Chemical Engineering Science 58 (2003) 577 – 582

www.elsevier.com/locate/ces

A novel cyclic process for synthesis gas production

Y. Zeng∗ , S. Tamhankar, N. Ramprasad, F. Fitch, D. Acharya, R. Wolf
The Group Technical Center, The BOC Group, 100 Mountain Avenue, Murray Hill, NJ 07974, USA

Abstract

This paper reports a novel cyclic partial oxidation process for the production of synthesis gas with the in situ separation of oxygen
from air. A perovskite-type oxide, La0:8 Sr 0:2 Co0:5 Fe0:5 O3− , is employed in the experimental study of the process as an oxygen retaining
material. Air and methane are periodically brought into contact with the oxide packed in a 3xed-bed reactor. The oxide, during the air
step, exclusively retains oxygen while partial oxidation reaction occurs during the methane step utilizing the retained oxygen. Although
combustion and cracking reactions occur in addition to the partial oxidation reaction during the methane step, high methane conversion
is achieved and hydrogen and CO are produced with high selectivity.
? 2003 Elsevier Science Ltd. All rights reserved.

Keywords: Chemical reactors; Product processing; Separations; Transport processes; Synthesis gas; Partial oxidation

1. Introduction Synthesis gas can also be produced by the steam methane

Partial oxidation of hydrocarbons, with air or oxygen, is
one of the processes conventionally used to produce syn-
thesis gas (H2 + CO), which is required for the synthesis
of several valuable chemicals. The partial oxidation process
is also the key step for gasi3cation or GTL technology. Al-
though air is less expensive and more convenient to use
in the partial oxidation process, it is less attractive because
the large quantities of nitrogen must be subsequently sep-
arated from the product gas prior to its use. However, the
use of oxygen brings additional cost of the air separation
unit (ASU). Air separation processes currently used indus-
trially include cryogenic distillation, adsorption and mem-
brane separations. For large scale air separation requirement
(¿ 200 MT=D), cryogenic distillation technology is more
likely to be used since it is more economical at large scale
as compared to the other two technologies. Partial oxidation
process usually aims at large scale synthesis gas produc-
tion and therefore requires large amounts of oxygen, which
is produced by cryogenic distillation. The capital cost of a
cryogenic distillation unit is high and could constitute more
than 30% to the total capital cost for the overall process.
Even more important, ASU is very energy intensive with
large power requirements.
∗ Corresponding author.
reforming (SMR) process, in which methane reacts with
steam to make hydrogen, carbon monoxide and carbon diox-
ide. This reaction is highly endothermic and requires high
temperature (¿ 850◦ C) and fast transport of huge amount
of heat into the reaction zone in order to sustain the reaction
at desire reaction rate and methane conversion. The cost of
reformer is high due to its shell-and-tube type design and
stringent metallurgical requirements. The advantages of par-
tial oxidation process over SMR process are: (1) simpler
and less expensive reactor design, (2) more desirable prod-
uct composition, i.e. H2 =CO ratio close to 2 with very small
amount of CO2 in the product, while the product from SMR
without modi3cation has a H2 =CO ratio higher than 3 with
signi3cant amounts of CO2 , and (3) auto-thermal process
with no external heating requirement. However, the use of
oxygen is a big disadvantage for partial oxidation process
as compared to SMR process due to the additional capital
and operating cost for an ASU.
Therefore, it is important to minimize the cost on
oxygen generation in order to reduce the overall cost
of the partial oxidation process. One approach to ac-
complish this is to generate oxygen within the process,
thereby eliminating or signi3cantly reducing the equip-
ment required for air separation. Economical methods
of in situ air separation for partial oxidation are con-
tinuously sought. Among them, oxygen ion transport
membrane technology (ITM) has attracted attention of

