Applied Catalysis A: General 224 (2002) 201–207

Comparatively high yield methanol production from

gas phase partial oxidation of methane
Qijian Zhang, Dehua He∗ , Jinlu Li, Boqing Xu, Yu Liang, Qiming Zhu
State Key Laboratory of C1 Chemistry and Technology, Department of Chemistry, Tsinghua University, Beijing, 100084, PR China
Received 28 May 2001; accepted 6 August 2001

Abstract
Gas phase partial oxidation of methane to methanol has been carried out in a specially designed reactor. A comparatively
high yield of methanol (ca. 7–8%, methanol selectivity of 60% at methane conversion 13%) was obtained over a quite wide
temperature range of more than 40 ◦ C at 5.0 MPa and CH4 /O2 /N2 = 100/10/10 (ml/min). The effects of the total flow rate,
CH4 /O2 ratio and pressure were examined and the superiority of the new reactor is discussed. © 2002 Elsevier Science B.V.
All rights reserved.
Keywords: Gas phase; Partial oxidation; Methane; Methanol

1. Introduction [8]. They both reported methanol selectivities higher

The direct partial oxidation of methane to methanol
is one of the attractive potential industrial processes
for the use of abundant nature gas resources. Being an
exothermic reaction, the direct conversion of methane
to methanol would be superior to the conventional
industrial process for the production of methanol via
syngas by steam reforming of methane in terms of
energy efficiency. Technoeconomic evaluation [1–4]
has demonstrated that, giving over 70% methanol
selectivity at 8–15% methane conversion, the direct
process is able to compete with the indirect one. Un-
fortunately, most of the reported methanol selectivities
have not broken through 70%, while methane con-
versions were always below 5% when high methanol
selectivity obtained. The most promising results were
from Gesser and co-workers [5–7] and Feng et al.
∗ Corresponding author. Tel.: +86-10-6278-4589;
fax: +86-10-6279-2122.
E-mail address: hedeh@mail.tsinghua.edu.cn (D. He).
than 70% at methane conversion over 8%. But under
similar conditions, Burch couldn’t reproduce Gesser’s
results [9]. Therefore, the direct process still needs to
be further developed.
The gas phase partial oxidation of methane is oper-
ated by a free radical mechanism, which is extremely
hard to control. Therefore, it is expected that the par-
ticipation of catalyst would improve methanol selec-
tivity and yield. But until now, the catalytic reaction
has not produced yields of methanol plus formalde-
hyde better than those of reported gas phase process,
except for a few excellent reports [10–15].
Reviews by Gesser et al. [16], Pitcher and Klier [17],
Brow and Parkyns [18], and Foulds and Gray [19] pro-
vided an overall view of the progress in the gas phase
homogeneous partial oxidation of methane. High pres-
sure seems to favor the formation of methanol. High
CH4 /O2 would give higher methanol selectivity and
lower methane conversion.
Gesser first reported high selectivity of methanol of
ca. 80% using a quartz-lined tubular reactor instead

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202 Q. Zhang et al. / Applied Catalysis A: General 224 (2002) 201–207

of the stainless steel (SS) one [20], although in a later

paper, he suggested that the wall composition did not
greatly affect methanol selectivity at high pressure
[21]. Burch et al. stated that by using a glass-lined
reactor, it was possible to ensure that the reaction
was essentially homogeneous [9], therefore quartz or
pyrex glass-lined reactors were recommended. But
because the reaction had better be operated at high
pressure, the glass-lined reactor has to be placed in a
pressure-resistant assembly, usually a SS tube. Then,
how to avoid the feed gas flow through the ringed gap
between the inner glass line and the SS tube becomes
a serious problem.
In the present paper, the ringed gap was insulated
using a Viton O-ring pressed by a locking nut. Some
interesting results were obtained, and some reasons
for those were discussed.

2. Experimental

The gas phase oxidation of methane was carried out

at 380–500 ◦ C and 1.0–5.0 MPa in a high pressure flow
reactor (Fig. 1). A 460 mm long quartz line (6.7 mm
i.d.) was tightly fixed in a SS line. A Viton O-ring
pressed by a locking nut was used to prevent the gas
Fig. 1. Reactor structure.
from leaking into the ringed gap so as to eliminate the
influence of the metal wall. The reaction temperature TDX-01 to separate N2 , O2 , CH4 , CO, etc. The addi-
was measured by a thermal couple, which was pro- tion of nitrogen in the feed gas acted both as diluent
tected with a quartz tube of 5.5 mm o.d. with a dead and as internal standard. The concentration of H2 in
end. Such an assembly was designed to prevent the the outlet gas was analyzed by another GC (Varian
contact of the reactants with the metal wall so as to 3400 GC, TCD, Ar carrier). The outlet gas was sam-
avoid deep oxidation. The quartz line was heated with pled after a cooling trap to remove H2 O, CH3 OH and
an electric furnace from the outside of the SS line. HCHO (if present).
The electric furnace was equipped with three inde- The methane conversion was defined as
pendently controlled heaters (90 mm, 750 W; 90 mm,

