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Applied Catalysis A: General 272 (2004) 353362

Evolution of several Ni and NiMgO catalysts during the hydrogenation reaction of adiponitrile
Marc Serra a , Pilar Salagre a, , Yolanda Cesteros a , Francisco Medina b , Jess E. Sueiras b
a

Dpt. Quimica Fisica i Inorgnica, Facultat de Qumica, Universitat Rovira i Virgili, Pl. Imperial Tarraco, 1, 43005 Tarragona, Spain b Escola Tcnica Superior dEnginyeria Qumica, Universitat Rovira i Virgili, Av. Pasos Catalans, 26, 43007 Tarragona, Spain Received in revised form 4 June 2004; accepted 7 June 2004 Available online 24 July 2004

Abstract The changes of the surface properties of two bulk Ni (one commercial Raney-Ni and one prepared crystalline Ni) and two NiMgO catalysts were studied after the hydrogenation of adiponitrile in the gas phase at atmospheric pressure for 216 h at two different reaction conditions. Catalysts before and after the catalytic reaction were characterized by different techniques. Raney-Ni and NiMgO catalysts show an evolution of activity with the reaction time until reaching constant conversion and selectivity values. The metallic area decreases after reaction for all catalysts. Interestingly, this decrease is lower and the surface area slightly increases when using reaction conditions of high space velocity, which favour the desorption of condensation products and results in a certain disagglomeration of particles. The high hydrogenation ability of Raney-Ni and the basicity of NiMgO catalysts allow them to achieve much higher conversions than the bulk Ni catalyst prepared. The presence of dened octahedral particles, observed for the crystalline Ni and NiMgO catalysts by SEM, has been related to the constant high value of selectivity to 6-aminohexanenitrile (around 80%) maintained after 216 h of reaction at less hydrogenating conditions. 2004 Elsevier B.V. All rights reserved.
Keywords: Lifetime studies; Nickel catalysts; Nickelmagnesia catalysts; Adiponitrile; 1,6-Hexanedinitrile hydrogenation; 6-Aminohexanenitrile

1. Introduction The hydrogenation of adiponitrile (1,6-hexanedinitrile) is an interesting industrial process to obtain 1,6-hexanediamine [16], which is a precursor of Nylon-6,6, and also to obtain 6-aminohexanenitrile [7,8], which is used in the preparation of caprolactam (precursor of Nylon-6) [912]. Nitrile hydrogenation products are mainly composed of a mixture of primary, secondary ant tertiary amines [13,14]. Condensation reactions can appear when the highly reactive intermediate imine reacts with the primary amine leading to secondary and tertiary amines [15,16]. The selectivity of the process can be partially controlled by using different catalysts. Thus, mostly primary amines are obtained when Co, Ni and Ru are used [5,6,1723]. In the industry, this reaction is performed in liquid phase, at high hydrogen pressures, and the Raney-Ni is probably the most frequently used catalyst [6,17]. Although Raney-Ni and Raney-Co are very active,

Corresponding author. Tel.: +34-977-559571; fax: +34-977-559563. E-mail address: salagre@quimica.urv.es (P. Salagre).

usually an excess of ammonia is necessary to decrease side reactions, which lead to the secondary and tertiary amines [2022,24]. The condensation compounds can remain on the metallic surface and block the catalytic active sites [16]. Verhaak et al. proposed that the deactivation of nickel catalysts in the hydrogenation of acetonitrile is due to the formation of surface nickel carbides and other partially dehydrogenated species, which were strongly adsorbed on the nickel surface blocking active sites [25]. A great number of attempts have been made to replace Raney-Ni by catalysts with a cleaner preparation, for the adiponitrile hydrogenation [2632]. However, it seems difcult to avoid the deactivation of nickel catalysts due to the causes commented above. In a previous work, we found that nickelmagnesia catalysts give lower amount of high-molecular-weight products than a bulk nickel catalyst for the hydrogenation of 1,4-butanedinitrile [33]. More recently, when some of these NiMgO catalysts were tested in the hydrogenation of adiponitrile, they showed at 24 h of reaction high conversion and high selectivity to