0009-2509/03/$ - see front matter ? 2003 Elsevier Science Ltd. All rights reserved.
doi:10.1016/S0009-2509(02)00582-1
578 Y. Zeng et al. / Chemical Engineering Science 58 (2003) 577 – 582
academic and industrial researchers, and development
eDorts in this area have accelerated in the past decade
(Mazanec & Cable, 1990). In this technology, the reactor is
made of dense ceramic membrane tubes through which oxy-
gen ions can be transported under oxygen partial pressure or
electric potential gradient across the membrane. This mem-
brane is made of mixed-conducting ceramic oxides that have
both signi3cant oxygen ion and electrical conductivities at
high temperature. For the partial oxidation reaction, air and
hydrocarbon, e.g. natural gas, are Fown over the two sides
of the membrane. Since the membrane is semipermeable to
oxygen, oxygen in the air can be transported through the
membrane via ionic conduction and reaches the other side
of the membrane to react with the methane in that chamber.
A catalyst may also be used in the membrane reactor to
promote the partial oxidation reaction and to enhance the
transport of oxygen through the membrane.
ITM technology seems to 3t well with the requirement
of the partial oxidation process. However, there are signif-
icant challenges on the path to commercialize this technol-
ogy. (1) It is diGcult to produce, at large scale, membrane
structures that are leak-proof and able to withstand harsh
reaction environment. (2) There is a lack of experience in
engineering design and process operation for the applica-
tions of membrane reactors in industrial processes. (3) The
high cost associated with membrane fabrication, integration
and installation. (4) There are serious safety concerns, since
even pin-holes in the membrane will result in a catastrophic
failure of the system due to the direct mixing of the highly
explosive feed gas with air at high temperatures (Pei et al.,
1995).
At the BOC Group, we have developed a novel par-
tial oxidation process with in situ air separation based on
the principle of adsorption separation instead of membrane.
In this process, materials capable of retaining oxygen at
high temperatures are used (Zeng, Tamhankar, Limbach, &
Krishnan, 2000; Lin, MacLean, & Zeng, 2000). This paper
will discuss the development of the concept and report some
preliminary results of bench-scale tests.
2. Process concept
The process is carried out in a 3xed-bed reactor packed
with the solid materials capable of retaining oxygen at high
temperatures. As shown in Fig. 1, it consists of at least two
steps. (1) Passing an oxygen-containing gas, e.g. air, through
the reactor, during which the oxygen is selectively retained
by the solid materials, thereby becoming oxygen-enriched;
(2) passing hydrocarbon, e.g. CH4 , through the reactor,
during which CH4 reacts with the oxygen-enriched solids,
thereby producing a product gas comprising hydrogen and
carbon monoxide. In the 3rst step, a gas stream containing
primarily nitrogen can be produced as a by-product. Besides
the above two major steps, other steps may be incorporated
into the process, such as to purge out the remaining gases
Fixed-bed reactor
(with O2 retaining ceramic)
Air Nitrogen
Heat Oxygen
Methane Synthesis gas
Fig. 1. Illustration of proposed cyclic process for synthesis gas production
with in situ oxygen generation.
in the voids and to burn out the deposited carbon on the
ceramic particles.
To achieve desirable performance of this process, the ma-
terial selected must have the following properties. (1) It must
possess suGcient oxygen exchange capability with fast ki-
netics at high temperatures (¿ 700◦ C). (2) It should be able
to withstand the harsh environment of the partial oxidation
reactions. (3) It should be catalytically active for partial oxi-
dation reactions or can work together with additional partial
oxidation catalysts. (4) It should be easy to fabricate and be
cost eDective. At such high reaction temperatures, the trans-
fer of oxygen from the gas phase to the solid phase can only
take place via chemical sorption rather than physical sorp-
tion. Based on the above requirement, non-stoichiometric
ceramic oxides represent the appropriate choice of materi-
als for the process. Among them, mixed-conducting ceramic
oxides, such as those used for the ITM technology are suit-
able candidates as long as they also have oxygen storage
capacity in addition to their oxygen transport property as
shown in the membrane application.
Preferred oxygen-selective mixed conductors include ce-
ramic materials selected from: (1) perovskite substances
having the structural formula A1−x Mx BO3− , where A is a
rare earth ion, M is Sr, Ca, Ba or mixtures of these, B is
Co, Mn, Cr, Fe or mixtures of these, x varies from ¿ 0 to 1
and  is the deviation from stoichiometric composition re-
sulting from the substitution of Sr, Ca and Ba for rare earth
ions; (2) ceramic materials selected from compounds such
as Bi2 O3 , ZrO2 , CeO2 , ThO2 , HfO2 and mixtures of these,
wherein the ceramic material is doped with CaO, a rare earth
metal oxide, such as, for example, Y2 O3 , Nb2 O3 , Sm2 O3 ,
Gd 2 O3 and mixtures of these; a brownmillerite oxide; and
mixtures of any of these.
It is necessary that the mixed-conducting oxides are
formed into appropriate shapes to achieve high mass and
heat transfer eGciency, high surface area, enhanced resis-
tance to attrition and Fuidization compared to other shapes.
These shapes include beads, rings, extrudates, pellets with
any cross-sectional shapes, with or without holes, honey-
comb structures with uniform channels and monolithic ones
with random porosity and/or foam structure. The preferred
shapes are extrudates and monolithic structures. The mono-
