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A: GENERAL
ELSEVIER Applied Catalysis A: General 156 (1997) 19-27

A new preparation method of catalyst

for ammonia synthesis
A.W. Morawski*, Z. Lendzion-Bielufi, K. Katucki, R.J. Kaleficzuk
Institute of Inorganic Chemical Technologj, Technical Universi~, of Szczecin, Putaskiego 10,
70-322 Szczecin, Poland

Received 10 July 1996; received in revised form 29 October 1996; accepted 27 November 1996

Abstract

The preparation of a new catalyst for ammonia synthesis on the basis of a carbon support relies
on a thoroughly mixing of polyacrylonitrile (PAN) with inorganic salts Fe(NO3)3 and KNO3 being
previously dissolved in dimethylformamid (DMF). A catalyst was reduced at the flow of N2-H2
mixture before activity measurements. The preparation conditions, leading to the manufacture of
catalyst showing higher activity at atmospheric pressure than an industrial iron fused catalyst, were
found. The optimal composition of precursor and the temperature carbonization were found.

Keywords: Ammonia synthesis; Iron catalyst; Carbon catalyst

1. Introduction

The starting point of searching of new catalysts active in ammonia synthesis

derived from the studies of Aika and his co-workers [1] from Research Laboratory
of Resources Utilization Tokyo Institute of Technology. Examined materials
Ru-K/C showed activity at room temperature. Aika and Ozaki have found that
active carbon promoted with alkali metals is more effective as a ruthenium support
than other supports, such as for example A1203. A high activity of the carbon
supported promoted ruthenium catalyst was explained by ability to alkali metals
electrons transfer in the graphite lattice of the active carbons [2]. These unique
electronic properties of graphite-like structure of carbon support were utilized in
Kellogg Advanced Ammonia Process (KAAP) developed by The M.W. Kellogg
(Houston, USA) in cooperation with British Petroleum (Sunbury-on-Thames, UK)

* Corresponding author.

0926-860X/97/$17.00 @ 1997 Elsevier Science B.V. All rights reserved.

P l l S 0 9 2 6 - 8 6 0 X ( 9 6 ) 0 0 4 1 0-3
20 A.I~ Morawski et al./Applied Catalysis A: General 156 (1997) 19-27

[3]. In this technology the iron fused catalyst was replaced by ruthenium-on-
graphite catalyst based on the high surface area graphite (HSAG) [4]. That new
catalyst is several times more active than a traditional iron catalyst.
Carbon materials are usually applied in heterogeneous catalysis as the supports
of metals. It is well known that their structure results from the properties of
precursors. Activated carbons, prepared from the natural materials, characterize
themselves a wide variety of their properties. This reflects the heterogeneous nature
of the most precursors [5]. Recently, there is an interest in porous carbon materials,
whose precursors are polymers. The polymer precursors have evidenced special
interest because of their well-defined macromolecular structure. The carbons
prepared from these precursors may be expected to have the reproducible
characteristics and controlled pore size [6]. Structure of carbon materials can
be modified achieving better performance as supports applied in the heterogeneous
catalysis. It can be obtained by impregnation of a polymer precursor with a solution
of some inorganic salts before carbonization [7]. The selection of proper conditions
of the thermal treatment, which means particularly the carbonization temperatures,
allows to design properties of prepared carbon-metal material.
The present studies were concerned with the preparation of carbon supported
catalyst active in ammonia synthesis. Polyacrylonitrile (PAN) is the precursor of
carbon support and active phase is iron introduced as iron(III) nitrate promoted
with potassium nitrate. The effect of the carbonization temperature and initial
compositions on the catalytic properties and structure of obtained catalysts were
studied.

2. Experimental

Polyacrylonitrile (PAN-molecular weight 93 800) and inorganic salts

Fe(NO3)3.9H20 and KNO3 were thoroughly mixed by dissolving them in
dimethylformamide (DMF). The solution was heated at 343 K while stirring in
a closed glass vessel for 2 h to ensure the complete dissolution of all components.
The solution was then poured into a flat glass dish and dried in the air to remove the
solvent. Detailed initial compositions are shown in Table 1. The obtained pre-
cursors were crushed into pieces (2-3 mm of a diameter) and carbonized in a
nitrogen atmosphere. Carbonization was carried out to 973 K with the heating rate
of 200 K/h from the room temperature. Carbonization at final temperature was