0926-860X/$ see front matter 2004 Elsevier B.V. All rights reserved. doi:10.1016/j.apcata.2004.06.008

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6-aminohexanenitrile (around 85%) and 1,6-hexanediamine (100%) at different reaction conditions [34]. We concluded that the crystal morphology of these catalysts could induce the selectivity to the monoamine. Also, the presence of basic magnesia favours the desorption of amines avoiding condensation reactions. Therefore, this could prevent catalyst deactivation. However, we observed some modications of the surface properties in the catalysts after 24 h of reaction [34]. The economic importance of producing 1,6-hexanediamine and, especially, 6-aminohexanenitrile, is reected in the contents of the articles published in the last years about this subject [2634] and in the great number of patents registered [36,10,1720,3540]. Nevertheless, it is important to note that the hemihydrogenation of adiponitrile still shows difculties in achieving selectively the monoamine with high conversion [7,8,3032]. In this way, our previous results with NiMgO catalysts were very promising [34]. We think that now more information about the activity evolution of the catalysts at different reaction conditions is needed to conrm that NiMgO catalysts are suitable for the industrial hydrogenation of adiponitrile to 6-aminohexanenitrile. In this work, we propose to study the changes of the surface properties of several nickel catalysts after the adiponitrile hydrogenation and their inuence on the catalytic activity evolution. With this goal, one crystalline Ni catalyst and two NiMgO systems will be prepared, studied, and compared with a commercial Raney-Ni for the hydrogenation of adiponitrile in the gas phase at atmospheric pressure for several days. Catalysts before and after different reaction conditions will be characterized by different techniques in order to explain the differences of activity observed for each catalyst in function of time and correlate their performances with the structural properties after reaction.

Sample (PB) First, Ni(NO3 )2 6H2 O was decomposed under static air at 373 K for 14 days to obtain Ni3 (NO3 )2 (OH)4 as a single phase. Then, this basic species was physically mixed with MgO, in the appropriate amount, and subsequently heated at 573 K owing argon through the sample for 13 h. The catalysts were obtained by reduction of the catalytic precursors mentioned above. The NiO sample was reduced under pure H2 at 573 K for 4 h whereas PA and PB precursors were reduced under pure H2 at 673 K for 6 h. The corresponding catalysts were named as Ni, A and B, respectively. The Raney-nickel catalyst used was a commercial nickel sponge suspension in water (Fluka, 99%) and was dried under pure H2 ow at 453 K for 1 h (referred to as Raney-Ni).

2.2. Characterization methods The catalysts were always handled under air-free conditions after the reduction step. They were transferred in degassed isooctane and under hydrogen atmosphere at room temperature. The isooctane surface-impregnated samples were further isolated form the air either with gold lm for the scanning electron microscopy (SEM) or with sticky tape for X-ray diffraction (XRD) monitoring. A glove box was used for mounting. The catalytic activity was measured in situ, in the reactor after reduction. Gas purges, positive gas pressures and Schlenk techniques were used when necessary. Powder X-ray diffraction patterns of the samples were obtained with a Siemens D5000 diffractometer using nickel-ltered Cu K radiation. This technique was also used to determine the reduction degree () of the catalysts by means of the Rietveld method [42]. BET surface areas were calculated from the nitrogen adsorption isotherms at 77 K using a Micromeritics ASAP 2000 surface analyzer and a value of 0.164 nm2 for the cross-section of the nitrogen molecule. Temperature-programmed reduction studies (TPR) were carried out in a Labsys/Setaram TG DTA/DSC, equipped with a 2731273 K programmable temperature furnace. Each sample was rst heated at 423 K in an Ar ow until no change of weight was detected. Then, the sample was heated in a 5 vol.% H2 /Ar ow from 423 to 1173 K at a rate of 5 K min1 . Hydrogen chemisorption was measured with a Micromeritics ASAP 2010C equipped with a turbomolecular pump. Samples had been previously reduced under the same conditions as for preparing the catalysts and the hydrogen was analyzed at 303 K. The nickel surface area was calculated assuming a stoichiometry of one hydrogen molecule per two surface nickel atoms and an atomic cross-sectional area of 6.49 1020 m2 /Ni atom. Scanning electron micrographs (SEM), were obtained with a JEOL JSM6400 scanning microscope operating at an accelerating voltage in the range 3035 kV.

