Nickel Molybdate Catalysts and Their Use in The Selective Oxidation of Hydrocarbons

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Catalysis Reviews: Science and Engineering

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Nickel Molybdate Catalysts and Their Use in the Selective Oxidation of Hydrocarbons
L. M. Madeira , M. F. Portela & C. Mazzocchia
a a b c
LEPAE, Departamento de Engenharia Qumica, Faculdade de Engenharia, Universidade do Porto, Porto, Portugal
b
GRECAT (UQUIMAF, ICEMS, Lisboa), Departamento de Engenharia Qumica, Instituto Superior Tcnico, Universidade Tcnica de Lisboa, Av. Rovisco Pais, 1049001, Lisboa, Portugal
c
Dipartimento di Chimica, Materiali e Ingegneria Chimica, Politecnico di Milano, Milano, Italy Available online: 17 Oct 2008
To cite this article: L. M. Madeira, M. F. Portela & C. Mazzocchia (2004): Nickel Molybdate Catalysts and Their Use in the Selective Oxidation of Hydrocarbons, Catalysis Reviews: Science and Engineering, 46:1, 53-110 To link to this article: http://dx.doi.org/10.1081/CR-120030053
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CATALYSIS REVIEWS Vol. 46, No. 1, pp. 53110, 2004
Nickel Molybdate Catalysts and Their Use in the Selective Oxidation of Hydrocarbons
Downloaded by [UNAM Ciudad Universitaria] at 11:19 24 February 2012
L. M. Madeira,1 M. F. Portela,2, * and C. Mazzocchia3
LEPAE, Departamento de Engenharia Qumica, Faculdade de Engenharia, Universidade do Porto, Porto, Portugal 2 GRECAT (UQUIMAF, ICEMS, Lisboa), Departamento de Engenharia Qumica, Instituto Superior Tecnico, Universidade Tecnica de Lisboa, Lisboa, Portugal 3 Dipartimento di Chimica, Materiali e Ingegneria Chimica, Politecnico di Milano, Milano, Italy
1
CONTENTS ABSTRACT . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 54 1. 2. Introduction . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 54 Preparation of Catalysts . . . . . . . . . . . . . . 2.1. Coprecipitation Techniques . . . . . . . . 2.2. Other Techniques . . . . . . . . . . . . . . 2.2.1. Molybdenum-Enriched Catalysts 2.2.2. Nickel-Enriched Catalysts . . . . 2.3. Supported and Doped Catalysts . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 55 55 58 60 61 61
3. 4.
Thermal ActivationTransition of Phases . . . . . . . . . . . . . . . . . 63 Characterization of Catalysts . . . . . . . . . . . . . . . . . . . . . . . . . 66
*Correspondence: M. F. Portela, GRECAT (UQUIMAF, ICEMS, Lisboa), Departamento de Engenharia Qumica, Instituto Superior Tecnico, Universidade Tecnica de Lisboa, Av. Rovisco Pais, 1049-001, Lisboa, Portugal; Fax: 351-21-8477695; E-mail: mfportela@ist.utl.pt. 53
DOI: 10.1081/CR-120030053 Copyright # 2004 by Marcel Dekker, Inc. 0161-4940 (Print); 1520-5703 (Online) www.dekker.com
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Madeira, Portela, and Mazzocchia
4.1. 4.2.
4.3.
Composition of Phases for Catalysts with Different Ni : Mo Ratios . . . . . . . . . . . . . . . . . . . . . . . . . . . Other Physicochemical Characterizations . . . . . . . . . 4.2.1. Stoichiometric Nickel Molybdate . . . . . . . . . 4.2.2. Catalysts with Excess Molybdenum or Nickel . . 4.2.3. Catalysts Prepared Using Organic Precursors and Sol Gel Methods . . . . . . . . . . . . . . . . . . 4.2.4. Doped and Supported Nickel Molybdates . . . . Characterization of the High Temperature b-Phase . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .
. . . .
. . . .
. . . .
. . . .
. . . .
66 67 67 71 75 76 79 80 81 85 85 89 93 97 98
. . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .
5.
Applications of Ni Mo O Catalysts . . . . . . . . 5.1. Oxidation of Hydrocarbons . . . . . . . . . . 5.2. Oxidative Dehydrogenation of Light Alkanes 5.2.1. Undoped Ni Mo Catalysts . . . . . . 5.2.2. Doped and Supported Catalysts . . . 5.2.3. Kinetics and Mechanism . . . . . . . 5.3. Nature of Active Sites . . . . . . . . . . . . .
6.
Conclusions and Future Trends . . . . . . . . . . . . . . . . . . . . . . .
