Applied Catalysis A: General 468 (2013) 3843

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Applied Catalysis A: General

journal homepage: www.elsevier.com/locate/apcata

FischerTropsch synthesis: effect of ammonia impurities in syngas

feed over a cobalt/alumina catalyst
Venkat Ramana Rao Pendyala, Muthu Kumaran Gnanamani, Gary Jacobs, Wenping Ma,
Wilson D. Shafer, Burtron H. Davis
Center for Applied Energy Research, University of Kentucky, 2540 Research Park Drive, Lexington, KY 40511, USA

a r t i c l e

i n f o

Article history:
Received 26 March 2013
Received in revised form 23 July 2013
Accepted 30 July 2013
Available online 20 August 2013
Keywords:
FischerTropsch synthesis
Cobalt/alumina catalyst
Ammonia
Product selectivity

a b s t r a c t
The effect of co-fed ammonia in syngas on the performance of a traditional cobalt catalyst (platinum
promoted cobalt/alumina) was investigated during FischerTropsch synthesis (FTS) using a continuously
stirred tank reactor (CSTR). The addition of 1, 10, 100, and 1200 ppmw (concentration of ammonia with
respect to the syngas feed) of ammonia resulted in signicant irreversible deactivation of the catalyst
under identical reaction conditions. The percentage of deactivation was almost constant (5%) at all
the concentrations (11200 ppmw) of ammonia exposure. The addition of ammonia (either NH3 gas or
aqueous NH4 OH) particularly at higher concentrations exhibits lower methane selectivity compared to
ammonia-free synthesis conditions. This enhancement in C5 + hydrocarbon formation may be attributed
to the selective poisoning of metallic cobalt sites by addition of ammonia.
2013 Elsevier B.V. All rights reserved.

1. Introduction
FischerTropsch (FT) synthesis is an effective technology to
indirectly upgrade coal, natural gas, and biomass resources to
hydrocarbons that can be further upgraded to ne chemicals and
fuels [1,2]. Recently, because of increased focus on energy security and the implementation of more stringent environmental
legislations on liquid fuels, FT synthesis has received considerable worldwide attention in both industrial and academic domains
[14]. FT synthesis produces clean products that are lower in sulfur
and in heavy metals compared to those derived from crude oil. The
product distribution is related to the catalytically active species.
Iron-based catalysts, generally operating at high temperatures,
have high selectivities to oxygenates and branched hydrocarbons
[5]. Cobalt-based catalysts have been widely investigated for FT
synthesis due to high activity at low temperature (below 513 K),
high resistance to deactivation, low water-gas shift activity and
high selectivity to C5 + linear hydrocarbons. Two of the most important factors in determining the active cobalt surface site density
that are relevant to the FTS reaction are reducibility and surface
dispersion.
Gasication and reforming are processes in which a carbon
source (biomass, coal, petcoke or natural gas) is converted to synthesis gas in the presence of oxygen and/or steam. This synthesis

Corresponding author. Tel.: +1 859 257 0251; fax: +1 859 257 0302.
E-mail address: burtron.davis@uky.edu (B.H. Davis).
0926-860X/$ see front matter 2013 Elsevier B.V. All rights reserved.
http://dx.doi.org/10.1016/j.apcata.2013.07.060