2. Experimental 2.1. Catalysts preparation One NiO precursor was prepared by thermal decomposition of Ni(NO3 )2 6H2 O under static air at 373 K for 14 days to obtain Ni3 (NO3 )2 (OH)4 as a single phase which was then heated at 573 K for 11 h owing argon through the sample (referred to as NiO). Two NiOMgO samples (PA and PB), with a weight ratio of 4:1, were prepared using a commercial magnesia (BET surface area 120 m2 g1 ) according to the methods previously described [33,34,41] in order to obtain systems with and without solid solution and, therefore, with different interaction levels between the NiO and MgO phases. These preparative procedures are briey summarized as follows. Sample (PA) A homogeneous physical mixture of Ni(NO3 )2 6H2 O and MgO was heated under static air at 433 K for 7 days to obtain Ni3 (NO3 )2 (OH)4 as a single phase. The Ni3 (NO3 )2 (OH)4 /MgO precursor was later calcined under static air at 573 K for 4 h.

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2.3. Determination of the catalytic activity The gas phase hydrogenation of adiponitrile (ADN) at atmospheric pressure (1 bar) was studied in a tubular xed-bed ow reactor heated by an oven equipped with a temperature control system. The reactor was lled with the catalytic precursors (400 mg of NiO, 500 mg of PA and PB samples), which after reduction give the corresponding catalysts. The wet Raney-Ni sample was dried in situ in the reactor in a hydrogen ow to obtain 314 mg of catalyst before the activity test. These different amounts allow us to obtain the same theoretical amount of Ni for all catalysts. The catalytic experiments were performed at two different reaction conditions to obtain high or lower conversion values for each catalyst. The common reaction conditions used with Ni, A and B catalysts were: 423 K, vapour pressure: 571 Pa and H2 /ADN ratio: 178. Only space velocity was changed to achieve (1) high conversion (1790 h1 ), and (2) lower conversion (7162 h1 ). The reaction conditions used with Raney-Ni were different from those used for the other catalysts in order to obtain high conversion avoiding the cracking reaction when the same nickel amount was used for all catalysts. (1) High conversion: Reaction temperature: 423 K, adiponitrile vapour pressure: 571 Pa, H2 /ADN ratio: 178, and space velocity 23 873 h1 . (2) Lower conversion: Reaction temperature: 413 K, adiponitrile vapour pressure: 312 Pa, H2 /ADN ratio: 163, and space velocity of 34 139 h1 . To obtain these conditions, hydrogen was diluted with argon (10% H2 , 90% Ar). Reaction products were analyzed by an on-line gas chromatograph HP 5890 equipped with a 30 m commercial Rtx-5 amine capillary column and a ame ionization detector. Conversion and selectivity were dened by the following equations: conversion (%)= [moles of adiponitrile consumed] 100/[moles of adiponitrile charged]; selectivity (%) = [moles of one product of reaction] 100/[moles of adiponitrile consumed].

Table 1 Characterization of the catalytic precursors NiO Crystalline phases (XRD) Crystallite sizes (nm)a Surface area (m2 g1 )b TR (K) (TPR)c
a b c

PA NiOMgO solid solution 35.2 36.4 604

PB NiO 19.7 85.3 523

NiO 27.1 84.9 523

Using Scherrer equation. Using BET area method. TR = initial reduction temperature, obtained by TPR experiments.

of an argon atmosphere owing through the sample during the heat treatment. This argon ow favours the efcient desorption of the decomposition products and, therefore, the agglomeration is lower. The SEM micrograph of the NiO sample clearly shows octahedral particles with sizes between 200 and 500 nm (Fig. 1a). It is interesting to note that this NiO has less homogeneity in the particle sizes than the NiO prepared by calcining under static air [33]. Powder diffraction patterns of the NiOMgO systems show important differences. The pattern of catalytic precursor PA has diffraction lines which correspond to a crystalline

3. Results and discussion 3.1. Characterization of catalytic precursors and catalysts before reaction Table 1 shows some characterization results of the catalytic precursors. Sample NiO exhibits XRD peaks that can be identied as crystalline NiO phase. The NiO obtained by this new procedure has higher surface area (84.9 m2 g1 ) than the NiO prepared from calcining the Ni3 (NO3 )2 (OH)4 species under static air (11 m2 g1 ) [33]. This is probably due to the use

Fig. 1. Scanning electron micrographs of the catalytic precursor NiO (a) and its corresponding catalyst Ni (b).

