RESEARCH ARTICLE

Engineering evaluation of direct methane to methanol

conversion
Arno de Klerk
Department of Chemical and Materials Engineering, University of Alberta, Edmonton, Alberta, T6G 2V4, Canada

Keywords Abstract
Gas-to-liquids, methane, methanol, natural
gas, partial oxidation Investigations into direct methane to methanol conversion are justified based
on the avoidance of synthesis gas generation, which accounts for around 60%
Correspondence of the capital cost of synthesis gas to methanol conversion. A significant body
Arno de Klerk, Department of Chemical and of information already exists on the process chemistry, but little has been
Materials Engineering, University of Alberta, reported on the engineering of such a process. An engineering evaluation of the
Edmonton, Alberta T6G 2V4, Canada. Tel:
process was performed and the potential of this process as a platform technol-
+1 780-248-1903; Fax: +1 780-492-2881;
E-mail: deklerk@ualberta.ca
ogy for small-scale gas-to-liquids (GTL) applications was evaluated. It was
found that direct methane to methanol conversion had 35% carbon efficiency
Funding Information and 28% thermal efficiency, which were about half of the process efficiencies of
No funding information provided. indirect methanol synthesis using synthesis gas. The poor process efficiency was
mainly a consequence of the irreversible loss of carbon to COx during conver-
Received: 12 October 2014; Revised: 15 sion. The direct methane to methanol process also required an air separation
November 2014; Accepted: 18 November
unit, which eroded the stated benefit of avoiding a synthesis gas generation step
2014
in the process. The utility footprint was typical of GTL processes, with large gas
Energy Science and Engineering 2015;
compression duties and cooling duties. Overall, the engineering evaluation indi-
3(1): 6070 cated there was no benefit to employ direct methane to methanol conversion
instead of indirect methanol synthesis (the industry standard), and there was
doi: 10.1002/ese3.51 no specific benefit of direct methane to methanol conversion, irrespective of
scale, for GTL applications.

methane to methanol conversion [4]. It is one of a class

Introduction
of processes that involves the reaction of methane with an
Methanol is a large volume commodity chemical. Indus- oxidant and direct oxidative methane conversion is often
trially methanol is produced mainly by indirect liquefac- discussed collectively [5, 6, 7, 8]. Studies that consider the
tion of natural gas [1]. The indirect liquefaction process engineering aspects of processes for direct oxidative meth-
involves three steps (Fig. 1). The first step is reforming of ane conversion are less abundant [9, 10].
natural gas to synthesis gas, which is then in the second On paper the direct conversion of methane to metha-
step converted into methanol. Synthesis gas conversion to nol seems like a good idea. The trade-off between con-
methanol is conducted over a Cu-ZnO-based catalyst and version and product selectivity is anticipated and can in
methanol is obtained with high selectivity. The conversion principle be overcome by the recycling of unconverted
of synthesis gas to methanol is equilibrium limited [2]. In methane. Examples of industrial processes for the direct
the third step, the crude methanol is recovered from the oxidation of methane to methanal (formaldehyde) can
unconverted synthesis gas and purified, while the uncon- be found [4, 11, 12], but there are no examples of
verted synthesis gas is recycled. The most expensive step direct oxidation of methane to methanol, which techni-
in process is synthesis gas generation, which accounts for cally requires only a change in reactor operation. Yet,
60% of the capital cost of the process [3]. the industrial methane to methanal conversion cited was
Methanol can also be produced by the direct partial of such low capacity (<1 t/day) that it would only be
oxidation of methane to methanol. There is a consider- referred to as large pilot-scale in current terms. To
able body of literature on the process chemistry of direct quote Arutyunov [4]:

60 2014 The Authors. Energy Science & Engineering published by the Society of Chemical Industry and John Wiley & Sons Ltd.
This is an open access article under the terms of the Creative Commons Attribution License, which permits use,
distribution and reproduction in any medium, provided the original work is properly cited.
A. de Klerk Direct Methane to Methanol

Gas recycle

Syngas Methanol Product

Methane Methanol
generation synthesis recovery

60 % of cost

Figure 1. Simplified block flow diagram of indirect methanol synthesis.