gas or syngas can then be converted to transportation fuels via

FischerTropsch (FT) synthesis. This conversion process may be
affected by the presence of impurities such as H2 S, COS, NH3 , HCN,
and tars, formed during gasication. Even ppb level concentrations
of these impurities may be detrimental [6]. The concentrations of
these impurities are not uniform and depend strongly on the carbon source, gasication conditions and type of gasier used [7].
Generally, their concentrations are small when biomass is used as
the carbon source while with coal or petcoke, their concentrations
may be as high as 12% [7]. Poisoning studies of carbon conversion processes are extremely important, as they give benchmarks
regarding the amount of a particular poison that the catalyst can
tolerate without signicant deactivation. This, in turn, gives further
insight into: (1) the development of poison resistant catalysts and
(2) optimum levels in terms of cost to which the syngas needs to
be cleaned. Although present in moderate amounts, the impurities
can have a signicant impact on the downstream cobalt FT catalyst.
Among these impurities, sulfur compounds may cause
irreversible deactivation of catalysts used for FT [8]. The effects
of nitrogen containing compounds are unclear; some researchers
have reported no effect [9,10] while some have reported an immediate impact [1113] on catalytic activity. Claeys et al. [9] reported
that co-feeding of up to 25% NH3 in the synthesis gas did not affect
FT activity, and similar ndings were observed by Borg et al. [10]
with 4.2 ppmv of ammonia. Poisoning of cobalt-based FTS catalysts
by means of nitrogen containing compounds like NH3 and HCN
has been previously published [1113]. It was shown that cobalt
catalysts are rapidly but reversibly deactivated by HCN and NH3

V.R.R. Pendyala et al. / Applied Catalysis A: General 468 (2013) 3843

50

45

CO conversion (%)

[11]. Syntroleum showed that cobalt catalysts can be deactivated

by 1638%, depending on the type and level of N containing poison
[13]. LeViness et al. [14] investigated the effects of NH3 , HCN, and
NOx . It was found that small amounts of the N-contaminants (even
at ppb levels) have an immediate effect on catalyst activity. In the
present study, an effort has been made to investigate the impact of
ammonia on alumina supported cobalt catalysts at ppm level concentrations. The effects of the addition of 1, 10, 100, and 1200 ppmw
of nitrogen as NH4 OH on CO conversion, methane selectivity, C5 +
productivity and the activity factor of a Co-based FT catalyst are
presented.

39

1 ppm NH4 OH

40

35

30

25

2. Experimental
20
250

300

350

400

450

500

550

Time on stream (h)

Fig. 1. The effect of 1 ppm ammonia (NH4 OH) addition on CO conversion (T = 220 C,
P = 1.9 MPa, H2 /CO = 2, SV = 3 SL/gcatalyst /h).

Series Micro GC, providing molar compositions of C1 C7 olens and

parafns, as well as H2 , CO and CO2 . Hydrogen and carbon monoxide conversions were calculated based on GC analysis of the gas
products, the gas feed rate, and the gas ow that was measured at
the outlet of the reactor.
3. Results and discussion
The effect of ammonia during FT synthesis over a platinum
promoted cobalt catalyst was studied by co-feeding different concentrations of ammonia (1, 10, 100, and 1200 ppmw) added to the
feed gas. The partial pressures of the inlet hydrogen and carbon
monoxide were kept constant during all periods. After attaining a
steady state CO conversion level, the water was rst introduced
(1 mL/h) for a period of 34 days before adding the ammonia to the
reactor. After reaching a stable CO conversion with water addition,
1 ppm of ammonia (1 mL/h water containing NH4 OH) was co-fed
with the syngas. As shown in Fig. 1, a signicant drop in CO conversion was observed during the initial period of addition of NH4 OH.
However, continuous addition did not cause any further change in
CO conversion. Likewise, 10 ppm of ammonia as NH4 OH was cofed with the syngas stream. The effect of ammonium hydroxide
(10 ppm) on CO conversion for the Pt-Co/Al2 O3 catalyst is shown in
Fig. 2. The addition of 10 ppm NH4 OH led to a signicant drop in CO
50

45

CO conversion (%)

