to
ane C,,E. 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. In fact, at the end of several extended runs, it
was found that the carbon plugged the tube to the extent
that it restricted the gas flow. Thus, the fine submicron
carbon particles tend to catalyze the thermal decompo-
sition of the methane. [9, lo] clearly indicate that different
Applying the experimental data, Table 1, gives the materials increase the rate of the methane decomposition
calculated k, rate constants at the three temperatures. in the decreasing order of iron oxide, alumina, graphite
In Fig. 4, the rate constants, k,, for methane decompo- and quartz. In the tubular reactor the small submicron
sition are plotted versus reciprocal temperature. 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, 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 1.3 kcal/mol the rate constant of methane decomposition was inves-
(8)
tigated. By plotting the value of k, x t versus the residence
k, = 5.4 x 10exp (- E/RT)l/sec. time t at the three different pressures investigated at
The activation energy appears to indicate a diffusion 900 C the rate constant k, can be determined from the
controlled process which usually has values up to about slopes of the lines. The k, values are listed in Table 2.
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. Rate constants at 900

Table 1. Rate constants at 56.1 atm
Pressure k, value
Temperature k, value
28.2 atm l.O66E-2 l/s
700 C 5.657E-4 l/s 41.8atm 1.380E-2 I/s
800 C 1.753E-4 I/s 56.1 atm 9.306E-3 l/s
900C 9.3066-4 l/s
~ Average rate constant = 1.12E,-2 1 is.
422 M. STEINBERG

with pressure. 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]. The rate equa-
tion (6) modeled in this paper indicates that the rate
constant should be constant and independent of pressure.
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.
Our data indicate that although the thermochemical
equilibrium for methane decomposition is favored by
lower pressures, the rate is favored by higher pressure and
appears to be catalyzed by the carbon particles formed by
the reaction.

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. Table 3 compares fossil fuel
processes and includes biomass reforming. 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 (71.0 kcal/mol)
which includes the energy in the methane feedstocks.
However, when considering CO* emission, methane
decomposition and biomass process yields the least CO,
emission. From an economic point of view at present, the
cost of biomass energy cost is twice as high as that for
natural gas [l 11.
Table 4 compares the hydrogen basic energy require-
ments for fossil with non-fossil energy processes.
It can be seen that the process and total energy require-
ments for electrical, nuclear, solar and thermochemical
water splitting processes are much higher than for fossil
energy feedstock processes. However, when hydroelectric
power is available it is very efficient to use it for the
electrolysis of water. When considering CO*, the non-
fossil systems provide zero CO, emissions. 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, emission system.

METHANOL PRODUCTION
The Carnol Process System is shown in Fig. 5. The
Carnol Process consists of a methane decomposer and a
conventional catalytic methanol synthesis reactor shown
in the inset. The system takes CO, recovered from a coal-
fired power plant and reacts it with hydrogen from the
methane decomposer. The energy required to recover
CO, by a hindered amine solvent is provided by the
exothermic heat of reaction in methanol synthesis. The
methanol formed then is used as fuel in automotive IC
engines. Thus, the CO, emissions from the coal-fired is
practically reduced to zero. Methanol production by the
Carnol Process is also practically reduced to zero. The
use of methanol in automotive IC engines is reported to
be 30% more efficient than the use of gasoline [12]. The
 Table 4. Hydrogen production. Comparison of basic energy requirements and CO2 emission

Energy efficiencv CO:

- Process Feedstock Energy (kcal/mol H,) emission
Process Overall fuel Ratio mot mol Colt
Process energy fuel H,/mol CH4 Process Total mol H,

1. Methane thermal decomposition CH, = C + 2H1 (A) 80%(t) 53.3%(t) H, CH, 1.67 11.3 126.9 0.00
(B) 80%(t) 58.1%(t) CH, CH, 1.81 11.3 117.1 0.05
(C) 80%(t) 64.2%(t) C CfL 2.00 11.3 106.0 0.12

Combined cycle power for electrical heating (D) 55%(e) 53.9%(t) CH, CH, 1.68 11.3 126.2 0.10
XO%(e~
CH,=C+2H2 ;
8
2. Methane steam reforming CH, + 2H,O = CO* + 4H2 80%(t) 94.6%(t) CH, CH, + Hz0 2.95 18.8 71.9
0.34 i
3. Natural gas combined cycle power for water electrolysis 55%(e) 44.0%(t) CH, Hz0 1.37 154.5 154.5
80%(e) 0.73 5
H,O=H*+ l/20> 44%(t) 4;
4. Thermochemical cycle-coal fired heat for water splitting 60.0%(t) Hz0 113.3 113.3 1.14 ,F
60%(t) coal 0.88 H,/coal
KS
5. Nuclear energy for electrolysis of water 30%(e) 24.0%(t) U-235 Hz0 283.3 283.3 0.0 w