. . . partial oxidation of dry natural gas, which requires If heavier hydrocarbons are present, such as ethane and
more stringent conditions and gives lower yield of the tar- propane, the reaction proceeds more readily, since it is
get products [than heavier hydrocarbon gases], has never easier to oxidize heavier hydrocarbons.
been mastered by the industry. The main carbon-containing products that are pro-
duced during the partial oxidation of methane at temper-
What is it then that prevents direct methane to metha-
atures below 450C are methanol (eq. 1), methanal
nol conversion to be applied?
(eq. 2), methanoic acid (eq. 3), carbon monoxide (eq. 4),
The objective of this work was to perform an engineering
and carbon dioxide (eq. 5):
evaluation of the direct methane to methanol conversion
process. Of specific interest was to evaluate the potential of 1
CH4 O2 ! CH3 OH; (1)
this process to be employed as a platform technology for 2
small-scale gas-to-liquids (GTL) applications. CH4 O2 ! CH2 O H2 O; (2)
1
CH4 1 O2 ! HCOOH H2 O; (3)
Process Chemistry 2
1
The first challenge in the direct conversion of methane is CH4 1 O2 ! CO 2H2 O; (4)
2
overcoming the stability of the CH bonds in methane.
CH4 2O2 ! CO2 2H2 O: (5)
Strategies to activate CH in methane are discussed in lit-
erature, for example, [13], but activation of the CH The reaction engineering strategy that is employed to
bond is only part of the challenge. Free radical partial maximize the methanol selectivity during gas phase oxi-
oxidation is a quite successful strategy to activate CH dation of methane is to limit the single-pass conversion.
bonds in methane. Despite many claims in literature of This is achieved by limiting the concentration of the oxi-
the beneficial effects of employing catalysts, catalysts do dant. When the oxidant is the limiting reagent, successive
not appear to offer meaningful yield advantages [4, 14]. It oxidation reactions are inherently limited and the selectiv-
appears that the role of catalysis is mainly to reduce the ity to primary oxidation products is increased. Some gen-
severity of process conditions. The partial oxidation of eral observations about the operating conditions and
methane to methanol is therefore more simply conducted process chemistry can be made: [4, 17, 18]
as a gas phase free radical process, which avoids gas (1) Typical operating temperatures for noncatalytic par-
cleaning to remove potential catalyst poisons. The free tial oxidation of methane to methanol are in the range
radical partial oxidation of methane to methanol is not 370470C. It is impractical to perform the reaction at
deleteriously affected by the presence of hydrogen sulfide temperatures below 350C, because the induction time is
or other contaminants that may be present in natural long and the methane oxidation rate is low. At higher
sources of methane, such as natural gas. temperatures, there is an increase in oxidative coupling
The other part of the direct methane conversion chal- reactions to form heavier hydrocarbons, such as ethane
lenge is to prevent further reaction of the products from and ethene. No literature to the contrary was found and
partial methane oxidation. The homolytic bond dissocia- there is high confidence in the operating temperature
tion energy of the CH in methane (439 kJ
mol1) is range indicated.
higher than that in methanol (402 kJ
mol1), methanal (2) Methanol and other desirable products are interme-
(369 kJ
mol1), or in methanoic acid (402 kJ
mol1) diate oxidation products. Oxidation of methanol and the
[15]. Whatever CH bond activation strategy, it will work other oxygenates is easier than oxidation of methane. This
better on the products of methane conversion than on is an example of an A?B?C reaction where B is
methane itself. (An analogous problem presents itself for desired product. With increasing O2 feed concentration
microbial conversion, where it is necessary to inhibit the selectivity to methanol decreases, irrespective of the
methanol conversion in methane to methanol processes, temperature. Since the O2 concentration in the feed limits
because methanol is more easily metabolized) [16]. the conversion, this is a typical conversion-selectivity

2014 The Authors. Energy Science & Engineering published by the Society of Chemical Industry and John Wiley & Sons Ltd. 61
Direct Methane to Methanol A. de Klerk