Condea Vista Catalox alumina (high purity -alumina, 150 m2 /g)

was used as the support for the cobalt catalyst. The catalyst was
prepared by a slurry impregnation method, and cobalt nitrate was
used as the precursor. In this method, which follows a Sasol patent
[15], the ratio of the volume of solution used to the weight of alumina was 1:1, such that the volume of solution was approximately
2.5 times the pore volume of the catalyst. Two impregnation steps
were used, each to load 12.5% of Co by weight. Between each step
the catalyst was dried under vacuum in a rotary evaporator at 60 C
and then the temperature was slowly increased to 100 C. After the
second impregnation/drying step, the catalyst was calcined under
air ow at 350 C. The promoter was added by incipient wetness
impregnation, and the precursor utilized for noble metal addition
was tetraammineplatinum (II) nitrate. After Pt addition, the sample was dried and calcined again at the same conditions as used
previously.
The FTS experiments were conducted using a 1 L CSTR equipped
with a magnetically driven stirrer with turbine impeller, a gas-inlet
line, and a vapor outlet line with a stainless steel (SS) fritted lter
(2 m) placed external to the reactor. A tube tted with a SS fritted
lter (2 m opening) extending below the liquid level of the reactor was used to withdraw reactor wax (i.e., rewax, which is solid at
room temperature), thereby maintaining a relatively constant liquid level in the reactor. Separate mass ow controllers were used
to control the ow rates of hydrogen and carbon monoxide. Carbon
monoxide, prior to use, was passed through a vessel containing lead
oxide on alumina to remove traces of iron carbonyls. The gases were
premixed in an equalization vessel and fed to the CSTR below the
stirrer, which was operated at 750 rpm. The reactor temperature
was maintained constant (1 C) using a temperature controller.
The catalyst (12.0 g) was ground and sieved to 45100 m
before loading into a xed-bed reactor for 12 h of ex situ reduction at 623 K and atmospheric pressure using a gas mixture of
H2 /He (60 NL/h) with a molar ratio of 1:3. The reduced catalyst
(10.0 g) was transferred to a 1-L continuously stirred tank reactor
(CSTR) containing 310 g of melted Polywax 3000, under the protection of inert nitrogen gas. The transferred catalyst was further
reduced in situ at 503 K at atmospheric pressure using pure hydrogen (20 NL/h) for another 24 h before starting the FT reaction. A
Teledyne ISCO Model 500 D syringe pump with Series-D pump controller was used to add water and ammonia to the reactor. In this
study, the FTS conditions used were 493 K, 1.9 MPa, H2 /CO = 2, and
a stirrer speed of 750 rpm.
Gas, water, oil, light wax, and heavy wax samples were collected daily and analyzed. Heavy wax samples were collected in
a 200 C hot trap connected to the lter. The vapor phase in the
region above the reactor slurry passed continuously to the warm
(100 C) and then the cold (0 C) traps located external to the reactor. The light wax and water mixture was collected daily from the
warm trap along with an oil plus water sample from the cold trap.
Tail-gas from the cold trap was analyzed with an online HP Quad

10 ppm NH4 OH
40

35

30

25

20
250

300

350

400

450

500

550

600

Time on stream (h)

Fig. 2. The effect of 10 ppm ammonia (NH4 OH) addition on CO conversion
(T = 220 C, P = 1.9 MPa, H2 /CO = 2, SV = 5 SL/gcatalyst /h).

V.R.R. Pendyala et al. / Applied Catalysis A: General 468 (2013) 3843

80

80

75

75

10 ppm NH4 OH

C1
70
14

Selectivity (%)

Selectivity (%)

40

C5 +

12

100 ppm NH4 OH

C1
70
14

C5 +

12
10

10

8
250

300

350

400

450

500

550

800

600

900

1000

1100

1200

Time on stream (h)

Time on stream (h)

Fig. 3. The effect of 10 ppm ammonia (NH4 OH) addition on product selectivity
(T = 220 C, P = 1.9 MPa, H2 /CO = 2, SV = 5 SL/gcatalyst /h).