REFERENCES . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 102
ABSTRACT
This paper reviews the preparation techniques, characterization, and use of nickel molybdate catalysts in the selective oxidation of hydrocarbons, particularly of light alkanes. Catalysts with different Ni : Mo ratios, unsupported and supported, undoped and doped, were considered. Particular attention is given to the thermal activation process for the transition of the low temperature a-phase into the metastable b-phase, which was shown to be more selective in some cases. Special reference is also made to the results of kinetic studies performed, to the mechanisms proposed for some important reactions, and to the nature of the active sites. Finally, after some general conclusions, future trends are analyzed. Key Words: Nickel molybdate; Preparation; Characterization; Selective oxidation; Hydrocarbons; Oxidative dehydrogenation; Light alkanes.
1.
INTRODUCTION
Olens, aromatics, and many oxygenates are widely used as important raw materials in industrial processes,[1,2] and thus the strong pressure of international markets has led to constant optimization of production processes. Cost reduction can be achieved by using cheaper raw materials (for instance alkanes), combined in some cases with the use of more sophisticated catalysts. Indeed, in the last years a clear trend has been observed for the use of light alkanes for the direct production of oxygenatesthrough
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partial oxidation[3 5]or to manufacture olens through dehydrogenation or oxidative dehydrogenation (ODH) processes,[5 7] due to the ready availability and low price of natural gas. However, this is a challenging problem for the chemical industry because alkanes are less reactive than the products obtained, such as alkenes, dienes, or aldehydes and acids, which are easily totally oxidized at the high temperatures required to activate alkanes properly. Therefore, around the world much effort has been put into developing new catalytic systems providing selective oxidation of hydrocarbons, particularly light alkanes with useful yields. However, the search for better and more effective catalyst compositions, preparations, and processes continues and, up to now, few promising catalysts were found for these applications. For instance, metal molybdates were successfully employed in selective oxidation reactions and are quite versatile catalysts for important industrial processes.[5] Among them, nickel molybdates show very interesting potential for oxidation reactions, and particularly for ODH of light alkanes. A large number of papers and patents is found in the literature regarding these applications (mentioned throughout this text). But nickel (Ni) molybdenum (Mo) catalysts are also very important for other processes, such as the hydrodesulfurization and hydrodenitrogenation of petroleum distillates;[8 17] the water gas shift reaction;[18] the steam reforming, hydrogenolysis, and cracking of n-butane;[19] the oxidative coupling of methane;[20] and other industrially important hydrogenation and hydrotreating reactions.[8,21 24] Despite this large number of important industrial applications, a review that systematically analyzes the preparation techniques used, the more important characterization results, and the main catalytic studies performed for oxidation reactions with Ni Mo O catalysts, is not found in the open scientic literature. With this review we intend to ll this gap. We should remark that we will only consider reaction investigations involving selective oxidation of hydrocarbons.
2.
PREPARATION OF CATALYSTS 2.1. Coprecipitation Techniques
During the preparation, through the coprecipitation method, of nickel molybdenum catalysts with different Ni : Mo ratios, Andrushkevich et al.[25] found in 1973 that both the chemical composition and composition of phases of the obtained precipitate depend strongly on the precipitation conditions (concentration of reactant ions in solution, temperature, and duration of the aging process). The unsatisfactory aspects of the coprecipitation method, involving direct mixture of the solutions, and particularly the lack of reproducibility in the results, were eliminated by using an experimental setup that allowed continuous preparation of the catalysts by precipitation.[25] The nickel nitrate and ammonium paramolybdate solutions were mixed at constant ow rate at 868C. The NH 4 ion concentration in the molybdenum-solution was equal to the NO2 ion concentration in 3 the nickel solution. The Ni : Mo ratio in the solution was varied by changing the respective ratio in the original solutions. When steady-state conditions for precipitation were established, the pH in the reaction volume was 5.4. The obtained precipitates were air dried at room temperature and calcined at 5008C.[26]
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Andrushkevich et al. also knew that, for preparation of nickel molybdates, the pH of the medium during precipitation has a signicant inuence on the composition of the precipitates. Thus, they decided to investigate the problem thoroughly.[27] They found that by increasing the ammonia concentration in the paramolybdate, while the other precipitation conditions were kept constant, an increase in the nickel concentration in the nal precipitate was recorded due to solubilization of molybdenum with ammonia. After the 1980s, several works were published in which the NiO MoO3 system was studied because of its use as a hydrodesulfurization catalyst. However, the preparation methods adopted varied slightly from one group to another:
Vagin et al.[28] prepared NiO MoO3 samples with various compositions by coprecipitation of analytical salts [Ni(NO3)2 and (NH4)6Mo7O24], from the corresponding solutions at 908C and pH 6.0 6.5. The solutions containing the precipitates were then evaporated in a water bath, dried at 1108C, and calcined at 6008C for 6 hr. Brito et al.[29] also prepared a series of Ni Mo mixed oxides by coprecipitation (either in continuous or discontinuous mode), always controlling the precipitation conditions in order to change the Ni : Mo ratio of the nal product, namely by the pH of the medium. The hydrated precursor of the hydrodesulfurization catalysts[11] was synthesized by coprecipitation of nickel nitrate (pH 4.7) and ammonium heptamolybdate (pH 5.6) aqueous solutions. The methodology used to obtain the phase that is stable at high temperatures (b-NiMoO4) will be described later (see Section 3). The investigations carried out at the Polytechnic of Milan, Italy, have helped, among other aspects, to clarify the experimental conditions that determine the formation of oxides with different compositions in the NiO MoO3 system. In two preliminary studies,[30,31] special attention is given to the methodology that enables the precursor of the catalytically active phase to be obtained. The solvated precursor was prepared by mixing, with stirring, equimolar solutions of ammonium molybdate and nickel nitrate [Ni(NO3)2 . 6H2O] at pH 5.6 and at a temperature of 858C. The molybdenum solution was prepared by dissolution of molybdic acid (H2MoO4 . H2O) in an ammoniacal solution at 858C and pH of 6.2. The precursor obtained, partially crystalline and with a pale yellow color, was dried at 1208C and thermally activated at 5508C for 2 hr. It is noteworthy that the NiMoO4 prepared by coprecipitation was also patented;[32] however, nickel molybdate was also synthesized by the dry mode, from NiO and MoO3.[30,31] As shown by Mazzocchia et al.,[30 34] the precipitation process can lead to different precursors with the general formula: xNiO yMoO3 nH2 O mNH3 (1)
Small changes in experimental conditions such as pH, precipitation temperature, H2MoO4/NH4OH ratio, ltration temperature, duration of aging of the precipitate in the mother liquor, and duration and temperature of drying may lead to precursors with different x, y, n, and m values. The effect of some of these parameters is shown in Fig. 1.
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Figure 1. Effect of the precipitation parameters on the type of precursor obtained. Each arrow refers to the effect of a given parameter. (Information adapted from Refs.[30,33].)
Attention should be paid to the fact that each arrow refers to the effect of a given parameter on the type of precursor obtained. For formation of the precursors, the following equilibria are established between the different species:[33]
6 7MoO2 8H 4(aq:) (aq:) !Mo7 O24(aq:) 4H2 O
(2) (3)
6
Ni2 MoO2 (aq:) 4(aq:) !NiMoO4(s) Ni2 (aq:) Ni2 (aq:)

10 Mo7 O6 24(aq:) !NiMo6 O24(aq:) 2OH (aq:) !Ni(OH)2(s)
(Mo )
(4) (5)
The conditions required for preparation of pure a-NiMoO4 are highly critical.[31] In order to avoid polymerization of the molybdate ions it is not sufcient to control the environmental conditions (Fig. 1). The rate at which the nickel solution is added is also a determining factor, probably because the rate of Eq. (4) is a critical condition. For formation of the precursor with Formula (1), the main reactions involved are the following: 1 x , , 1)Eqs. (3) (4); 6 y 1, x , 1)Eqs. (3) (5) y x y)Eq. (3);
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Thus, at pH 6 the G precursor is obtained (see Fig. 1), which becomes more green as pH is increased due to coprecipitation of nickel hydroxide [cf. Eq. (5)], yielding an x/y ratio higher than 1. In fact, in the patented preparation method, in which the temperature was maintained at 858C, but with a pH of 6, the nal catalyst had the following composition: Ni1.5MoO4.5.[32] On the other hand, if room temperature is used, without changing the other experimental conditions, a pale blue (B) precursor is obtained for which y/x 6 (cf. Fig. 1). After thermal activation, the sample exhibits the infrared spectrum and x-ray diffraction (XRD) pattern characteristic of excess MoO3. The yellow precursor (Sof stoichiometric), where x y 1, is obtained in the conditions already mentioned. If, during ltration, the solution is allowed to cool (between 658C and 858C), a pale yellow precursor (E) is obtained with a ratio y/x . 1. For this precursor in particular, both the time of aging in the mother liquor and the temperature of the solution determine the y/x ratio. Using, for instance, a pH of 5.6 but mixing the solutions at 708C, a precursor is obtained, which after calcination (during 2 hr at 5508C) yields a catalyst with the formula NiMo1.5O5.5.[32] The stoichiometric catalyst has been used in several studies, but the preparation procedure employed was not always exactly the same. For instance, 0.5 M solutions of Ni(NO3)2 . 6H2O and H2MoO4 were employed, with a nal pH of 5.1 and at 858C.[35] In other cases 0.25 M solutions were used, with precipitation at pH 5.2 and a temperature of 908C,[36] with ltration of the precipitate at 858C and drying for 4 hr at 1108C, followed by calcination for 2 hr at 5508C.[37] The parameters m and n in the precursor with Formula (1) are affected by slight variations in the temperature or in the amount of ammonia. For instance, in a study where the yellow precursor (S) was prepared by using 0.25 M solutions of molybdic acid and nickel nitrate, at 858C and pH 5.4, thermogravimetric analyses revealed the following composition for the precursor: NiMoO4 . 3/4 H2O . 3/4 NH3.[33] A green precursor (G) was also prepared with the following composition: Ni1dxMoO4 . 1/3 H2O . 5/3 NH3, from a 0.25 M solution of ammonium heptamolybdate [(NH4)6Mo7O24 . 4H2O] at 858C, the pH of the solution being adjusted with ammonia in order to yield an NH3/Mo ratio of 1.5. The 0.25 M solution of nickel nitrate, at the same temperature, was added at a controlled rate (7 mL/min). The green precipitate was immediately formed and the pH dropped from its initial value of 8.48 to 7.09 in 1 hr.