trade-off. In order to minimize combustion reactions not a reaction network. A far more complex interrelation-
(eqs. 4 and 5), it was claimed that the oxidant concentra- ship exists between the various species. Not all reactions
tion must not exceed 2.8% and should ideally be in the in such a reaction network require oxygen to be present.
range 2.02.8% [17]. There is also a restriction on the Thermal decomposition and disproportionation reactions
methane to O2 ratio, with methanol selectivity being can proceed without oxygen. For example, the thermal
quickly eroded as the methane to O2 ratio decreases decomposition of methanal to produce CO, H2 and
below 30:1. methanol (eqs. 67) [24].
(3) Operating at higher pressures is beneficial to methanol CH2 O ! CO H2 (6)
selectivity and the overall yield of oxygenates (eqs. 13).
This is understandable from Le Chateliers principle, 2CH2 O ! CH3 OH CO (7)
because methanol synthesis causes molar contraction, There is no lack of information on the chemistry, but
whereas the converse is true for oxidation to COx (eqs. 4 constructing a credible reaction network and obtaining
5). At pressures below 8 MPa, the oxygenate yield decreases kinetic data for the individual reactions are more chal-
monotonously with pressure, but at pressures above 8 MPa lenging tasks. This information was conspicuously absent
the reaction becomes fairly insensitive to pressure. The sug- from discussions on the process chemistry of direct meth-
gested minimum practical pressure of operation is, there- ane to methanol conversion.
fore, around 8 MPa. Less was published on pressure effects
and the threshold pressure value is a best estimate. There is
moderate confidence in the minimum operating pressure Process Description
threshold. Process flow diagrams for partial oxidation of hydrocar-
(4) In the temperature range 370450C at typical oper- bons with recycle, can be found in the literature [4, 9, 11,
ating conditions described above, the selectivity to metha- 12]. For the purpose of an engineering evaluation, it is
nol is around 40%, the selectivity to methanal increases necessary to develop the key elements of the process more
from 5% to 13% with increasing temperature and the fully, so that the utility requirements can be determined.
selectivity to carboxylic acids increased from 0.5% to The utility footprint of GTL processes that employ syn-
0.7% with increasing temperature. There is only moderate thesis gas is substantial [25]. Although the direct methane
to low confidence in the selectivity values, which repre- to methanol conversion process does not involve synthesis
sent a best estimate based on literature. gas generation, many of the process elements leading to a
(5) Cofeeding free radical initiators can initiate the oxi- high utility footprint are still present, such as oxidant
dation reaction and eliminate the induction time when compression, gas recycling, and high temperature opera-
employing O2 as oxidant. This strategy was employed for tion.
formaldehyde production by direct partial oxidation of The process flow diagram of direct methane to metha-
methane, where a small quantity of NO was cofed [4, 11]. nol conversion is shown in Figure 2. The equipment table
Direct methane to methanol conversion making use of is given in Table 1.
N2O with a catalyst to conduct the reaction at lower tem- There are two raw material streams, natural gas and
perature was reported [19], and low temperature methane the oxidant. These input streams are compressed and pre-
to methanol synthesis could also be achieved by NO cata- heated separately to avoid premature oxidation. Oxida-
lyst activation [20]. tion must be controlled to obtain good selectivity to
As an alternative to oxygen as oxidant, hydrogen per-
oxide (H2O2) in combination with a catalyst enables low Table 1. List of equipment shown in the process flow diagram in
Figure 2.
temperature oxidation of methane to methanol [21].
Other examples can also be found in the literature. Many Number Equipment
oxidants are capable of oxidation at the carbon atom [22,
C-01 Natural gas feed compressor
23]. The selection of an appropriate oxidant is an eco- C-02 Oxidant feed compressor
nomic decision, since oxidant consumption is stoichiome- C-03 Recycle gas compressor
tric with respect to the oxidation products. Air or O2 E-01 Interstage cooler for compressor C-01
separated from air is often the most economical choice E-02 Interstage cooler for compressor C-02
for oxidation of a total feed stream, as is the case in E-03 Oxidant heater (doubles as start-up heater)
methane to methanol conversion. E-04 Feed-product heat exchanger
E-05 Product coolers
The reaction network is complex, which is typical of
R-01 Partial oxidation reactor
any partial oxidation reaction involving a free radical V-01 High-pressure phase separator vessel
mechanism. The reactions that were listed (eqs. 15) are

62 2014 The Authors. Energy Science & Engineering published by the Society of Chemical Industry and John Wiley & Sons Ltd.
A. de Klerk Direct Methane to Methanol

15 14 13
Purge gas

8
C-03

12
1 2 6 7
Natural gas
R-01
C-01/E-01 E-04 9 10

5 E-05 V-01 11
3 4
Oxidant Liquid product

C-02/E-02 E-03

Figure 2. Process flow diagram of direct methane to methanol conversion.

methanol and much of the technology know-how is 800

related to the design of the partial oxidation reactor. In 700 Outlet pressure: 8 MPa abs

Duty (kJ/kg methane)

the partial oxidation reactor, the methane is partially oxi- 600
dized to produce methanol, with the oxidant being the 500
limiting reagent. The product gas is cooled and the meth-
400
anol is recovered by condensation. The recovered crude
300
methanol and side-products can be separated and purified Ideal shaft work
200 Cooling duty
by conventional distillation. Product work-up is not
100
unique to the direct methane to methanol synthesis pro-
0
cess and it is not shown or considered in this evaluation. 0 1 2 3 4 5
Part of the unconverted natural gas is recycled and part is Natural gas inlet pressure (MPa abs)
purged. The purge of some unconverted natural gas is
necessary to limit the build-up of inert material in the Figure 3. Ideal shaft work and cooling duty for natural gas
process. compression to 8 MPa.
The main elements of the design and design decisions
associated with each will be discussed. requires cryogenic distillation, or some form of pressure
swing adsorption. Thus, of all the natural gas components
nitrogen will have the most impact on the purge rate. For
Natural gas feed the purpose of this evaluation, a generic natural gas com-
The hydrocarbon feed to the process is natural gas and position was employed (Table 2). This gas composition
not pure methane. In most instances, the natural gas will does not include H2S or Hg, which are likely to be pres-
be available at an elevated pressure. The gas pressure will ent in some sources of natural gas [27].
depend on the source of the natural gas. If it is associated
gas, which is coproduced with crude oil, the gas may only Oxidant feed
be available at low pressure, for example, 0.2 MPa, while
connected natural gas in a distribution network will typi- It is in principle possible to use air, oxygen-enriched air,
cally be available at higher pressure, for example, 8 MPa or oxygen as oxidant feed for the direct methane to meth-
[26]. The extent of compression and intercooling required
for the process depends on the feed conditions and the
Table 2. Generic natural gas composition.
calculated relationship is shown (Fig. 3). The ideal shaft
work is shown, from which the actual shaft work and Compound Natural gas
utility requirements can be calculated. The cooling duty Composition (mol fraction)
was calculated based on the intercooling requirements for Methane (CH4) 0.950
a realistic compressor design. Cooling duty becomes zero Ethane (C2H6) 0.005
at an inlet pressure of ~1.2 MPa, when no intercooling is Nitrogen (N2) 0.030
required for the compressor design. Carbon dioxide (CO2) 0.015
The composition of natural gas is origin dependent Average molecular mass (g
mol1) 16.89
Normal gas density (kg
m3)1 0.754
and the main associated gases are other hydrocarbons,
Lower heating value (MJ
m3) 34.3
carbon dioxide (CO2), nitrogen (N2), and hydrogen sul- Higher heating value (MJ
m3) 38.0
fide (H2S) [27]. Of these, nitrogen is the most difficult to
1
separate from the unconverted natural gas, because it Normal conditions: 0C (273.15 K) and 1 atm (101.325 kPa).