Fig. 5. The effect of 100 ppm ammonia (NH4 OH) addition on product selectivity
(T = 220 C, P = 1.9 MPa, H2 /CO = 2, SV = 3 SL/gcatalyst /h).

conversion during the rst day and after that, CO conversion was
virtually constant with further addition of ammonium hydroxide
(i.e., a step decrease in catalytic activity). After ammonium hydroxide addition was stopped, CO conversion remained at the lower
level even after over 100 h of ammonium hydroxide free operation.
Fig. 3 shows the effect of 10 ppm NH4 OH on methane and C5 +
selectivities of a Pt-Co/Al2 O3 catalyst. Methane and C5 + selectivity
were found to be similar before and after the addition of NH4 OH.
In general for the cobalt catalyst, with decreasing CO conversion
methane selectivity increases and C5 + selectivity diminishes [10].
But the present result shows that there is no change in selectivity even after a decrease in CO conversion caused by the addition
of NH4 OH. In another experiment, after attaining the steady state
conversion level, 100 ppm ammonia as NH4 OH was co-fed with the
syngas. 100 ppm NH4 OH addition also resulted in a step decrease
in CO conversion during the rst day and after that there was no
further step change in activity with further addition (Fig. 4).
Fig. 5 shows the effect of 100 ppm NH4 OH on selectivity of
methane and C5 + of a Pt-Co/Al2 O3 catalyst. Prior to ammonium
hydroxide addition, methane and C5 + selectivities were found to
be 11.5% and 76% respectively. After 100 ppm of NH4 OH addition,
the methane selectivity dropped to 10% and C5 + selectivity was
increased to 78% even after a decrease in CO conversion from 37%
to 30%. Finally, the concentration of ammonium hydroxide was

increased to 1200 ppm and a similar step change (i.e., decrease)

in CO conversion was observed in the initial period and with further addition of NH4 OH there was only a slight decline in activity
(Fig. 6). To summarize, no positive effect of NH4 OH on CO conversion on a per gram catalyst basis was observed at all concentration
levels tested, but a consistent negative step decrease was observed.
Fig. 7 shows the effect of 1200 ppm ammonium hydroxide on selectivity of methane and C5 + of a cobalt/alumina catalyst. Prior to
addition, methane and C5 + selectivities were found to 10.5% and
75%, respectively. After addition of 1200 ppm NH4 OH, methane
selectivity dropped to 8.5% and C5 + selectivity increased to 79%
even though CO conversion decreased from 38% to 31%. After
termination of NH4 OH addition, the selectivities were returned
to the trend previously observed without NH4 OH addition. The
selectivity of Co/Al2 O3 is signicantly altered by adsorption of
ammonia on the catalyst; as activity decreased from to 60% of
its prior condition, there is an increase in high molecular weight
(C5 +) hydrocarbon production. This may be caused by adsorption
of ammonia molecules onto Co metal sites that normally adsorb
hydrogen, creating a relatively hydrogen poor surface. It may also
relate to the obvious decrease in CO conversion and hence production of water, the presence of which can inuence product
selectivity.

50

45

45
100 ppm NH4 OH

CO conversion (%)

CO conversion (%)

40

35

30

25

1200 ppm of NH4OH

40

35

30

25

20

20

15
900

1000

1100

1200

1300

Time on stream (h)

Fig. 4. The effect of 100 ppm ammonia (NH4 OH) addition on CO conversion
(T = 220 C, P = 1.9 MPa, H2 /CO = 2, SV = 3 SL/gcatalyst /h).

600

700

800

900

1000

Time on stream (h)

Fig. 6. The effect of 1200 ppm ammonia (NH4 OH) addition on CO conversion
(T = 220 C, P = 1.9 MPa, H2 /CO = 2, SV = 3 SL/gcatalyst /h).

V.R.R. Pendyala et al. / Applied Catalysis A: General 468 (2013) 3843

41

80
80

75

Selectivity (%)

Selectivity (%)

75
1200 ppm NH4 OH
70
14

C1
C5 +

12
10

100 ppm of NH3

C1

70
14

C5 +

12
10

8
600

700

800

900

1000

100

200

Time on stream (h)

500

60

100 ppm NH3

40

30

Fig. 9. The effect of 100 ppm ammonia (NH3 gas) addition on product selectivity
(T = 220 C, P = 1.9 MPa, H2 /CO = 2, SV = 4 SL/gcatalyst /h).