2.2.
Other Techniques
New techniques have been developed for preparation of catalysts that enable clarication of specic aspects in multicomponent catalytic systems. Better control of the contact between phases is achieved when compared with catalysts prepared by precipitation or impregnation. In these situations, it is also difcult to control the thickness and structure of the supercial layer. With these goals in mind, Zou and Schrader[38] used reactive sputtering, an advanced technique for materials processing, in order to produce catalysts of the NiMoO4 MoO3 system with controlled compositions and structures, especially thin lms with well-dened architectures. Another advantage of the samples prepared in this way, compared to materials obtained by precipitation, is that they are more easily characterized by several techniques. They prepared very thin lms of MoO3, of NiMoO4, and of combinations of both oxides over different supports (including SiO2),
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which were later characterized by various techniques. In the samples containing both components, the lms were prepared through a sequential process, the NiMoO4 being deposited over the predeposited MoO3. More recently, they have examined in detail the deposition parameters for the reactive sputtering technique and found that the multilayer lms of NiMoO4 on a-MoO3 include an interfacial material identied as b-NiMoO4, which was detected at relatively low temperatures in the bilayer structures.[39] The use of organic salts for preparation of active catalytic systems, such as Ni Mo O, has the advantage of providing a lower crystallization temperature. Using an oxalic precursor (a product that decomposes at a lower temperature than ammonia) and different thermal treatments, Mazzocchia et al. have obtained several catalysts with different compositions.[34] The NiC2O4 . 2H2O and MoOC2O4 . 4H2O mixture was prepared by adding ammonium heptamolybdate to 250 mL of a solution containing a large excess of oxalic acid. After dissolution, nickel nitrate is added at room temperature such that the Ni : Mo ratio is 1. The solution (0.14 M in Ni and in Mo) is then slowly warmed under vacuum to 408C. Precipitation starts immediately and increases as the water evaporates. The precursor is nally dried at 1208C for 15 hr. Another method of catalyst preparation that has been recently used resorts to natural substances or polymers. A polymeric network is created, containing the ionic compounds of the active catalyst inside the organic matrix. In this context, Anouchinsky et al. tested a new methodology for NiMoO4 preparation in which the precursor is an organic gel (agaragar) containing the Ni and Mo ions in a 1 : 1 atomic ratio.[40] This approach offers several advantages: it is cheap and simple and multicomponent catalytic systems can be prepared by simple dissolution of the desired elements, at the appropriate concentrations, in the aqueous solution. In this way one may change, for instance, the Ni : Mo ratio with the simultaneous presence of promoters. The gel was prepared from 0.5 M solutions of nickel nitrate and ammonium heptamolybdate and mixed at room temperature with continuous stirring. A load of 1% (by weight) of powdered agar-agar is added and the solution warmed at 808C to solubilize the agar-agar. Rapid cooling of the solution yields the gel, which is subsequently dried by slow heating (108C/hr) from room temperature up to 1208C. This temperature is then maintained for 4 hr and nally the gel is calcined. The agents that control pH in the synthesis of precursors of mixed oxides must be easily removed from the precipitate. From this point of view, oxalic precursors have been shown to be advantageous since they crystallize at low temperatures.[34] It would then be expected that, for the Ni Mo O system, the use of the sol gel technique could be benecial. The sol gel technique offers a low-temperature method for synthesizing materials that are either totally inorganic in nature or both inorganic and organic. The process offers many advantages, including the use of simple and inexpensive equipment, excellent control of the stoichiometry of precursor solutions, and ease of compositional modications. Good control of the stoichiometry may be very useful for ne control in the preparation of Ni Mo O catalysts, as their composition is crucial for catalytic applications. With this goal in mind, as well as the fact that precursor decomposition can be achieved at low temperatures, several authors decided to apply the sol gel route for preparation of nickel molybdate catalysts. Although papers on this subject are somewhat scarce, we should mention the work of Anouchinsky et al., who have prepared several catalysts by the sol gel method.[40] As expected, homogeneous dispersion of the Ni and