2014 The Authors. Energy Science & Engineering published by the Society of Chemical Industry and John Wiley & Sons Ltd. 63
Direct Methane to Methanol A. de Klerk

anol conversion process. The cost and the complexity of tive material from the inert material. In direct methane to
the process increase in the same order. In practice, methanol conversion, the process chemistry dictates that
purified oxygen is the only viable oxidant feed for the a low single-pass conversion of methane is required,
process: which necessitates the recycling of methane. Nitrogen and
(1) The oxidant feed is available at low pressure and the argon that enter the process through the natural gas feed
oxidant feed must also be compressed to the process pres- and the oxidant feed are difficult to separate from meth-
sure, around 8 MPa. The ideal shaft work for the com- ane. The purge is needed to ensure material balance. The
pression of pure O2 is 400 kJ
kg1 O2 and a realistic same amount of N2 and Ar that enter the process must
compressor design requires a cooling duty of 300 kJ
kg1 leave the process.
O2 for interstage compressor cooling. For air, these duties In practice, there are three design decisions that affect
change to 1.9 and 1.4 MJ
kg1 O2, respectively. the purge rate. First, the feed composition can be selected
(2) Any inert material introduced as part of the oxidant or manipulated to ensure that the least amount of inert
feed and that is difficult to separate from methane, affects material enters the process. Second, a separation technol-
the purge rate of the process. Purified O2 from cryogenic ogy can be installed to selectively remove inert material
separation typically has a purity of around 99.5% O2, the from the recycle gas. This is unlikely to be a practical
remainder being argon [28]. The composition of standard option for this process. The separation of methane from
dry air is 21% O2, 78% N2, and 1% Ar. Both nitrogen N2 and Ar requires cryogenic distillation with prior CO2
and argon are difficult to separate from methane. When removal to avoid solid CO2 plugging of the cryogenic sec-
air is used as oxidant, it increases the purge rate. tion [28]. Third, the concentration of the inert material
in the recycle gas can be manipulated.
The implication of the preceding discussion is that the
The impact of the inert composition of the oxidant
direct methane to methanol process requires purified O2
feed and the inert concentration in the recycle gas on the
as oxidant feed. For smaller installations that require less
purge rate of methane was calculated and it is illustrated
than 5000 m3
h1 normal (2 kg
sec1) of O2, vacuum
by Figure 4. In the calculations, the natural gas feed com-
pressure swing adsorption (VPSA) can be considered, but
position in Table 2 and 30:1 methane to O2 feed ratio
the purity of the oxygen is only in the range 9093% O2
were employed. For 99.5% O2 from cryogenic separation
[28]. For larger capacities or to reduce the impact of the
the least amount of methane is lost through the purge.
inert gas in the oxidant feed, cryogenic air separation is
For air, which has only 21% O2, the methane loss
required. This is a utility unit and it is not reflected in
through the purge is substantial, even at a high inert con-
either Figures 1 or 2, but it clearly will have an impact on
centration in the recycle gas.
the size and cost of the process.
The calculated methane loss through the purge gas
(Fig. 4) is also affected by the inert content in the natural
Liquid product gas feed. The effect of the inert content in the natural gas
feed decreases in significance as its contribution to the
The oxygenate products, methanol, methanal, and metha- overall inert content entering the process decreases. For
noic acid (eqs. 13), are recovered as a crude liquid aque- example, if the N2 content in the natural gas is 1%
ous product mixture by condensation under pressure. In instead of 3% (Table 2), the methane loss with a 99.5%
addition to these products, some of the CO2 and H2S are
removed by dissolution under pressure in the liquid phase
[29, 30]. The temperature at which phase separation is per-
100
formed affects the relative amounts of products and soluble 21 % O2 (air)
Methane lost by purge (%)

gases that are removed in the liquid phase. A small amount 80

of the inert gases are also removed, but it is insufficient to
affect the purge rate. For example, the solubility of N2 in 60 93 % O2
water is about 0.1 mol % at 7 MPa [31].
40

20 99.5 % O2
Purge gas product
It was pointed out that the inert gas content of the natu- 0
0 10 20 30 40 50
ral gas feed and the oxidant feed both affect the purge Inert concentration in recycle gas (%)
rate. This is a generic chemical engineering problem that
is encountered whenever a gas recycle is employed. The Figure 4. Impact of O2 purity in oxidant feed and inert concentration
problem stems from the difficulty in separating the reac- in the recycle gas on the methane loss through the purge gas.