100

Relative CO conversion (%)

Similarly, in another experiment, after attaining the steady state

conversion, 100 ppm of dry ammonia (NH3 gas) instead of NH4 OH
was co-fed with the syngas. 100 ppm NH3 gas addition also resulted
in a step decrease in CO conversion level during the rst day and
after that there was no further step change in activity with further
addition (Fig. 8). The effects of 100 ppm NH3 gas on the selectivities
to methane and C5 + with a Pt-Co/Al2 O3 catalyst are shown in Fig. 9.
Prior to dry ammonia gas addition, methane and C5 + selectivities
were found to be 11.8% and 74.5%, respectively. After 100 ppm of
NH3 gas addition, the methane selectivity dropped to 10.8% and C5 +
selectivity increased to 77% even after a decrease in CO conversion
from 40% to 25%.
The relative CO conversion performance for the cobalt catalyst
at various concentrations of ammonia (NH4 OH) relative to the preexposure conditions is shown in Fig. 10. This clearly shows that the
percentage of deactivation is almost the same (5%) at all concentrations (11200 ppmw) of ammonia exposure. The same extent of
poisoning is consistent with the chemisorption of the same amount
of ammonia at the pressures represented by 11200 ppm NH3 .
This is consistent with a Langmuir type of isotherm for ammonia
adsorption and that at 1 ppm the pressure is sufcient to essentially reach saturation coverage. More importantly, catalyst activity
did not recover to the expected value after ammonia addition
was terminated under normal FTS conditions, indicating that the

CO conversion (%)

400

Time on stream (h)

Fig. 7. The effect of 1200 ppm ammonia (NH4 OH) addition on product selectivity
(T = 220 C, P = 1.9 MPa, H2 /CO = 2, SV = 3 SL/gcatalyst /h).

50

300

90
80
70
1 ppm NH4 OH

60

10 ppm NH4 OH
100 ppm NH4 OH

50

1200 ppm NH4 OH

40
1

Number of days
Fig. 10. Effect of NH3 concentration on CO conversion, related to the pre-exposure
conditions.

catalyst had deactivated (i.e., ammonia molecules are irreversibly

adsorbed onto cobalt active sites). In one instance, the activity was
partly recovered after the catalyst had been subjected to a mild
in situ hydrogen treatment (i.e., similar reaction conditions with the
exception of no carbon monoxide ow) for a 24 h period (Fig. 11).
However, more experimental work is needed to conrm this observation.
The AndersonSchultzFlory (ASF) model is a common model
used to describe the chain growth mechanism in FTS and was developed based on Florys pioneering studies on the fundamental nature
of polymerization. Chain growth probability () values are reported
in Table 1 for the addition of various concentrations of ammonia
to syngas. At baseline conditions (prior to the ammonia addition),
the value was found to be 0.88 and after the addition of 10 ppm
ammonia it increased to 0.93. With further increases in ammonia

20
Table 1
Chain growth probability () values at different concentrations of ammonia addition.

10
100

200

300

400

500

Time on stream (h)

Fig. 8. The effect of 100 ppm ammonia (NH3 gas) addition on CO conversion
(T = 220 C, P = 1.9 MPa, H2 /CO = 2, SV = 4 SL/gcatalyst /h).

S. No.

Ammonia concentration

Chain growth probability ()

1.
2.
3.
4.

0
10 ppmw
100 ppmw
1200 ppmw

0.88
0.93
0.94
0.93

42

V.R.R. Pendyala et al. / Applied Catalysis A: General 468 (2013) 3843

50

Olefin/paraffin ratio (%)

SV-3

H2 treatment

40

SV-4

100 ppm of
NH3 gas

CO conversion (%)

SV-4

100 ppm of
NH3 gas

2.0

30

20

10

1.5

1.0

Water addition
10 ppm ammonia addition
At similar CO conversion before and after the
addition of 10 ppm ammonia

0.5

0.0
200

400

600

800

Time on stream (h)