Table 1
The amounts of starting materials used for preparation of the precursors

Code of catalyst PAN (g) DMF (g) Fe(NO3)3.9H20 (g) KNO3 (g)
El 18 180 3.25 1.12
E2 18 180 10.27 1.12
E3 18 180 10.2 7 3.37
 A. IE Morawski et al./Applied Catalysis A: General 156 (1997) 19-27 21

carried out for 24 h. After termination of that process the temperature was reduced
to 773 K and the reduction of carbonized catalysts was started at the flow of Nz-H2
mixture (molar ratio 1 • 3) with a space velocity of 2000 h -1. The reduction was
generally performed at 773 K. An activity of prepared catalysts defined as mol
percentage of ammonia in the outlet gases was measured under atmospheric
pressure and space velocity 1000 h 1. The activity of the commercial catalyst was
measured under the same conditions to compare with obtained catalysts activity. A
prereduced industrial catalyst, reduced at the same conditions as the obtained
precursors, was utilized for the comparison (these reduction conditions are not
ideal for a prereduced industrial catalyst).
The four new catalysts with the same composition as the catalyst denoted as E3
were prepared in the same way. The carbonization was carried out at four
temperatures (1273, 973, 873 and 823 K) under the conditions described pre-
viously.
All obtained catalysts after passivation were tested by XRD method using CoKc,
radiation. Average size of c~-Fe crystallites were determined from the broadening
of diffraction line Fe(002) with Scherrer method. The correction for instrumental
broadening was made using a quartz standard. Adsorption and desorption iso-
therms of N 2 w e r e recorded on ASAP 2010 Micromeritrics instrument. Liquid
nitrogen was used as a cooling medium during the adsorption at 77 K. The samples
were degassed at 523 K before the measurements of adsorption. Surface areas
were determined with BET method from the adsorption isotherms at relative
pressure P/Poof up to 0.2. The N 2 molecular area of 0.162 n m 2 w e r e used for the
calculation [8]. The DFT (Density Functional Theory) method [9,10], the most
suitable one, was used for micropore size distribution evaluation. The results
presented relate to the catalysts used for activity measurements. An average pore
size is defined as 2V/S~ETwhere V--pore volume, SBET=SUrface area.

3. Results and discussion

Surface areas, average pore sizes, average sizes of o~-Fe crystallites and
ammonia yield at 673 K of the investigated catalysts are presented in Table 2.

Table 2
Specific surface area, average pore size, ~-Fe crystallites size and activity at 673 K of obtained catalysts with
different initial composition. Activity measurements under atmospheric pressure and with s.v. of 1000h t

Code of catalyst Surface area Average pore Crystallites size NH 3 at 673

(m2/g) size (nm) ct-Fe (nm) (%vol)

El 34.9 1.67 69.6 0.069

E2 24.44 1.57 19.1 0.073
E3 22.9 1.54 14.5 0.098
Industrial catalyst 9.1 6.46 22 0.079
22 A.W. Morawski et al./Applied Catalysis A: General 156 (1997) 19-27

0.16

,..J

Z
o 0.12

0.08
f
0.04

0 I P I I I I
610 63 0 650 670 690 710 730 750

Temperamre, K

Fig. 1. Influence of carbonization temperature on activity of prepared catalysts. Activity in ammonia synthesis
reaction under atmospheric pressure and with s.v. of 1000 h - k E31-carbonized at 1273 K, E32-carbonized at
973 K, E33-carbonized at 873 K, E34-carbonized at 832 K.

A catalyst E 3 shows the highest activity (0.098% NH3) in comparison with other
catalysts. One should also notice its lowest surface area (22.99 m2/g) and an
average pore radius 1.54 nm. Probably the activities of the catalysts do not depend
on their areas but on their active areas. Catalysts E 1 and E2 show activity
approaching to the industrial catalyst (0.079% NH3). It was observed that increase
of nitrates (iron and potassium) content in precursor, caused a decrease of the
obtained catalysts surface area (Table 2), but concurrently average pore size and
average size of ~-Fe crystallites become relatively small. The presence of the
smallest crystallites was observed in a catalyst E3 that also showed the best
dispersion of the ~-Fe on the surface of the microporous carbon, which was
confirmed by its activity.
The influence of carbonization temperature on the activity and the properties of
obtained catalyst was also investigated. The effect of carbonization temperature on
the activity of the catalysts (with the same initial compositions as the catalyst E 3
from Table 1) is shown in Fig. 1. Catalyst E33, carbonized at 873 K, showed the
Table 3
Carbonization temperature, specific surface area, average pore size, pore volume and c~-Fe crystallites size of
obtained catalysts with identical initial composition

Code of catalyst Carbonization Surface area Average pore Pore volume Crystallites size
temperature (K) (mZ/g) size (nm) (cm3/g) c~-Fe (nm)

E31 1273 76.1 1.3 0.05 21.9

E32 973 22.9 1.5 0.02 14.5
E33 873 51.7 4.2 0.11 <2
E34 823 32.8 6.7 0.11 <2
 A.W. Morawski et al./Applied Catalysis A: General 156 (1997) 19-27 23

e~0 40

35
O
30
O
25
O
20
<
15
o
E 10
O
>
I L I I

0 0.2 0.4 0.6 0.8

a)
Relative Pressure (P/P0)

14

12
o
10

0 2
>
o i q i i
0.2 0.4 0,6 0,8

b) Relative Pressure (P/P0)

100

80
o
~ 6o
o
,.Q
o
rm 40
<
E 2o

>0 0 J I I I
0.2 0.4 0.6 0.8

c) Relative Pressure (p/p0)