64 2014 The Authors. Energy Science & Engineering published by the Society of Chemical Industry and John Wiley & Sons Ltd.
A. de Klerk Direct Methane to Methanol

O2 feed is 60% smaller than that indicated in Figure 4,

but with a 93% O2 feed the methane loss is decreased by
only 20%. The methane loss is determined by the total
amount of inert material that enters the process.
The methane in the purge gas can be employed as fuel
gas in the process. Since the volumetric heating value of
the purge gas decreases with increasing inert concentra-
tion, there is a trade-off between the fuel gas needs, fuel
gas quality and the design of the gas recycle.

Gas recycle
Figure 5. Impact of O2 purity in oxidant feed and inert concentration
The size of the gas recycle determines the sizing of equip- in the recycle gas on the recycle to fresh feed ratio of the process.
ment in the gas loop. With reference to Figure 2, the
equipment in the gas loop is the partial oxidation reactor dealing with direct methane to methanol conversion. To
(R-01), feed-product heat exchanger (E-04), product add to this uncertainty, reaction rate and selectivity are
coolers (E-05), phase separator vessel (V-01), and recycle affected by the construction material of the reactor [4, 18].
gas compressor (C-03). Some general observations about reactor design can be
The gas recycle is particularly large in comparison to made that agree with experimental observations and reac-
the fresh feed streams due to the low single-pass conver- tor designs suggested for this process.
sion. For an ideal reactor and separator with no inert (1) Temperature will affect the reaction rate of oxida-
materials in the feed, the ratio of the recycle flow rate to tion, but it will also affect the contribution of thermal
the fresh feed flow rate can be calculated in terms of the decomposition. Since partial oxidation reactions are exo-
single-pass conversion, x (eq. 8): thermic (Table 3), it is preferable to limit the tempera-
Recycle ratio 1  x=x: (8) ture, in particular to avoid loss of methanal (eqs. 67)
even though some methanal is converted to methanol by
In the direct methane to methanol process, the single-
thermal decomposition. Heat management is important.
pass conversion is limited to around 3% by limiting the
(2) Control of the residence time is not independent of
oxidant in the feed to the partial oxidation reactor. A
temperature. There are three aspects to consider. First,
recycle to fresh feed ratio of ~30:1 is anticipated from
thermal decomposition reactions can take place indepen-
equation 8, the exact ratio depending on the efficiency of
dently of the other species present and there will be a
separation and the impact of the purge rate. The recycle
threshold temperature below which these reactions become
to fresh feed ratio increases as the design concentration of
negligible. Control of the residence time, independent of
inert material in the gas recycle is increased. The recycle
oxygen consumption, is therefore important when the tem-
to fresh feed ratio also increases as the inert content in
perature is high enough for thermal decomposition reac-
the feed materials decrease, because the system becomes
tions to take place. Second, yield of an intermediate
more efficient and less methane is lost through the purge
product in a simple reaction is determined by the rate con-
(i.e., not recycled). The calculated impact of O2 purity on
stant of the formation of the intermediate product (k1) in
the inert concentration in the recycle is shown in Fig-
relation to the rate constant for the consumption of the
ure 5. A lower recycle ratio does not necessarily imply
intermediate product (k2). Since these reactions typically
that in absolute terms the flow rate through the partial
have different activation energies, the ratio of k1/k2 is
oxidation reactor is less, because purge losses are com-
dependent on the temperature. In a complex reaction
pensated for by an increased fresh feed flow rate.
network, the timetemperature relationship becomes

Table 3. Standard heats of reaction (DHr) for methane oxidation

Partial oxidation reactor
reactions.
Product selectivity depends on temperature, pressure, O2
Product Equation DHr (kJ
mol1)
concentration, and residence time. The proposals for reac-
tor designs and improvements in reactor designs are based Methanol 1 127
partly on an appreciation of the reaction variables that need Methanal (formaldehyde) 2 276
Methanoic acid (formic acid) 3 546
to be controlled and on empirical observations. It was
Carbon monoxide 4 519
pointed out that a well-founded reaction network with Carbon dioxide 5 802
kinetic data is conspicuously absent from the literature

2014 The Authors. Energy Science & Engineering published by the Society of Chemical Industry and John Wiley & Sons Ltd. 65
Direct Methane to Methanol A. de Klerk