lithic and honeycomb structures can be used either in a
single piece or stacked pieces packed randomly in a reactor
 Y. Zeng et al. / Chemical Engineering Science 58 (2003) 577 – 582
bed. The mixed-conducting oxides can be coated on a suit-
able support to achieve better mass transfer and mechanical
stability. In addition to the selected mixed-conducting ox-
ides, other appropriate materials can also be included in
the 3xed-bed reactor in order to promote partial oxidation
reaction and heat transfer characteristics of the reactor.
There have been few studies on oxygen sorption proper-
ties of perovskite-type oxides (Mizusaki, Mima, Yamauchi,
& Fueki, 1989; Zeng & Lin, 1998). Oxygen sorption ca-
pacities of perovskite-type oxides are directly related to the
changes of their nonstoichiometric oxygen in the lattice,
which is a function of the oxygen partial pressure change in
the gas phase. These changes are reversible as long as the
oxides maintain the perovskite-type phase structure. The re-
lationship between the extent of non-stoichiometry and the
oxygen partial pressure can be predicted from an appro-
priate defect model or can be measured experimentally by
thermo-gravimetric analysis (TGA) methods (Zeng & Lin,
1998).
3. Experimental
In this study, a perovskite-type oxide, La0:8 Sr 0:2 Co0:5 Fe0:5
O3− (LSCF-8255) was used as the oxygen retaining mate-
rial to study the above-described process. LSCF-8255 was
synthesized with citrate method, in which the appropriate
metal nitrates are dissolved in a dilute nitric acid solution.
After the addition of an appropriate amount of citric acid,
the solution is heated to 80 –120◦ C and kept at that tem-
perature while stirring for 3–6 h. The metal atoms are in-
corporated into the hydrocarbon structure thereby forming
complex metallo-organic compounds through a series of
polymerization and condensation reactions. A gel-like solid
is formed after water is removed from the system. This gel
is dried and pyrolyzed at temperatures less than 400◦ C. The
ash is then ground and compacted into a ceramic crucible
and treated at 1000◦ C for 8 h. The resulting sample is an-
alyzed and characterized with ICP-AES, XRD, SEM/EDX
and BET surface area analysis methods.
The proposed cyclic process for synthesis gas produc-
tion was 3rst tested in a bench scale reactor system, which
primarily contained three parts: gas Fow control and deliv-
ery, reactor and product analysis. The Fows of feed gases,
methane, air and nitrogen, were controlled by mass Fow
controllers. The reactor was made of a dense alumina tube
(4:85 mm, OD and 60 mm long). A tubular electric furnace
was used to heat and maintain the reactor at the required
temperature. The eMuent gases from the reactor were ana-
lyzed by a series of on-line gas analyzers for H2 (Nova),
CO, CO2 (Ultramat-22, Siemans) and CH4 (Ultramat-21p,
Siemans). An amount of 1:67 g of the LSCF-8255 sample
was packed in the middle of the reactor. The experiments
were carried out with the following steps in each cycle: (1)
air; (2) N2 ; (3) CH4 =N2 mixture; and (4) N2 . Steps (1) and
(3) are the primary steps of the process. The use of N2 to
579
purge the reactor in Steps (2) and (4) was to ensure max-
imum safety in the lab experiments as well as to clean up
the carbon deposit on LSCF-5555 sample before air is in-
troduced into the reactor in the following step.
4. Results and discussions
The composition of the synthesized LSCF-8255 sam-
ple was analyzed with inductively coupled plasma atomic
emission spectroscopy (ICP-AES). The deviation on the
composition from the desired one was less than 5%. X-ray
diDraction patterns of LSCF-8255 sample is given in Fig.
2. It shows that the sample had the desired perovskite-type
phase structure. The SEM/EDX analysis revealed that the
sample contained sharp-edged particles with size ranging
from 10 to 50 m, with quite uniform distribution of metal
and oxygen elements on the surface. This is consistent
with the ICP-AES analysis. There were some irregular
macro-pores on the particles. The BET surface area of the
sample was lower than 1 m2 =g, suggesting that there were
no micro- or meso-pores within the particles.
The experiments were carried out to test the pro-
posed process at diDerent temperatures (furnace), reactant
compositions and Fow rates. Figs. 3–7 show products
formation rates and methane conversion as a function
of time during the CH4 =N2 step at temperatures of
750◦ C; 800◦ C; 850◦ C; 900◦ C and 950◦ C. It was found
that at temperatures lower than 850◦ C, methane was ex-
clusively converted to CO2 , indicating that only complete
combustion reaction occurred. This is consistent with reac-
tion thermodynamics, according to which at lower temper-
atures total oxidation is favored compared to partial oxida-
tion. At temperatures higher than 850◦ C, there were three
clearly distinguishable periods during the CH4 =N2 step: (1)
combustion; (2) synthesis gas generation; and (3) thermal
cracking. Methane conversion during the CH4 =N2 step was
higher than 85% with Fuctuations between the periods of
combustion and synthesis gas generation. Selectivity to hy-
drogen during the synthesis gas and the cracking periods
was higher than 99%, and that for CO during the synthesis
gas period was also close to 100%.
The oxygen is believed to be transported by both the
surface reaction and the bulk ion conduction mechanisms.
The methane participates in either gas phase combustion
or surface dissociation reactions depending on the oxygen
release rate from the solid and the concentration of methane
in the gas phase. Reaction mechanism can be described by
the following reaction equations using a general formula for
the perovskite oxide.
ABO3−
+ O2 → ABO3−