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Table 2 Characterization of the catalysts before and after reaction at different reaction conditions Catalysts Reaction conditions H2 /ADN ratio Raney-Ni (fresh) (1) (2) Ni (fresh) (1) (2) A (fresh) (1) (2) B (fresh) (1) (2)
a b c d

Space velocity (h1 ) 23873 34139 1790 7162 1790 7162 1790 7162

Reaction temperature (K) 423 413 423 423 423 423 423 423

Crystal Ni sizes (nm)a

Metallic area (m2 g1 )b

Surface area (m2 g1 )c

Reduction degree, d

178 163 178 178 178 178 178 178

9.2 8.8 9.5 206.0 190.0 186.6 10.1 13.9 12.1 132.0 120.9 117.1

31.0 14.7 7.5 0.31 0.07 0.14 16.1 1.3 8.3 1.8 0.4 1.4

72.8 26.5 24.5 2.4 1.1 2.6 44.6 13.6 41.8 20.5 26.5 29.4

1 1 1 1 1 1 0.65 0.60 0.64 1 1 1

Using the Scherrer equation. Using the BET area method. Metal surface area (m2 g1 catalyst), calculated from chemisorbed H2 . Reduction degree obtained by using the Rietveld method [42].

NiOMgO solid solution phase whereas the pattern of sample PB mainly shows one phase identied as NiO phase and some less-intensity peaks which correspond to a less crystalline MgO phase. The use of an argon ow through the sample during the heat treatment probably hinders the diffusion between the NiO and MgO phases. This explains the absence of solid solution for sample PB. The low crystallinity of the MgO phase should be due to some disarrangement process, which takes place as a consequence of its interaction with water and/or nitrous vapours formed during the heating processes. Sample PB has higher surface area than sample PA (Table 1). This can be again explained by the effect of the argon ow used for preparing PB since it probably decreases the agglomeration effect of the MgO particles and also can hinder the sintering of the NiO phase formed during the heat treatment. As expected from previous works [34,41], sample PA showed by SEM homogeneous particles with not very well-dened morphologies whereas sample PB shows well-dened octahedral particles around 150 nm, which can be assigned to the NiO phase. The reducibility of the catalytic precursors was determined by TPR by comparing their initial reduction temperature values (TR ). The initial reduction temperature of sample PB is considerably lower than that of sample PA and the same than the NiO precursor (Table 1). This conrms the low interaction between the NiO and MgO phases for sample PB. Table 2 shows several characterization results for the four catalysts before reaction referred to as fresh catalysts. The Raney-Ni, Ni and B catalysts have crystalline nickel as single phase and show total reduction. In contrast, catalyst A shows a partial reduction ( = 0.65) as expected from the lower reducibility (higher initial reduction temperature) of the PA

precursor observed by TPR, which is related with the higher interaction between NiO and MgO phases when form a solid solution [34]. Although the NiO and PB precursors showed similar reducibility (Table 1), after reduction, Ni catalyst has lower surface area, lower metallic area, and higher crystallite size than catalyst B. This is related to the higher sintering of metallic particles suffered by Ni catalyst, in spite of using a lower reduction temperature (573 K) to prepare it (Fig. 1b). The main difference between these samples is the presence of magnesia, which makes more difcult the sintering of Ni particles for catalyst B. 3.2. Lifetime studies of catalysts In order to obtain information about the inuence of the reaction conditions with time on the catalyst properties and on its activity for the adiponitrile hydrogenation, we designed two catalytic experiments: one at high conversion and the other at lower conversion. The products obtained for each conversion depend on the catalyst and also on the reaction conditions used (see Scheme 1), as reported before [34]. High conversion is favoured at high temperature, high H2 /ADN ratio and at low space velocity. Under these conditions, an active catalyst leads to the formation of azacycloheptane as a main product, 1,6-hexanediamine in fewer amounts and, as a minor product, 6-aminohexanenitrile. Also, cracking products for the more active catalysts, and sometimes 3,4,5,6-tetrahydro-2H-azepine (THAPN) can be produced. On the other hand, the use of high space velocities and lower H2 /ADN ratio decrease the conversion values but increase the selectivity to one of the products of more industrial