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Mo ions in the precursor was achieved, which led to formation of the NiMoO4 phases, whose crystallization occurs at temperatures lower than those prepared by coprecipitation. This process also leads to the stabilization of the b-phase at room temperature. Lezla et al.[41] have also adopted the sol gel methodology to prepare the stoichiometric catalyst using citric acid (1 mol/Ni), which was added to a solution of nickel nitrate (0.4 M). Then a solution of (NH4)6Mo7O24 . 4H2O was added very slowly so as to avoid precipitation. The solution was evaporated until a gel and then a solid were obtained. Finally, the solid was ground and heated in air at 5008C for 24 hr.[41] The solgel technique also was used recently for the preparation of supported catalysts, with particular advantages in the case of the NiMoO system (see Section 2.3). Nanocrystalline NiMoO4, among other molybdates, was also recently prepared from the complete evaporation of a polymer-based metal-complex precursor solution.[42,43] These ne-grained materials (with particle diameters less than 100 nm) are expected to have potential applications in many technological areas. 2.2.1. Molybdenum-Enriched Catalysts
Catalysts containing excess MoO3 are often prepared by drying the nal solution, after mixing the reactants in appropriate ratios. However, this method gives rise to numerous problems regarding the nature of the dried precursor, because the concentration of the solution changes during the drying process, leading to precipitation of heteropolymolybdates or to a mixture of molybdate and molybdic acid.[44] Thus, Mazzocchia et al. decided to prepare several catalysts with excess Mo, all with the same composition but obtained from different precursors. They used decomposition of the heteropolymolybdate or dry-mixing of nickel molybdate and excess of molybdenum trioxide. A catalyst studied, derived from the heteropolymolybdate, was NiMoO4 . 5MoO3, obtained through thermal decomposition of (NH4)4H6NiMo6O24 . 5H2O.[44] In other works a certain excess of MoO3 was introduced by cooling the solution of the a-NiMoO4 precursor, with consequent coprecipitation of (NH4)4H6NiMo6O24 . nH2O (cf. Fig. 1).[31] Both the temperature and the cooling period depend on the excess of molybdenum desired. In a very interesting work published by Ozkan and Schrader, the synthesis of nickel molybdates containing an excess of molybdenum through several methods is described in detail.[45] The excess of Mo (relative to the stoichiometric) is present as a new phase, MoO3, substantially increasing the complexity of the system. The authors report the following methods for incorporation of MoO3 into the catalyst: precipitation, solid state reaction, and impregnation. Nickel molybdates prepared through precipitation were obtained from aqueous solutions of ammonium heptamolybdate [(NH4)6Mo7O24 . 7H2O] and nickel nitrate [Ni(NO3)2 . 6H2O], the pH being changed with ammonium hydroxide or nitric acid solutions. In order to obtain pure nickel molybdate, pH during addition and reaction was kept at 6 (with a temperature of 638C). The catalysts with excess MoO3 are obtained by acidication of the medium during addition of the solutions, the pH depending on the excess of MoO3 desired. It should be stressed that with this procedure the catalyst composition is insensitive to both concentration and composition of the reactants, the pH of the medium during the precipitation being the key factor. The solid-state synthesis basically consists of heating NiO together with MoO3, or MoO3 mixed with NiMoO4. Nickel molybdate, obtained by precipitation, was also impregnated with ammonium
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heptamolybdate to provide catalysts with an excess of MoO3 between 2% and 55%. Molybdenum trioxide was also impregnated with NiMoO4. The experimental procedure used for these syntheses has been described in detail.[45] More recently, Lezla et al. have also prepared Ni Mo O catalysts with Mo : Ni ratios between 0.90 and 2.15 using several methods, which include precipitation, evaporation to dryness, sol gel, impregnation, and mechanical mixing. They analyzed the inuence of the preparation method on the catalytic performances for propane ODH.[41] 2.2.2. Nickel-Enriched Catalysts
Catalysts with an excess of Ni have usually been prepared in two ways: (i) precipitation at 858C and pH 6.2, using 0.25 M solutions of H2MoO4 and Ni(NO3)2, which yields an Ni : Mo ratio of 1.40 and provides formation of NiO together with the a- and b-phases of NiMoO4; and (ii) mechanical mixing of NiMoO4 . H2O and Ni(OH)2, which provides Ni : Mo ratios in the range 1.1 1.6, followed by activation at various temperatures.[46] Chemical impregnation of a-NiMoO4, using an aqueous solution of nickel acetate, was also adopted for preparation of Ni-enriched catalysts.[47] Using molybdenum oxalate instead provided catalysts with excess molybdenum.[47]
2.3.