(1)
ABO3−

+ CH4 → ABO3−
+ CO2 + 2H2 O (2)
ABO3−

+ CH4 → ABO3−
+ CO + 2H2 (3)
580 Y. Zeng et al. / Chemical Engineering Science 58 (2003) 577 – 582

6000

5000

4000
Intensity

3000

2000

1000

0
20 25 30 35 40 45 50 55 60 65 70

2θ

Fig. 2. XRD pattern of synthesized LSCF-8255 perovskite-type oxide.

120 120
120 120
Product formation rate

CO2
Product formation rate

100 100
CH4 Conversion (%)

CH4 Conversion (%)

CO2
100
(umol/g.min)

(umol/g.min)

80 CH4 Conversion 80
80 CH4 80
60 60
60

40 40 40
40

20 20
20

0 0
0 0
0 2 4 6 8
0 2 4 6 8 10 12
Time (min) Time (min)

Fig. 3. Methane conversion and product formation rates during CH4 =N2 Fig. 4. Methane conversion and product formation rates during CH4 =N2
step at 750◦ C. step at 800◦ C.

Reaction (1) occurs during the air step while reactions (2) molecules dissociate into oxygen ions on the solid surface by
and (3) take place during the CH4 =N2 step. receiving free electrons from the solid. These oxygen ions
For the sample used in this study, LSCF-8255, La and then transport into the bulk of the solid through the passage
Sr are located at A-sites while Co and Fe are located at of oxygen vacancies. The movement of oxygen from the
B-sites. Due to the substitution of La3+ with Sr 2+ at the gas phase into the solid phase is thermodynamically driven
A-site, signi3cant oxygen vacancies are created in order to by the partial pressure diDerence between the air and the
maintain overall electric charge neutrality for the material. methane steps.
These vacancies provide passages for oxygen ions in the The situation during methane step is slightly complicated
solid lattice to move around in response to the changes in by the oxidation reactions taking place on the solid surface
the surrounding gaseous atmosphere, i.e. temperature and and/or in the gas phase. Oxygen ions travel from the bulk
oxygen partial pressure. On the other hand, the multi-valent of the solid to the surface of the solid. Depending on the
metals at the B-site, i.e. Co and Fe, can accept or release rate of oxidation reactions, oxygen ions either directly re-
free electrons from or onto the solid surface by changing act with methane on the surface or combine to form oxy-
their oxidation states. During the air step, gas phase oxygen gen molecules and release into the gas phase. Zeng and Lin
 Y. Zeng et al. / Chemical Engineering Science 58 (2003) 577 – 582 581

