~

ELSEVIER

APL S PAYI I CTES ALD

A: GENERAL

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

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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-ongraphite 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 precursors 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 El E2 E3 PAN (g) 18 18 18

DMF (g)
180 180 180

Fe(NO3)3.9H20 (g)
3.25 10.27 10.2 7

KNO3 (g)
1.12 1.12 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 previously. 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 isotherms 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 (m2/g) 34.9 24.44 22.9 9.1 Average pore size (nm) 1.67 1.57 1.54 6.46 Crystallites size ct-Fe (nm) 69.6 19.1 14.5 22 NH 3 at 673 (%vol) 0.069 0.073 0.098 0.079

El E2 E3 Industrial catalyst

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A.W. Morawski et al./Applied Catalysis A: General 156 (1997) 19-27

0.16

,..J o

0.12

0.08

f
z
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0.04

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650

670

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

E31 E32 E33 E34

1273 973 873 823

76.1 22.9 51.7 32.8

1.3 1.5 4.2 6.7

0.05 0.02 0.11 0.11

21.9 14.5 <2 <2

A.W. Morawski et al./Applied Catalysis A: General 156 (1997) 19-27

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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.

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A.W. Morawski et al./Applied Catalysis A: General 156 (1997) 19-27

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Fig. 2. (Continued).

highest activity at the temperature range of 623-723 K, and catalyst E31, carbonized 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 adsorption 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

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Pore width, A % of Total Pore Surface

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Pore width, A % of Total Pore Surface

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Fig. 3. Pore distribution determined b y D F T method: (a) catalyst E3n, (b) catalyst E32 , (c) catalyst E33, (d) catalyst E34.

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A.!E Morawski et al./Applied Catalysis A: General 156 (1997) 19 27

% of Total Pore Surface

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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. Carbonization 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 unfavourably 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
[1] K. Aika, H. Hori and A. Ozaki, J. Catal. 27 (1972) 424, [2] K. Aika, K. Tamaru, in: A. Nielsen (Ed.), Ammonia Catalysis and Manufacture, Springer, Berlin, Heidelberg, 1995. [3] M. Appl, Nitrogen, November-December, No 200 (1992) 7. [4] US Patent, 4163 775 British Petroleum (1979). [5] A.B. Burerr, E. Fitzer, M. Heym and B. Terwiesch, Carbon 13 (1975) 149. [6] M. Inagaki, L.J. Meng, T. Ibuki and M. Nakashima, Carbon 29 (1991) 1239. [7] A.W. Morawski, K. Katucki, M. Nakashima and M. Inagaki, Carbon 32 (1994) 1457. [8] S.J. Gregg, K.S.W. Sing, Adsorption Surface Area and Porosity, Academic Press, London and New York, 1967. [9] N.A. Seaton, J.ER.B. Walton and N. Quirke, Carbon 27 (1989) 853. [10] M. Von Szombathely, P. Brauer and H. Jaroniec, J. Comput. Chem. 13 (1992) 17. [11] J.J. Freeman, EG.R. Gimblett and K.S.W. Sing, Carbon 27 (1989) 85-93.