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Scheme 1. Possible products obtained by catalytic hydrogenation of adiponitrile.

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interest: the less hydrogenated 6-aminohexanenitrile. The different reaction conditions were achieved by modifying the reaction temperature, the space velocity, and the H2 /adiponitrile (ADN) ratio, as explained in Section 2. The results of characterizing the catalysts after the two reaction conditions are shown in Table 2. 3.2.1. Conditions of high conversion Fig. 2 shows the lifetime studies obtained for all catalysts at conditions of high conversion for the hydrogenation of adiponitrile. Raney-Ni (Fig. 2a) and A (Fig. 2c) catalysts have a similar catalytic behaviour with time. Interestingly, these catalysts have higher metallic areas than the other two (Table 2). In the rst hours of reaction, they show a partial conver-

sion (80% for Raney-Ni and 75% for A catalyst). After 24 h, these catalysts reach the total conversion, which is maintained until the end of the experiment at 216 h. They present some differences with respect to the selectivity in the rst hours of reaction. At 5 h, the main product for Raney-Ni catalyst is azacycloheptane (53%) with high amounts of cracking products (30%) whereas, at this time, catalyst A shows 43% of selectivity to 1,6-hexanediamine followed by 20% of both 6-aminohexanenitrile and azacycloheptane. However, at 216 h the main products for the two catalyst are azacycloheptane and 1,6-hexadiamine with higher amounts of azacycloheptane for the A catalyst. The initial partial conversion observed for these catalysts can be explained by a strong interaction of the reaction products with some active sites, which favour condensation

Fig. 2. Lifetime studies at high conversion conditions for: (a) Raney-Ni catalyst, (b) Ni catalyst, (c) A catalyst, and (d) B catalyst. Symbols: conversion ( ), azacycloheptane selectivity ( ), 6-aminohexanenitrile selectivity ( ), 1,6-hexanediamine selectivity ( ), cracking products selectivity (), and condensation products selectivity ( ).

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and cracking reactions. This can produce an important initial decoration of the nickel particles with the condensation products formed. However, the hydrogen ow used could favour the partial desorption of some lightweight condensation products with time. This could explain the increase of conversion observed after 24 h. Nevertheless, the remaining decoration of Ni particles is responsible for the decrease of the surface and metallic areas observed for these catalysts after these reaction conditions (Table 2). The product distribution obtained at total conversion for both catalysts shows the main presence of azacycloheptane and 1,6-hexanediamine with low amounts of condensation and cracking products. This conrms the high hydrogenation capacity of these two catalysts in spite of their initial partial deactivation. The higher selectivity to azacycloheptane (around 60%) observed for the A catalyst could be related to the lower space velocity used. On the other hand, the catalytic behaviour of Ni catalyst with time is very different (Fig. 2b). There is an important decrease of the conversion in three steps. For each step, conversions values of 90, 60 and 15% seem to be stable for intervals of time between 048, 72144 and 168216 h, respectively. The selectivity also changes with time and, interestingly, the selectivity to 6-aminohexanenitrile increases progressively for each step. From 72 h, high amounts of 6-aminohexanenitrile (70%) are obtained. This value increases until 85% between 168 and 216 h. The highest selectivity to this product is obtained at a conversion of 15%. The great loss of activity is probably related to the higher difculty to remove the basic reaction products in a catalyst without magnesia and with very small metallic area (0.31 m2 g1 ). These reaction products can be more easily eliminated using NiMgO systems due to the presence of the basic sites, or in a Raney-Ni catalyst that has very small nickel particles, and consequently higher metallic area, which involves a higher hydrogenation activity compared to condensation, as reported before [34]. At these reaction conditions, the formation of the condensation products is favoured and a progressive decoration of the nickel particles with these compounds is produced. The important decrease of surface and metallic areas after reaction (Table 2) corroborate this loss of activity. The last catalyst tested, B catalyst, shows initially low conversion (around 30%) that increases until 90% at 72 h and, nally, reaches the total conversion at 120 h (Fig. 2d). The main product, at all the reaction times, is 6-aminohexanenitrile. The selectivity values are stable enough from 72 to 96 h with values around 45% to 6-aminohexanenitrile, similar amounts to 1,6-hexanediamine and azacycloheptane (20%) and a 10% of condensation products. The initial partial conversion of this catalyst can be related to the partial decoration of the Ni particles in the rst hours of reaction, as commented above for Raney-Ni and A catalysts. In this case, this effect should be more important since this catalyst has lower metallic area (1.8 m2 g1 ). However, the