important, because it is the global optimum that must be and a natural gas feed rate of 1 kg
sec1. The feed basis
achieved, not the optimum for a single product. Third, is equivalent to a volumetric natural gas flow rate at stan-
there is an induction period in free radical oxidation that dard conditions of 115,000 m3 per day (4 million scf per
can be shortened or eliminated by the use of an initiator. day). With reference to Figure 2, other important
During the induction period, oxidation is negligible. The assumptions and design decisions that were made in the
length of the induction period is dependent on the temper- preparation of the material balance are:
ature and it is actually the timetemperature profile once (1) The natural gas feed (stream 1) is available at 25C
O2 comes into contact with the methane that determines and 2.0 MPa absolute. In practice, this value will be
the length of the induction period. There is of course also dependent on the nature of the natural gas resource. For
an implicit risk for the reactor design if the absence of initi- example, natural gas from deep reservoirs will have a
ators in the reactor feed cannot be guaranteed. much higher pressure, whereas associated natural gas
(3) Oxygen availability determines product selectivity. available after crude oil depressurization may be available
The methane to O2 ratio threshold assumes a well-mixed at lower pressure [26].
system. What this implies is that after mixing the meth- (2) The recycle (stream 15) to fresh feed (stream 1) ratio
ane and O2, the mixture must be homogenized before the was fixed at 30:1 on a volumetric basis. It is not claimed
end of the induction period. that this is the optimum, but it provides a credible trade-
off between recycling, inert content in the recycle and purg-
The detailed reactor design is very important. Although
ing rate. In principle this number can be increased, but not
the reactor is not very complex, the design of the reactor
by much, otherwise it invalidates the constraints on reactor
is very complex. Scale-up without a fundamental descrip-
operation for the product selectivity values employed.
tion of the reaction network and the flow dynamics is
(3) The oxidant feed (stream 3) is 99.5% O2 from a
likely to involve trail-and-error. In this respect, history
cryogenic air separation unit. The only inert introduced
serves as lesson. The oxygenate yield that was predicted
in this way is 0.5% Ar. The oxidant is available at 25C
Gutehoffnungsch utte-process for direct methane to meth-
and 0.1 MPa absolute.
anal conversion was 35%, but on scale-up the actual yield
(4) The oxidant feed rate was fixed at 2.5% O2 concentra-
was only around 10% [4].
tion on a volumetric basis in the combined reactor feed.
This value resulted in a methane to O2 ratio just over 30:1.
Process Evaluation (5) The reactor inlet conditions are 8 MPa and 370C.
(6) The overall pressure drop between the feed supply
Material balance and product recovery is 500 kPa.
(7) Recoveries for the oxygenate products in the liquid
A material balance for the process (Table 4) was calcu- phase is 99.9%. This is based on high-pressure recovery at
lated based on the natural gas composition in Table 2 25C by phase separation (V-01).

Table 4. Material balance for direct methane to methanol conversion process shown in Figure 2.

Flow rate (kg
sec1)1

Gas feed Oxidant feed Reactor feed Reactor product Liquid product Purge gas Recycle
Compounds #1 #3 #7 #8 #11 #13 #15

CH4 0.902 25.485 24.892 0.309 24.583

C2H6 0.009 0.009 0.000 0.000 0.000
O2 1.514 1.551 0.038 0.000 0.037
N2 0.050 3.999 3.999 0.050 3.949
Ar 0.009 0.764 0.764 0.009 0.755
CO 0.409 0.414 0.005 0.409
CO2 0.039 3.035 3.792 0.758 0.038 2.996
H2O 0.000 0.716 0.716 0.000 0.000
Alcohols 0.000 0.480 0.479 0.000 0.000
Aldehydes 0.000 0.146 0.146 0.000 0.000
Carboxylic acids 0.000 0.012 0.012 0.000 0.000
(kg
sec1) 1.000 1.523 35.252 35.252 2.111 0.412 32.729
Molar flow (mol
sec1) 59.2 47.5 1882.8 1882.8 77.0 22.4 1776.0

Values that are 0.000 represent flow rates that are <0.0005 kg
sec1.
1

66 2014 The Authors. Energy Science & Engineering published by the Society of Chemical Industry and John Wiley & Sons Ltd.
A. de Klerk Direct Methane to Methanol

(8) The CO2 removal due to dissolution in the aqueous

Energy and utility use
product is 20% based on partial pressure of CO2 of the
system [30]. Although some of the other gases also dis- The main energy and utility consumers in the direct
solve to some extent in the liquid product, these contri- methane to methanol process are the compressors, heat
butions were neglected. exchangers, and air separation unit. Additional energy
(9) Conversion of O2 in the reactor (R-01) is complete. and utilities are required during product purification and
(10) Conversion of CO present in the recycle gas to the treatment of waste streams, but as indicated before, these
reactor is complete. The ratio of CO:CO2 produced by units were excluded from the scope of the evaluation.
partial oxidation of methane was assumed to be 85:15 The energy and utility consumption for the process is
based on typical values from literature [4, 18]. given in Table 5. The values for utility use are influenced
(11) The product selectivities are based on what has by the process design and equipment selection.
been claimed in literature [4, 17]. Both material and atom Due to the potential application of this process for
balance closure was ensured. Water production was calcu- small-scale GTL, reciprocating compressors, rather than
lated under the assumption that no H2 will be produced. axial compressors might be a more realistic selection [32].
The molar ratio of water to methanol reported was 2.4 A compression efficiency of 0.9 and a mechanical effi-
[4], and was reasonably close to the value of 2.7 obtained ciency of 0.9 were employed for shaft work calculations.
from material and atom balance closure. The use of natural gas powered internal combustion
(12) Ethane in the natural gas feed is converted into etha- engines is more practical for a small-scale GTL applica-
nol, ethanal (acetaldehyde), and ethanoic acid (acetic acid). tion since the infrastructure for delivering the required
Conversion of ethane is assumed to be complete, because it amount of electric power might not be available [33].
is easier to convert heavier hydrocarbons than methane. The power consumption was converted into a natural gas
consumption for internal combustion engine drives, with
The natural gas feed and oxidant feed flow rates are
a drive efficiency of 0.37 [34]. As an alternative, the purge
of the same order of magnitude, but even combined,
gas can be employed instead of natural gas, albeit with
these flow rates are an order of magnitude smaller than
some loss in efficiency. The purge gas is 86 vol % meth-
the recycle (Table 4). The low single-pass methane con-
ane with a lower heating value (LHV) of 31.0 MJ
m1
version and the need for a large methane recycle domi-
and higher heating value (HHV) of 34.4 MJ
m3.
nates the material flow in the process. The material
The heat exchanger network was not optimized and it
balance supports the qualitative predictions that were
is likely that a slightly lower utility use can be achieved
made using simplified calculations (Fig. 5). Likewise,
by better heat integration. One fired heater is necessary
the methane loss through the purge is substantial, as
for start-up, even though a steady-state optimization will
qualitatively predicted using simplified calculations
show that it is not necessary. Product cooling (E-05) is
(Fig. 4).
Table 5. Energy and utility use in direct methane to methanol conversion process shown in Figure 2 and material balance in Table 4.