HZ0 = HZ + 1/202 &2

6. Solar photovoltaics for electrolysis of water 10%(e) 8.0%(t) solar Hz0 725.0 725.0 0.0

H>O=HZ+1/20,

7. Hydropower, windpower and geothermal power for electrolysis of 80%(e) 64.%(t) waterfall, Hz0 106.0 io6.0 0.0
water 80%(e) (thermal wind and
HZ0 = HZ + l/20: 64%(t) equiv.) geothermal
(thermal heat
equiv.)
 M. STEINBERG

Natural gas
methane
$2.0O/MMBTU
Pay carnal Pay carnal
$O.l4/GaI MeOH SO.2liGal MeOH
to dispose of CO2 to reduce CO2
r r, emtssion
I t
CLlrIl01
POWF
methanol
plant plant
1 and disuersed

Coal + 02 = CO2 + H20 r 3/2CH4 = 3l2C + 3H2

bOKCS
CH30H +
J
Carbon
CO2 + 3H2 = CH30H + H20 l,2o2 = co2
2H20
+

S.P.-$O.OS/lb
F0.21/Gal MeOH)

For zero CO2 emission

1.5 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 .zero CO2 ermssmn.
1
Fig. 5. Carnol Process for methanol production to reduce CO, emission from power plants and automotive engines.

CO, emission is, therefore, 40% less for methanol than
for gasoline.
Table 5 compares methanol produced by the con-
ventional steam reforming of natural gas and biomass
with the Carnol methane decomposition process. It is
seen that the CO, emission can be reduced by 83-100%
with a 24-29% reduction in production capacity per unit
of feedstock using the Carnol Process compared to the
conventional natural gas process. Steam reforming of
biomass also produces less methanol per unit feedstock
than the Carnol Process.
Table 6 compares the CO? emission from the current
system consisting of a coal-fired power plant and gaso-
line-fueled automotive engine with (1) methanol as a fuel
for IC engines, (2) Carnol System and (3) biomass hydro-
gen plant to convert CO2 from the coal plant to methanol
for use in automotive engines. It is seen that the CO2
emission can be reduced by 63-65% using the Carnol
Process and the biomass process, respectively, compared
to the current emissions from coal-fired power plant and
automotive engines. It should be pointed out that the
economics of the Carnol Process is enhanced when the
carbon produced can be sold on the market as a valuable
materials commodity.
CONCLUSION
The kinetics of methane decomposition indicate an
autocatalyzed reaction which is rapid at temperatures of
900C. Production of hydrogen by methane decompo-
sition requires the least process energy with the least CO,
emissions. Application to methanol synthesis by reacting
the hydrogen with CO, recovered from coal-fired power
plants by the Carnol Process and using the methanol in
automotive engines could reduce the CO, by two-thirds

Table 5. 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, 0.76' 0 180 0

Carnol Process from CH, (and CO,) 0.58 24 30 83
o.541 29 0 100
Steam gasification of biomass o.504 35 0 100

Based on thermal efficiency of 64% [I 31.

2 Heating methane decomposition reactor with CH, based on this study.
3 Heating methane decomposition reactor with H, based on this study.
4 Based on BNL process [14].
 PRODUCTION OF H2 AND CH, 425

Table 6. CO, emission from system of coal-fired power and liquid HC fueled automotive power. Emission units in Ibs/MMBTU
(HHV) (multiply by 0.43 to convert to kg/GJ)

% co,
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 21.5

Carnol MeOH plant (methane decomp) with methanol fueled automotive IC engine 76 63
117

Coal-fired power plant 21.5

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>.
Thermal efficiency is 64% for conversion of natural gas to MeOH-conventional steam reforming plant.
Carnol plant for methanol is 90% efficient with respect to CO, obtained from coal-fired power plant,
4 Net CO? emission from biomass gasification to methonal is zero due to photosynthesis.
MeOH fueled IC automotive engine is 30% more efficient than gasoline driven IC engine.

from the current power generation and transportation 9. Muradov, N. Z., How to produce hydrogen from fossil
sectors. fuels without CO2 emissions. Informal Report, Institute of
Petrochemical Processes. Azerbaijan, SSR. Baku, U.S.S.R.,
1989.
10. Pohlenz, A. and Jack, B. Method for hydrogen production
by catalytic decomposition of a gaseous hydrocarbon
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