300 120 (1998) have reported transient TGA data (weight change as
a function of time) for La0:2 Sr 0:8 CoO3− when the surround-
Product formation rate

250 100 ing gas changes between pure oxygen and helium or methane
at temperatures of 750◦ C, 800◦ C and 850◦ C. It was demon-

CH4 Conversion (%)

(umol/g.min)

200 80
strated in their study that the sample weight change was re-
150 60 versible with a change in oxygen partial pressure in the gas
phase. Their results showed that oxygen absorption rate was
100 40 much faster than the oxygen desorption rate. During desorp-
tion period, the release of oxygen from the solid seemed to
50 20 be fast at the beginning, but became slower with time.
The rate of oxygen release during the CH4 =N2 step
0 0
0 2 4 6 8 10 12 14 16 18 20 22
strongly aDects the products formed. If oxygen is released
Time (min) too fast from the solid, the eDective O2 =CH4 ratio on or
close to the solid surface is high, favoring combustion re-
CO2 H2 CO CH4 Conversion action. This explains the formation of CO2 in the beginning
of the CH4 =N2 step. As oxygen release rate slows during
Fig. 5. Methane conversion and product formation rates during CH4 =N2 the later part, partial oxidation reaction becomes dominant
step at 850◦ C.
since the eDective O2 =CH4 ratio is closer to 0.5 than 2.
However, if oxygen is released too slowly, methane crack-
ing takes place since there is insuGcient oxygen around to
sustain the partial oxidation reaction. The carbon deposited
CO2 H2 CO CH4 Conversion on the solid due to methane cracking can be partly cleaned
up during the N2 purge step as a consequence of the contin-
250 120 uous release of oxygen from the solid phase, which reacts
Product formation rate

with the deposited carbon.

CH4 Conversion (%)

200 100
It was found that the combustion period could be con-
(umol/g.min)

150
80
siderably suppressed by increasing either the temperature,
60 the Fow rate or the methane concentration. The remaining
100 carbon is burnt to produce CO2 (at ¡ 850◦ C) or CO (at
40
¿ 850◦ C) during the air step, in which no oxygen is de-
50 20 tected in the eMuent. The sample retains oxygen during the
0 0
air step very eGciently. Its oxygen exchange capacity, sub-
0 5 10 15 20 25 30 35 40 ject to air/CH4 cycle, can be as high as 6 –8 wt%.
Time (min) This process has been tested in a scaled-up reactor with
improved ceramic materials and optimized cycles. The re-
Fig. 6. Methane conversion and product formation rates during CH4 =N2 sults have been signi3cantly improved. Thus, methane con-
step at 900◦ C. version higher than 98% is obtained, with minimal combus-
tion reaction taking place. No methane cracking is observed
in the improved process. Economic analysis has shown that
this process can potentially save 20 –30% of the capital cost
350 120 as compared to the process using an air separation plant for
Product formation rate

300
supplying oxygen.
100
CH4 Conversion (%)
(umol/g.min)

250
80
200
60
5. Conclusions
150

100
40 A novel cyclic partial oxidation process for the produc-
20
tion of synthesis gas is described. The process achieves
50
in situ separation of oxygen from air. Based on the pre-
0 0 liminary proof-of-concept studies reported in this paper,
0 2 4 6 8 10 12 14 16 18 20 22
although combustion and cracking reactions occurred in
Time (min) addition to partial oxidation reaction during the
CO2 H2 CO CH4 Conversion methane step, high methane conversion and selectiv-
ity to H2 and CO (over H2 O and CO2 ) were achieved.
Fig. 7. Methane conversion and product formation rates during CH4 =N2 Signi3cant progress has been made toward develop-
step at 950◦ C. ing improved materials and suitable cycles that avoid
582 Y. Zeng et al. / Chemical Engineering Science 58 (2003) 577 – 582
combustion and carbon formation, and maximize syn-
thesis gas yield. The results will be reported in separate
papers.
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