Fig. 2. The a d s o r p t i o n ~ l e s o r p t i o n isotherms o f N2 at 77 K on the samples carbonized at different temperatures:
(a) 1273 K, (b) 973 K, (c) 873 K, (d) 823 K.
24 A.W. Morawski et al./Applied Catalysis A: General 156 (1997) 19-27

80

E
60

,.o
o 40

<
20
E
O
> I I I I
0 0.2 0.4 0,6 0.8

d) Relative Pressure (p/p0)

Fig. 2. (Continued).

highest activity at the temperature range of 623-723 K, and catalyst E31, carbo-
nized at 1273 K, showed the lowest activity. Average sizes of c~-Fe crystallites,
surface areas and total pore volumes are given in Table 3. Carbonization at 1273 K
leads to the manufacture of a material with a high surface area (76.1 m2/g).
Concurrently strong agglomeration of iron takes place (size of c~-Fe crystallites
21.9 nm) which unfavourably affect on its activity. Crystallites of ct-Fe also
become smaller while the carbonization temperature decreases (for E32
14.5 nm, for E33 and E34<2nm).
Adsorption-desorption isotherms at 77 K for catalysts carbonized at different
temperatures are presented in Fig. 2. The shape of adsorption isotherms of the
investigated carbon catalysts was attributed to pseudo-type 2 with hysteresis loop
H3 of IUPAC classification [11]. They are characterized by a very strong adsorp-
tion of nitrogen under a low relative pressure. Desorption needs much longer time
than adsorption to reach the equilibrium, particularly at a range ofp/po from 0.5 to
0.4. The capillary condensation is observed. The shape of hysteresis loop results
from the presence of pores with specific shapes. The shape of presented isotherms
proves that pores are "bottle" shaped or resemble deformed tubes with narrow
ends and other contractions. For the catalysts E3~, E32 and E33 hysteresis loops are
not closed even after a long time of desorption. It is known that forming of
micropores with diameter closed or even some times wider than adsorbate
molecule size makes difficult adsorption and particularly desorption even
under the relatively low pressures. This fact can be connected with a lower
activity of those catalysts. The pore distribution of each catalyst is shown in
Fig. 3. Micropores are in the majority of pores in catalysts E3~ and E32. In
catalysts E33 and E34 micropores with significant fraction of mesopores can be
observed.
 A. IE Morawski et al./Applied Catalysis A: General 156 (1997) 19-27 25

% of Total Pore Surface

40
/

30

20

10

0 50 100 150 200 250 300 350

a) Pore width, A

% of Total Pore Surface

50 - ~ ............................................................................................................

3o .... . . . .

20 -

10

0 5 10 15 20 25 30

b) Pore width, A

% of Total Pore Surface

40

30

20

l0

0
0 50 100 150 200 250 300 350
c) Pore width, A
Fig. 3. Pore distribution determined b y D F T method: (a) catalyst E3n, (b) catalyst E32 , (c) catalyst E33, (d)
catalyst E34.
26 A.!E Morawski et al./Applied Catalysis A: General 156 (1997) 19 27

% of Total Pore Surface

14

12

10

0
,¢ ¢/
0 100 200 300 400 5O0

d) Pore width, A
Fig. 3. (Continued).

4. Conclusions

A new preparation method of a novel catalyst for ammonia synthesis based on a

carbon support, prepared by the carbonization of polymer (PAN) containing
dissolved inorganic compounds of transition metal Fe(NO3)3 and alkali metal
KNO3 was presented. The effect of carbonization temperature was investigated.
The preparation conditions, leading to the activity higher than activity of double
promoted industrial iron fused catalyst in a low pressure range, were found. The
presented results indicate that the optimal composition for that catalytic system is
initial composition of E 3 catalyst (PAN-18 g, DMF-180 g, FeNO3-9H20-10.27 g
and KNO3-3.37 g), and optimal carbonization temperature was 873 K. The
carbonization carried out at that temperature leads to obtaining of catalyst Fe/
C/K with a very small c~-Fe crystallites (below 2 nm) and mixed pore structure
(micropores and mesopores) with a significant fraction of mesopores. Carboniza-
tion at 1273 and 973 K causes the agglomeration of iron into large particles and the
formation of micropore structure (dominating pore size 1.3 and 1.5 nm) which
makes difficult the diffusion of reagents through the pores that affects unfavour-
ably on the activity of prepared catalysts.
The new preparation method of Fe/C/K catalyst presented in that paper proceeds
in the following steps:

1. Dissolving of the mixture polymer (PAN) and Fe(NO3)3 and KNO3 in

DME
2. Drying and crushing into pieces of Fe(NO3)3/PAN/KNO3 precursor.
3. Carbonization of Fe(NO3)3/PAN/KNO3 precursor.
4. In situ reduction of catalyst before the activity measurements.
 A.W. Morawski et al./Applied Catalysis A: General 156 (1997) 19-27 27

Acknowledgements

These investigation were supported by The Polish Research Committee (KBN)

within Grant No 3 P405 020 06.

References

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Heidelberg, 1995.
[3] M. Appl, Nitrogen, November-December, No 200 (1992) 7.
[4] US Patent, 4163 775 British Petroleum (1979).
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