presence of the basic sites, which control the generation of the condensation products, makes the hydrogen ow used sufcient to remove some light condensation products, and therefore the conversion with time reaches the 100%. The higher selectivity to 6-aminohexanenitrile observed (a less hydrogenated product) for catalyst B than for catalyst A (also a NiMgO system but which forms a solid solution), indicates a lower activity for catalyst B than A. This can be also related to its lower metallic area (Table 2). 3.2.2. Conditions of lower conversion Fig. 3 shows the lifetime studies obtained for all catalysts at conditions of lower conversion for the hydrogenation of adiponitrile. For the Raney-Ni catalyst, there is a high decrease in the conversion value (from total conversion to 50%) during the rst 22 h (Fig. 3a). However, after 24 h, the conversion increases stabilising at 120 h at around 70%. When a stable value of conversion is reached, the selectivity is also constant. The main products at 216 h are 40% of 6-aminohexanenitrile and 22% of 1,6-hexanediamine. It is important to note the important amount of cracking products formed (17%). At these conditions of partial conversion, the results obtained from the characterization of the catalyst after reaction show a higher decrease of surface and metallic area than in the more active conditions (Table 2). This indicates that now a more important decoration of the small Ni particles occurs explaining the decrease of conversion. The deactivation observed may be related to the formation of higher amounts of condensation products. This is probably due to the use of a diluted ow (10% H2 in the total ow) which decreases the hydrogenating ability of the nickel systems favouring the increase of the condensation reactions since hydrogenation and condensation reactions are competing [33]. However, independently of the gas used, a higher space velocity can favour the desorption of the more volatile condensation products and, this can explain the slight increase of conversion with time observed after 24 h of reaction. It is important to remark that despite the use of reaction conditions more favourable to the formation of the product of interest, 6-aminohexanenitrile, than for the other catalysts tested in this work, the maximum of selectivity towards this product achieved for the Raney-Ni catalyst was only around 40%. For the other bulk nickel catalyst (Ni catalyst), the conversion decreases drastically in the rst 24 h of reaction (Fig. 3b), but between 48 and 72 h stabilizes (around 10%). At this reaction time, the selectivity to 6-aminohexanenitrile becomes almost constant (8090%). After reaction, there is also a decrease of metallic area (Table 2). However, the decrease is lower than at the high conversion reaction conditions. The higher space velocity used at these conditions probably hinders the hydrogenation reaction but the desorption of the products is easier. A slight increase of the BET

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Fig. 3. Lifetime studies at lower conversion conditions for: (a) Raney-Ni catalyst, (b) Ni catalyst, (c) A catalyst, and (d) B catalyst. Symbols: conversion ( ), azacycloheptane selectivity ( ), 6-aminohexanenitrile selectivity ( ), 1,6-hexanediamine selectivity ( ), cracking products selectivity (), and condensation products selectivity ( ).