Fig. 11. Complete representation of a run includes ammonia addition and hydrogen
treatment.

concentration, chain growth probability values were similar to the

10 ppm NH3 condition (for 100 ppm it is 0.94 and for 1200 ppm it
is 0.93). Thus, the addition of ammonia to a cobalt/alumina catalyst
resulted in an increase in the chain growth probability factor for
FischerTropsch synthesis but was not dependent upon the partial
pressure of ammonia.
Recently, Borg et al. [10] studied the effect of ammonia on a
0.3%Re12%Co/NiAl2 O4 catalyst and reported that no changes in
activity and selectivity were observed when 4.2 ppmv of ammonia was added to the synthesis gas. In contrast, the, present study
indicates that with a typical Pt-Co/Al2 O3 catalyst the addition
of ammonia causes a decrease in CO conversion and signicant
changes (i.e., improvements) in product selectivity. A blank experiment without the addition of ammonia was run (not shown for
the sake of brevity). A slight decrease in CO conversion with time is
observed with cobalt catalysts due to normal aging, but there is not
a step decrease in CO conversion as is observed with ammonia poisoning. The effect of ammonia may be explained by the adsorption
of ammonia molecules on exposed cobalt surface sites of an operating catalyst in competition with hydrogen and CO, thus changing
the selectivity due to a coverage of ammonia molecules on metal
sites that normally adsorb hydrogen, creating a relatively hydrogen poor surface. After the addition of ammonia to the synthesis
gas, the H2 /CO usage ratio is increased. From these results, it is further conrmed that the addition of ammonia generated a hydrogen
poor surface. There are two likely possibilities for the benecial
impacts on selectivity (methane and C5 +) with ammonia addition;
one is that ammonia may inhibit the methanation sites responsible for the deviation in methane selectivity above that produced
from ASF kinetics; another possibility is that ammonia inhibits termination of chain growth. The evidence for the former is a slight
decrease in the deviation from the ASF distribution for methane
and the evidence for the latter is an increase in the value of .
At constant CO conversion levels, the olen/parafn ratio was
found to be similar before and after ammonia addition, as shown
in Fig. 12. After the addition of ammonia, olen content for all carbon numbers increased with decreases in CO conversion, which
is the result of secondary reactions of 1-olens: hydrogenation,
isomerization, readsorption and/or reincorporation into growing
chains [1619]. Ethylene is the most reactive olen, and its selectivity is lower than that of C3 and C4 olens, whereas a decrease in
1-olen content with increasing carbon number (for C3 + hydrocarbons) is caused by differences in reactivity, intraparticle diffusional
effects and solubility variation with molecular weight [1621]. Diffusivity decreases with increases in molecular weights of species,

10

Carbon number
Fig. 12. Olen/parafn ratios for before and after the addition of ammonia.

and higher molecular weight 1-olens have longer residence times

within catalyst pores, thus increasing the probability for secondary
reactions [1618]. Increases in solubility with increases in carbon
number also result in increased residence times for higher molecular weight hydrocarbons in the reactor as well as their higher liquid
phase concentrations, resulting in a greater extent of secondary
reactions [1821].
4. Conclusions
The addition of ammonia during FischerTropsch synthesis can
lead to signicant changes in both activity and product composition. The extent of deactivation was nearly identical at all the
concentrations of ammonia added under similar reaction conditions. A slightly higher selectivity to higher olen concentrations
with the addition of ammonia was observed. Ammonia appears
to poison cobalt metallic sites to some extent; however, prolonged
exposure at similar concentrations did not result in further changes
in activity. A mild in situ hydrogen treatment partly recovered the
activity of the catalyst. The benecial change in selectivity may be
explained by adsorption of ammonia molecules onto cobalt metal
sites that normally adsorb hydrogen, creating a relatively hydrogen
poor surface.
Acknowledgments
This work carried out at the CAER was supported by the Commonwealth of Kentucky and DOE grant (DE-FC26-08NT0006368).
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