A i f i Ni
1500 W; 90 mm, 750 W, respectively). Adjusting the XCH4 =
× 100
electric voltage of each heater would vary the length of Ai fi Ni + ACH4 fCH4
the flat temperature zone and the temperature profile. where Ai is the integrated area of product i in the chro-
The flow rate of each reactant was controlled by matography; fi is the calibration factor of product i; Ni
a mass flow controller (Brooks 5850E serried) and is the number of carbon of product i. The selectivity
the pressure was controlled by a back-pressure regu- of product i was defined as
lator (Tescom Co.). The reaction effluent was kept at A i fi
about 150 ◦ C to prevent condensation of liquid prod- Si =
× 100
Ai fi
uct. The product mixture was sampled by a six-way
valve and analyzed by an on-line gas chromatograph carbon balance was defined as

 
(GC) (SHIMADZU GC-8A, TCD, H2 carrier), which
product A i f i N i + A CH 4 f CH 4 /A N2
was equipped with two columns: GDX-403 to sepa- T0
CB =
rate CH3 OH, HCHO, C2 H4 , C2 H6 , H2 O, CO2 , and (ACH4 fCH4 /AN2 )T
 Q. Zhang et al. / Applied Catalysis A: General 224 (2002) 201–207
where T0 is the temperature when no reaction oc-
curred, and T is the reaction temperature. The results
were considered believable only when CB = 1±0.05.
3. Results
The products of the gas phase oxidation of methane
were mainly CH3 OH, CO, CO2 , C2 H6 , and some-
times C2 H4 . The typical distribution of products as a
function of temperature is shown in Fig. 2. CO was
first produced and, when the temperatures was above
400 ◦ C, the oxygen conversion increased sharply to
100% in a very narrow temperature range. The selec-
tivity of CO decreased to ca. 32% while the selectivity
of CH3 OH increased to a steady level of ca. 63%, and
both remained constant for a wide temperature range
of about 40 ◦ C (430–470 ◦ C). Selectivity of CO2 was
kept no higher than 6%. Above 470 ◦ C, the selectiv-
ity of CH3 OH began to decrease, and the selectivity
of CO increased while the selectivity of CO2 did not
change significantly. Such results might indicate that
CO and CH3 OH were produced from the same inter-
mediate, perhaps the radical of CH3 or CH3 O. The
amount of C2 H6 in the effluent was very small, but
with temperature increasing, its selectivity increased
steadily up to 1%. (Fig. 3). Production of H2 was also
observed in the experiments. The ratio of H2 /CO was
about 0.4–0.5. The presence of hydrogen in the outlet
stream has been reported by Lødeng et al. [22] and
Chellappa et al. [23]. In view of the fact that no HCHO
was detected, it was supposed that under such reac-
Fig. 2. Effect of temperatures on feed gas conversions and product
selectivities P = 5.0 MPa, CH4 /O2 /N2 = 100/10/10 (ml/min)
conversion of CH4 (䉬); O2 (䊏); CH3 OH yield (䊉); selectivity
of CH3 OH (䊐); CO (); CO2 (䉫).
203
Fig. 3. Effect of temperatures on C2 selectivity and H2 production
P = 5.0 MPa, CH4 /O2 /N2 = 100/10/10 (ml/min).
tion conditions, HCHO decomposed quickly to H2 and
CO once it was formed in the reaction network. In the
mechanism studies, CO was supposed to be produced
from the HCO radical [22–24]. Maybe HCHO was not
formed practically in the reaction for the decomposi-
tion of HCO by some oxidizing species, such as H,
OH, HO2 or CH3 O, was much faster than its abstrac-
tion of H from reducible species to form HCHO.
In most experiments, the selectivity of methanol
was optimized at a certain temperature range when
oxygen was just used up. Methanol selectivity would
decrease quickly at higher temperature. The present
results were quite unique in that comparatively high
methanol selectivity was kept for a wide temperature
range. These interesting results will be discussed in
Section 4.
Fig. 4 shows the effect of the gas flow rate on the
oxidation of methane to methanol at 100% oxygen
conversion (450 ◦ C). When oxygen was completely
consumed, the increase in the flow rate resulted in a
slight decrease in CH3 OH selectivity and increase in
CO selectivity, while CO2 selectivity was not affected.
It is noticeable that the decrease of CH3 OH selectiv-
ity and increase of CO selectivity were not dramatic,
so the gas flow rate had no significant effect on
the product distribution at 100% oxygen conversion.