Utilities (kg
sec1)3

Duty Power Natural Cooling

Equipment or unit (MW)1 (MW)2 gas water Steam4

Natural gas feed compressor (C-01) 0.29 0.79 0.017

Oxidant feed compressor (C-02) 0.75 2.03 0.045
Recycle gas compressor (C-03) 0.35 0.94 0.021
Interstage cooler for C-01 (E-01)
Interstage cooler for C-02 (E-02) 0.46 5.4
Oxidant heater (E-03) 0.35 0.41 0.009
Feed-product heat exchanger (E- 31.02
04)
Product coolers (E-05) 7.20 86.0
Partial oxidation reactor (R-01) 7.89 3.7
Air separation unit 0.88 2.38 0.052 4.1
0.144 95.5 3.7

1
Shaft work for compressors, heat flow for heat exchangers.
2
Depends on compressor drive-type or heat source employed for heating.
3
Positive is consumption, negative is production.
4
Low pressure steam, 150C, 400 kPa gauge.

2014 The Authors. Energy Science & Engineering published by the Society of Chemical Industry and John Wiley & Sons Ltd. 67
Direct Methane to Methanol A. de Klerk

shown as a single exchanger, but in practice it will be lated efficiencies, but not for energy intensive processes.
multiple exchangers, which was considered in the calcula- For example, the carbon efficiency of indirect methanol
tions. The assumption was made that all cooling duty is synthesis based on the process streams only is better than
supplied by cooling water, although it is likely that in 95% [3], but for the overall process it is 6568% [9].
practice air coolers will be used for some of that cooling Somewhat lower efficiency is likely if the indirect metha-
duty. It was further assumed that cooling water is avail- nol synthesis process is scaled down.
able at 20C and that 40C was an acceptable cooling The overall process efficiency was assessed by compar-
water return temperature. For small-scale GTL applica- ing the thermal efficiency and the carbon efficiency of the
tion, a closed cooling water system is likely to be more direct methane to methanol conversion with indirect
practical, albeit more expensive, since sufficient fresh methanol synthesis (Table 6) [9]. In the calculation of the
water might not be available to allow evaporative cooling overall efficiency of the direct methane to methanol pro-
[33]. cess it was assumed that the purge gas can be used as fuel
Although product purification was outside of the scope gas to supply all of the energy of compression and heat-
of the evaluation, some steam will be required for distilla- ing requirements (Table 5), so that no additional natural
tion. Low pressure steam, 0.5 MPa absolute, was pro- gas is consumed for these purposes.
duced where practical. Strictly speaking the comparison in Table 6 is not on
The work required by the air separation unit to pro- the same basis, because the efficiency values for indirect
duce 99.5% O2 is 0.35 kWh per normal m3 of unpressur- methanol synthesis include carbon and energy losses from
ized oxygen [28]. This is equivalent to 0.88 MW
kg1 product purification, and it is at larger scale. However,
O2. The air separation unit also requires cooling water for the direct methane to methanol process has excess heating
the initial cooling of the outlet of the primary air com- value available as steam and from the use of the purge
pressor [28]. Using the same utility assumptions as for gas as fuel gas. However, the difference between the two
the rest of this evaluation, the required cooling water flow processes is so large that the difference in scale and bat-
is 4.1 kg
kg1 O2. tery limit does not change the conclusion.
It is best to view the utility requirements in Table 5 as It is clear that the overall process efficiency of indirect
indicators of the utility footprint. In an optimized design methanol synthesis is much higher than that of direct
the absolute numbers will differ, but the numbers will be methane to methanol conversion. The main reason for
of the same order of magnitude. The process requires this is reaction selectivity. During direct methane to
much cooling capacity and power for gas compression. methanol synthesis, the production of CO and CO2
Compared to the natural gas feed, an additional 14% nat- (eqs. 45) is undesirable and these reactions erode carbon
ural gas is required for heating and power. The cooling efficiency. Conversely, during indirect methanol synthesis,
water flow rate is 95 kg
kg1 natural gas, that is, almost CO and CO2 are potential product-forming reactants.
two orders of magnitude more on a mass flow basis. The single-pass conversion during indirect methanol syn-
A large utility footprint is a common feature of GTL thesis is equilibrium limited and not limited by side-reac-
facilities and one of the challenges in the development of tions. In fact, the selectivity to methanol even at near
a credible process configuration for small-scale GTL equilibrium conversion is of the order of 99% [2]. Thus,
applications [25, 35]. almost no carbon that enters the gas loop during indirect
methanol synthesis is lost due to irreversible side-reac-
tions, whereas the irreversible carbon loss due to side-
Process efficiency
reactions during direct methane to methanol synthesis is
There are various metrics that can be used to assess the 4050% (46% based on the assumptions used in this
efficiency of processes. Two of the most commonly work). Based on the calculated efficiencies (Table 6),
employed are carbon efficiency and thermal efficiency. direct partial oxidation of methane to methanol must
The carbon efficiency is defined as the fraction of the car-
bon in the feed to the process that is contained in useful Table 6. Comparison of overall process efficiency for direct and indi-
products. The thermal efficiency is defined as the fraction rect methanol synthesis.
of the LHV of the feed to the process that is retained by
Overall process efficiency
the useful products and it is more often employed when
(%)
the products are fuels. In both instances, it is important
to be clear on the system boundary. These values can be Description Carbon Thermal
calculated for the process streams only, or they can be Direct methane to methanol 35 28
calculated for the overall process. When the process is not Indirect methanol synthesis 6568 5154
energy intensive there will be little difference in the calcu-