Supported and Doped Catalysts
The use of supported nickel molybdate catalysts in ODH reactions is not very common. Some exceptions are recent works in which TiO2 (anatase)[48] and SiO2[49 52] were used to support the active phase. In the rst case, the catalysts were prepared using two procedures: (i) wet impregnation of the support with an aqueous suspension of NiMoO4, and (ii) direct precipitation of NiMoO4 on the support surface at 858C, using solutions of nickel nitrate and ammonium heptamolybdate.[48] The SiO2-supported catalysts were also prepared by wet impregnation[52] or by direct precipitation of NiMoO4 on the support,[49,52] or even by sol gel routes.[50,51] Nickel molybdenum catalysts are frequently used as supported catalysts in important industrial processes like hydrodesulfurization or hydrogenation, so many works exist in the literature regarding these issues. Conventional methods of preparation of hydrotreatment catalysts usually consist of depositing transition-metal salts onto the support, usually g-Al2O3, followed by calcination to produce stable oxidic materials that must be sulded either prior to or during the start-up of the hydrotreatment process. In a pioneering work, Laine et al.[12] found that it is advantageous to impregnate alumina with nickel before molybdenum. Later, Brito and Laine[53] prepared nickel molybdenum catalysts supported over g-Al2O3 through impregnation of commercial g-Al2O3. First Mo was addedusing an ammonium heptamolybdate solutionfollowed by drying (overnight at 1208C) and calcination (2 hr at 4008C). Portions of this solid were then submitted to dry impregnation with nickel nitrate solutions with the purpose of obtaining solids with several NiO loads. After drying, the samples were calcined at different temperatures between 4008C and 8008C. It is well known that for the preparation of silica-supported catalysts, the solgel route allows very good control of the composition, homogeneity, and textural properties of the nal products. In fact, the nanoscale chemistry involved in solgel methods appears to
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be the most straightforward way to prepare tailored nanocomposites, including organic inorganic hybrid materials. Moreover, solgel methods have been found to be effective for dispersing small metal oxide particles in nonmetallic matrices. With these features in mind, Cauzzi et al.[51] prepared NiMoO4/SiO2 composites by the solgel process via silicon alkoxides, involving Si(OMe)4 (tetramethoxysilane), Ni(NO3)2, and (NH4)6Mo7O24 as starting materials. The dried gels were treated at increasing temperatures until crystalline grains of nickel molybdate highly dispersed in the amorphous silica matrix were formed (6758C). Xerogels with different Ni : Mo ratios were synthesized and the preparation procedures are described in detail.[51] It is noteworthy that besides leading to the support of catalytic materials, the xerogel plays the important role of stabilizing b-nickel molybdate, which otherwise would turn into the a-phase at room temperature. Many other interesting investigations dealing with the preparation of Ni Mo supported catalyst could be mentioned. However, they are directed for use in processes other than oxidation of hydrocarbons, which is outside the scope of the present review. It is nonetheless important to stress that different materials have been used as supports for Ni Mo catalysts, namely alumina,[17,54,55] magnesia-alumina mixed oxides,[13] zeolites,[21,24] titania-alumina mixed oxides,[14,56] activated-carbon,[15,16,57] or zirconia.[58] In order to improve the catalytic performance of the Ni Mo O system in the selective ODH of alkanes, particularly n-butane, nickel molybdate was doped with several alkali (lithium, sodium, potassium, or cesium)[59] or alkaline-earth (calcium, strontium, and barium)[60] promoters. The samples were prepared through wet impregnation of the pure a-NiMoO4 material, using different loads of the respective nitrate solutions, followed by ltration, drying, crushing, and calcination in dry air for 2 hr at 5508C. For propane ODH, promoters such as K, Ca, and P were frequently used, the catalysts being prepared through an incipient wetness impregnation technique starting from an a-NiMoO4 calcined pure catalyst.[61 63] Still for application in oxydehydrogenation processes, we should note the preparation of catalyst compositions that contain other elements like phosphorus, antimony, bismuth, or arsenic, and that are effective in converting parafns or monoolens to a higher degree of unsaturation.[64] Methods described therein include coprecipitation, impregnation, dry mixing, and similar methods the nal catalyst compositions being unsupported or supported. While with the conventional impregnation method the doping element only stays on the catalyst surface, the sol gel route simultaneously produces surface and structural modications. In addition, better dispersion of the active species on the support can frequently be achieved, as well as appropriate compositional homogeneity. This led Soares et al.[65] to prepare, by the citric acid method, mixed Ni Mg molybdates, which were calcined under air ow at 5508C for 8 hr. These catalysts were tested for n-butane ODH and exhibited a noteworthy catalytic performance.[65] Dopants such as tellurium (Te) and phosphorus (P) were also added to Ni Mo catalysts, particularly for application in the direct oxidation of propane to acrolein and acrylic acids. Reported techniques for preparation of the Te-doped catalysts include the mechanical mixing of Te2MoO7 with NiMoO4 MoO3, the mixing of telluric acid with NiMoO4 MoO3,[66,67] and the impregnation of nickel molybdate with ammonium telluromolybdate.[68] For the P-doped system, the incipient wetness technique was used, with (NH4)2HPO4.[66,67] The preparation of doped nickel molybdenum catalysts can also be found in US Patent No. 3,968,054, by Cherry et al.,[69] who described an improved coprecipitation
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method for the preparation of antimony-doped Ni Mo catalysts, useful for oxidation of n-butane to maleic anhydride. Finally, Ferlazzo et al.[70] claimed a process for preparation of a complex molybdenum-based catalytic system, which is comprised by one or two crystalline phases (including beta nickel molybdate) and at least one modifying agent (promoter element), useful, for instance, for the selective conversion of unsaturated hydrocarbons into unsaturated aldehydes or diolens.