Therefore, it is possible to increase the time–space
yield of methanol by increasing the total flow rate.
Gesser’s result was obtained at very low gas flow rate
(only 30 ml/min [7]). Though high selectivity might
be achieved, the time–space yield would be poor.
204 Q. Zhang et al. / Applied Catalysis A: General 224 (2002) 201–207
Fig. 4. Effect of flow rates on the partial oxidation of methane to
methanol P = 5.0 MPa, T = 450 ◦ C, CH4 /O2 /N2 = 10/1/1 CH4
conversion (䉬); CH3 OH yield (䊉); selectivity of CH3 OH (䊐);
CO (); CO2 (䉫).
CH4 /O2 ratios had great effect on the product distri-
bution (Fig. 5). Higher CH4 /O2 ratios provided higher
CH3 OH selectivity and lower CH4 conversion, which
suggests that the concentration of the oxygen signif-
icantly influences the gas phase partial oxidation of
methane to methanol. These trends are in agreement
with most of the reported results [23,25–28], though
Burch et al. stated that oxygen concentration (CH4 /O2
ratio) had little effect on the products distribution in
the range of 2.5–6.6% [9]. But it is worthwhile to no-
Fig. 5. Effect of CH4 /O2 ratios on the partial oxidation of
methane to methanol P = 5.0 MPa, T = 450 ◦ C, total flow
rate = 120 m1/min CH4 conversion (䉬); CH3 OH yield (䊉); se-
lectivity of CH3 OH (䊐); CO (); CO2 (䉫).
Fig. 6. Effect of pressures on the partial oxidation of methane to
methanol P = 5.0 MPa, T = 450 ◦ C, CH4 /O2 /N2 = 100/10/10
(ml/min) CH4 conversion (䉬); CH3 OH yield (䊉); selectivity of
CH3 OH (䊐); CO (); CO2 (䉫).
tice that the CH4 /O2 ratios adopted in the present work
were lower than most of the reported ones although
these might be in the explosion limits of CH4 /O2 mix-
tures. The methanol yield did not drop dramatically
with decreasing of the CH4 /O2 ratio in the range of
4–10. The yields of methanol were all about 7–8%.
Therefore, the CH4 /O2 ratio had little effect on the
yield of methanol. With regard to the safety consider-
ations, and the effective use of CH4 , we recommend
the CH4 /O2 ratio to be at about 10.
The effects of pressure are illustrated in Fig. 6. At
a pressure of 1.0 MPa, the reaction did not take place
till 470 ◦ C. When oxygen was completely depleted
at 500 ◦ C, CO was the predominant product (77.3%).
With the increase of pressure, CO selectivity decreased
quickly while CH3 OH selectivity increased greatly. At
above 4.0 MPa, the increasing tendency of CH3 OH
selectivity began gently. Therefore a pressure of 5.0
MPa would be suitable for methane oxidation.
4. Discussion
The results mentioned above were quite different
from those in our earlier report [12,13] and most other
reports. It is interesting and important to clarify what
the discrepancy should be ascribed to. The most likely
reasons include the changes of the reactor structure:
(1) the heating manner, which would bring a new char-
acter to the temperature profile of the reactor; (2) the
 Q. Zhang et al. / Applied Catalysis A: General 224 (2002) 201–207
insulation of the ringed gap between the inner quartz
line and the outer SS tube (using an O-ring between
them at the top of the lines, see Fig. 1), which avoided
the influence of the wall of SS tube; (3) the peculiarity
of the quartz line and (4) the use of a spacer (a quartz
tube cover of the thermocouple, see Fig. 1), which
might affect the flow pattern and shorten the residence
time. In order to determine which is the main cause,
experiments were carried out with the variation of the
related operational factors.
Firstly, the temperature profile was varied by chang-
ing the heating manner so as to change the length of
the flat temperature zone. From Fig. 7, it can be seen
that the length of flat temperature zone of case I was
about 2 cm shorter than that of case II. Obviously, case
I was superior to case II. The longer the flat temper-
ature zone is, the more decomposition of methanol
Fig. 7. Effect of flat zone on the partial oxidation of methane to
methanol P = 5.0 MPa, T = 450 ◦ C, CH4 /O2 /N2 = 100/10/10
(ml/min).
205
Fig. 8. Effect of O-ring on the partial oxidation of methane to
methanol P = 5.0 MPa, T = 450 ◦ C, CH4 /O2 /N2 = 100/10/10
(ml/min).
would take place. So, the length of flat temperature
zone was an important factor. But a longer flat tem-