68 2014 The Authors. Energy Science & Engineering published by the Society of Chemical Industry and John Wiley & Sons Ltd.
A. de Klerk Direct Methane to Methanol

achieve a combined methanol and methanal selectivity of with air as the oxidant feed. The need for an air separa-
the order 90% to become competitive with indirect meth- tion unit diluted the benefit of avoiding synthesis gas gen-
ane to methanol synthesis. eration as a process step (Fig. 1). If one considers
synthesis gas generation by autothermal reforming and its
associated air separation unit, only part of the complexity
Discussion
and cost is avoided by direct methane to methanol con-
The objective of the present investigation was to perform version.
an engineering evaluation of the process and evaluate the (2) Natural gas is not pure methane and oxygen from air
potential of this process for small-scale GTL applications. separation is not pure O2. The introduction of some inert
There is reasonable agreement between the heat transfer gases is unavoidable and this affects the design. The recycle
and compression duties reported by Kuo [9], and that ratio, capacity of the gas loop, and purge gas loss all depend
calculated during the present investigation. These duties on the amount of inert gases introduced in the feed.
cannot be avoided even though more optimized heat inte- (3) The utility footprint of the process is significant, with
gration would change the numeric values somewhat. compressor and cooling duties dominating utility require-
However, the overall outcome of the evaluation was more ments. This is typical of GTL processes. The large utility
pessimistic than the evaluation by Kuo. This is primarily footprint of GTL processes is one of the key challenges for
due to a difference in process chemistry, with Kuos small-scale GTL applications and in this respect direct
analysis being based on the optimistic methanol selectivity methane to methanol conversion offers little benefit.
of 90% and 15% single-pass methane conversion. These (4) Overall the carbon efficiency is 35% and the thermal
optimistic values were based on the work by Gesser, Hun- efficiency is 28%, which is about half of that of indirect
ter, and coworkers [36]. The bulk of the literature sug- methanol synthesis (6568% and 5154%, respectively).
gests that such methanol selectivities are not obtained [4]. (5) Low oxygenate selectivity during direct partial oxida-
There are also fundamental reasons why such optimistic tion of methane is the largest contributor to the loss of
data are questionable, notably the implicit adiabatic tem- process efficiency compared to indirect synthesis of meth-
perature increase and the relative ease of further oxida- anol. The process chemistry is burdened by some funda-
tion of methanol compared to oxidation of methane. mental constraints. First, the reactivity of methanol and
One of the major disappointments from this study was methanal (desirable products) to further oxidation is
that a credible engineering design for the direct methane higher than that of methane. Second, there are thermal
to methanol process required high purity O2. The antici- reactions that can proceed in the absence of the oxidant
pated cost and complexity advantage over indirect meth- to decrease oxygenate selectivity, so that limiting oxidant
ane to methanol synthesis could, therefore, not be availability on its own is insufficient to achieve better
realized, because an air separation unit was required. selectivity. Third, CO and CO2 are fatal products and
Hence, for small-scale GTL applications, direct methane these products represent an irreversible carbon loss.
to methanol had no specific advantage over indirect
methane to methanol. When this is combined with the
low methanol selectivity and low single-pass methane Conflict of Interest
conversion, there is little technical incentive to justify fur-
ther interest in direct oxidation of methane as a potential None declared.
process for methanol synthesis. Furthermore, based on
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70 2014 The Authors. Energy Science & Engineering published by the Society of Chemical Industry and John Wiley & Sons Ltd.