3.
THERMAL ACTIVATIONTRANSITION OF PHASES
The structure of some molybdates changes with temperature, while for others it remains unchanged. For instance an irreversible structural conversion in Bi2MoO6 was observed at temperatures higher than 5508C. Transformation is complete at 6408C.[71] A reversible conversion in CoMoO4 occurs at 5008C while for NiMoO4 a temperature of about 6908C is needed.[72,73] In fact, as long ago as in 1973 Plyasova et al.[26] identied two polymorphic forms in the nickel molybdate. One of them has a monoclinic crystalline network with the molybdenum with number of coordination six and is stable at room temperature (then named the P-phase). When heated to ca. 6508C, this form was converted into another (then named the N-phase)isomorphic with a-MgMoO4 and a-MnMoO4in which the molybdenum has number of coordination four, but which is not stable at room temperature. After cooling a transition into P-phase was observed. The thermograms of samples with Ni : Mo ratios close to 1 that were previously calcined at 5508C, showed an endothermic effect at ca. 6508C when the solid was heated and an exothermic one at 508C when the solid was cooled.[26] The former was attributed to conversion of the low temperature into the high temperature phase (P ! N), and the latter to the reverse transformation, i.e., N ! P. The transformations of phases that occur when the precipitates are heated were studied for the rst time by Andrushkevich et al.[27] Differential thermal analysis showed an endothermal effect due to the removal of crystallization water at about 1808C and another at 4208C due to the decomposition of the hydrated molybdate. These results are in very good agreement with the data shown in Fig. 2, obtained recently by Zavoianu et al.[48] We can see that the thermal analysis performed over the precursor of NiMoO4 shows a loss of weight below 473 K, which corresponds to the desorption of water and ammonia. The strong exothermic processes occurring at 723 773 K are attributed to the decomposition of NH4(NiMoO4)2OH . H2O and ammonium nitrate present in the structure.[48] According to Andrushkevich et al.,[27] in samples with excess Mo the peak that appears at 7808C coincides with the melting point of the molybdenum oxide present in the catalyst. In their studies they still concluded that the crystallization temperature of the fresh precipitate (4308C for Ni : Mo ratio 0.7) increases with the nickel content, probably because the nonstoichiometric molybdate or the formed solid solution crystallize at higher temperatures than the stoichiometric molybdate. Indeed, the infrared spectrum of a sample with an Ni : Mo ratio 2.3 heated at 6508C shows the characteristic bands of the N-phase (now named b-phase), showing that crystallization occurs at 6258C and is accompanied by the exothermal effect observed in the thermal analyses. It should also be noted that these authors found that in samples with a great excess of Ni (Ni : Mo 2.3) the N ! P transformation was not recorded when the sample was cooled.
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Figure 2. Thermal analysis of the precursor of NiMoO4. (Adapted from Ref.[48], with the kind permission of Elsevier Science.)
The Ni Mo O system indeed presents certain particularities. It is now well known that NiMoO4 can have three different structures, two of them stable at atmospheric pressure, while the other is observed at higher pressures. The two atmospheric pressure isomorphs are now commonly named the a-phasestable at room temperature and with octahedral coordination of the Mo6 ionsand the b-phasehigh temperature phase, metastable, and with tetrahedral coordination of the molybdenum.[74] The b-phase is formed after heating the a-phase to ca. 7208C and undergoes reverse transition at low temperature on cooling to ca. 2008C.[63] Figure 3 shows the differential thermal analysis (DTA) cycle of phase transitions in the stoichiometric NiMoO4 system.
Figure 3. The DTA cycle of stoichiometric NiMoO4 phase transitions. (From Ref.[63], with the kind permission of Kluwer Academic Publishers.)