perature zone was unfavorable to methanol selectivity.
Results of experiments with and without the Viton
O-ring between the quartz line and SS line at the top
of the lines are shown in Fig. 8. In the case without the
Viton O-ring, the methanol selectivity decreased dra-
matically. Much of the earlier work has confirmed that
methanol selectivity diminished in the presence of SS
surface due to the competing deep oxidation reactions
catalyzed by the metal surface. To minimize surface
reactions, pyrex or quartz lines were recommended
[19]. The results presented here showed that the cat-
alytic effect of the surface of SS line on methanol or
HCHO should be considered seriously even when a
quartz line was used. How to avoid the contact of re-
actant with metal surface is an extremely important
factor.
Omata et al. [26] had clarified that the pyrex glass
is as inert as quartz glass in the partial oxidation of
methane in the temperature range of 300–500 ◦ C. Ex-
periments with a silicate glass line in place of the
quartz line were carried out. The results showed that
the silicate glass-lined reactor could produce methanol
selectivity only 9% less than that of quartz-lined one
(Fig. 9). So, the silicate glass can also be used in the
partial oxidation of methane. The material of the glass
line fitted in the SS line is less important.
In order to measure the temperature of the reaction
zone, a thermocouple protected with a quartz tube was
206 Q. Zhang et al. / Applied Catalysis A: General 224 (2002) 201–207
Fig. 9. Comparison of silicate glass and quartz line in the partial
oxidation of methane to methanol P = 5.0 MPa, T = 450 ◦ C,
CH4 /O2 /N2 = 100/10/10 (ml/min).
placed into the center of the reactor, which worked
as a spacer and might influence the flow pattern and
shorten the residence time of the gases. In order
to verify whether the spacer influenced the product
distribution, a comparable experiment was carried
out with the thermocouple drawn to the bottom of
the reactor, and the inner quartz tube protecting the
thermocouple removed. Drawing down the thermo-
couple resulted in a decrease of methanol selectivity
from 63 to 49% and methanol yield from 8.2 to 5.9%
(Fig. 10), which indicated that the spacer had some
effect on the yield of methanol though the effect was
not significant. Sokolovskii et al. [29] pointed out that
Fig. 10. Effect of spacer on the partial oxidation of methane to
methanol P = 5.0 MPa, T = 450 ◦ C, CH4 /O2 /N2 = 100/10/10
(ml/min).
reasonable methane conversion could be achieved by
removing the required product after a short residence
time. Discrepancies in methanol selectivity in differ-
ent research experiments can partly be attributed to
the local flow patterns [18,30]. Omata et al. adopted
a similar structure reactor in the partial oxidation of
methane, but they didn’t discuss the effect of the in-
ner quartz tube, and they only obtained a methanol
selectivity of no more than 30% [26].
From the above discussion, the insulation of the
ringed gap determines whether the reaction was es-
sentially homogeneous and whether high yield of
methanol could be achieved. Shortening the flat tem-
perature zone of the reactor, using quartz-lined reac-
tor and a spacer are helpful to further improve the
methanol selectivity and yield.
5. Conclusion
Using a newly designed reactor, a comparatively
high yield of methanol could be achieved over a
wide temperature range for the partial oxidation of
methane. Selectivity of ca. 63% at methane conver-
sion of 13% was obtained at 5.0 MPa, 430–470 ◦ C,
and CH4 /O2 /N2 = 100/10/10(ml/min, STP). Produc-
tion of CO2 was suppressed to a very low level and
much hydrogen was produced. The insulation of the
ringed gap between the inner quartz line and the SS
tube is of great importance to obtain high methanol
selectivity. If the feed gas could be isolated from con-
tacting with the metal wall, the gas phase oxidation
of methane could yield quite good results.
Acknowledgements
We acknowledge the financial support from the Na-
tional Key Fundamental Research Project Foundation
of China and the Research Foundation of Tsinghua
University.
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