area value, and a decrease of the nickel particle size have been also observed for this used Ni catalyst. Therefore, the use of higher space velocity probably produces some disagglomeration of nickel particles during reaction. This was conrmed by SEM since this used Ni catalyst showed a certain lower agglomeration of particles compared to the fresh Ni catalyst. This observation explains the BET area results. In order to increase the activity, other reaction conditions were tested for this Ni catalyst. For example, increasing the reaction temperature to 473 K and the H2 /ADN ratio to 596, and decreasing the adiponitrile vapour pressure at 53 Pa maintaining the space velocity at 7162 h1 . At the rst 5 h of reaction this catalyst shows a conversion around

100%. However, after 24 h, the conversion values again decrease until 10% and the selectivity evolves until a 70% of 6-aminohexanenitrile. From these results, we can assume that, on the whole, independently of the reaction conditions used, this Ni catalyst cannot achieve high conversion values. This is probably due to its very low metallic area (0.31 m2 g1 ). By regarding the results of catalyst A (Fig. 3c), we can see that in the rst 24 h there is an important decrease of conversion from 100% to 55%, followed by a slight increase until stabilization to near 70% at 96 h. On the other hand, the desired high selectivity to monoamine does not almost vary from 24 h, arriving above 80%.

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The high space velocity used at these conditions does not favour the hydrogenation reactions but allows to eliminate more easily the lower-weight molecular condensation products. This explains the similar surface area (41.8 m2 g1 ) but lower decrease of metallic area (8.3 m2 g1 ) than at the reaction conditions of high conversion. Interestingly, catalyst A after 216 h of reaction maintains the well resolution of octahedral morphology that we previously observed after using this catalyst for a shorter reaction time [34]. The consequence is an increase in the selectivity to 6-aminohexanenitrile at 24 h of reaction which is maintained until the 216 h tested. In previous works, we conclude that the presence of octahedral morphology seems to induce a higher selectivity to monoamine [33,34]. Finally, the results obtained for catalyst B shows a drastic decrease of conversion from 100% to 10% in the rst 24 h of reaction (Fig. 3d). This is followed by a slight increase until certain stabilisation near 30% at 48 h. The selectivity to monoamine is high (around 80%) and maintains constant practically during all the experiment. The higher conversion loss observed for this B catalyst could be related to its small initial metallic area (1.8 m2 g1 ) The selectivity to 6-aminohexanenitrile is similar (80%) than that obtained for catalyst A under the same conditions. This can be again explained by the presence of well-dened octahedral particles after reaction, as observed by SEM. The results of surface characterization for catalyst B after these reaction conditions show a higher increase of the BET area and a lower decrease of the metallic area than at the reaction conditions of high conversion. This lower decrease of metallic area can be related to the high space velocity used, which disagglomerates particles and minimizes the retention of reaction products. Therefore, the decoration is lower, as commented above for the other catalysts.

With respect to the selectivity to 6-aminohexanitrile, we concluded that the high selectivity to this product (around 80%) obtained for Ni, A and B catalysts at less hydrogenating conditions is related to the presence of particles with octahedral morphology, as observed by SEM after reaction. Catalyst A achieves this high selectivity for a higher conversion value (70%) than the other two catalysts due to its higher metallic area. These lifetime studies show that NiMgO systems with octahedral particles appear as promising catalysts for the industrial production of 6-aminohexanenitrile. However, a key point will be to choose the optimum reaction conditions in order to obtain the desired products, maintaining the maximum surface and metallic area values. References
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4. Conclusions Two bulk Ni and two NiMgO catalysts were tested in the hydrogenation of adiponitrile in the gas phase and at atmospheric pressure for 216 h. The evolution of activity reaches a constant value of conversion and selectivity practically for all catalysts. The metallic area decreases after reaction for all of them due to the partial initial decoration of nickel particles with the condensation products generated during reaction. The decrease of metallic area is lower and the surface area slightly increases when using reaction conditions of high space velocity since these conditions facilitate both the desorption of the lightweight condensation products and a certain disagglomeration of the particles. Raney-Ni and NiMgO catalysts achieved much higher conversions than Ni catalyst, due, in the case of Raney-Ni, to its high hydrogenation ability and for the NiMgO catalysts to the presence of basic sites which hinder the formation of the condensation products.

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