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The coordination of the molybdenum atoms in both phases was conrmed more recently by Rodriguez et al. using x-ray absorption near-edge spectroscopy (XANES), which has also shown that the Ni atoms are in octahedral sites.[75] However, in a subsequent paper these authors reported that in the a-phase the molybdenum exhibits a pseudo-octahedral coordination with two very long Mo O distances (2.3 2.4 A).[76] Regarding the stability of the phases, calculations of rst-principles density functional theory (DFT) have evidenced that the a-phase is 9 kcal/mol more stable than the b-phase, with an energy barrier for the a to b transition of 50 kcal/mol, while timeresolved XRD experiments point to an apparent activation energy of 80 kcal/mol.[76] The phase stable at high temperature, b-NiMoO4, is frequently formed by heating the precalcined a-NiMoO4 sample in situ, for instance at 7608C for 5 min. The sample is then quickly cooled to the desired temperature (which must always be higher than 2508C) for other treatments (e.g., sulding), characterization, or catalytic runs. It should be noted that when more severe treatments were applied for b-phase formation (temperatures higher than 7608C or for more than 5 min), after cooling to room temperature the sample exhibited not only the a-phase, but also a more complex diffractogram, with peaks characteristic of both phases. In this case the b-phase is stabilized at room temperature, which would be due, as detailed below, to an excess of NiO as a result of the decomposition of the mixed compound and sublimation of MoO3. When the normal treatment is applied for transition of phases, b ! a conversion is recorded when the sample is cooled to room temperature. To use the high temperature b-phase of NiMoO4 in catalytic runs, Mazzocchia et al. performed the a- to b-phase conversion in the reactor, by thermal activation of nickel molybdate. The reactor was usually heated in 25 min to 7008C under oxygen, and then this temperature was maintained for 515 min before cooling to the reaction temperature,[32,33,37] but always avoiding excessive cooling to prevent the b to a-phase transition. The temperature selected for transition of phases is in agreement with the high temperature XRD data that show that at 5958C the b-phase is already present, but a temperature of about 7008C is required to obtain full conversion into a pure b-phase.[37] The data found in the literature reveal some discrepancies regarding the temperature for phase transition in the NiMoO4 system. According to Di Renzo and Mazzocchia,[36] this is due to the strong inuence of the preparation conditions of the sample. Therefore, it was decided to investigate, by differential thermal analysis, how thermal treatment of the precursor affects the transition of phases in NiMoO4. It was found that the transition temperature of the a- to the b-phase increases, and that for the b ! a transition it decreases, due to a temperature-induced relaxation. Thus, when the activation temperature of the sample is increased, the activation energy for the a- to b-phase transition is increased. It should, however, be noted that the endothermic peak that corresponds to this transition (a ! b) was not detected when the previous calcination thermal treatment was performed at a temperature below 5508C. The temperature at which the exothermic peak (relative to the b ! a conversion) began ranged between 2578C and 2008C, depending on whether the previous heating temperature was 7008C or 9008C, respectively.[36] Later, the use of a high temperature diffraction camera showed that when activating NiMoO4 at temperatures between 7008C and 9008C the temperature of the b to a transition at no point differed signicantly from 1808C, but the transition rate in the sample heated to 9008C was slower than in the samples heated to lower temperatures. This effect was attributed to the loss of MoO3 in the NiMoO4 with formation of a nickel-rich solid solution and with the structure of the b-phase of NiMoO4.[46]
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4. 4.1.
CHARACTERIZATION OF CATALYSTS
Composition of Phases for Catalysts with Different Ni : Mo Ratios
Plyasova et al. studied, by XRD and infrared spectroscopy, the composition of phases of the NiMoO system with Ni : Mo ratios from 0.2 to 2.0.[26] As described in the previous section, two polymorphic forms have been identied in nickel molybdate catalysts: one that is stable at room temperature (then named the P-phase), which when heated to about 6508C is transformed into another (then named the N-phase), Which is unstable at room temperature. After cooling, the transition to the P-phase is observed. It has been reported that the high temperature modication reacts with excess nickel (relative to the stoichiometric), forming a solid solution that is stable at room temperature. The existence of the N-phase at room temperature and the absence of peaks characteristic of the P-phase or of NiO in the x-ray diffractogram for samples with well-dened compositions indicates that, in certain conditions, nickel is dissolved in the structure of the N-phase, stabilizing it at room temperature, thereby forming a solid solution of nonstoichiometric composition.[26] It was subsequently found that in samples containing excess nickel, relative to the stoichiometric NiMoO4, the solid solution formed has a solubility limit in Ni in the range Ni : Mo 1.10 1.20 (atomic).[77] A solid solution of the vacancy type is formed, i.e., the excess of dissolved Ni ions occupies the normal octahedral positions in the structure of the N-phase, while some tetrahedral positions of the Mo remain empty. Other investigations have also been carried out in which differential thermal analysis and XRD techniques were used to investigate the composition of the Ni Mo O system in a wide range of Ni : Mo ratios (from pure NiO up to pure MoO3). The four phases detected and identied were the following: nickel oxide, molybdenum trioxide, normal nickel molybdate, and nonstoichiometric nickel molybdate.[78] In all the samples, with the exception of the pure oxides, thermal analyses showed an irreversible exothermal effect at about 430 4408C (which corresponds to crystallization of the nickel molybdate with composition NiMoO4) and another at 620 6708C (which is presumed to be due to the transition of phases of nickel molybdate). It was found that samples with m , 1 (m Ni : Mo ratio) present two phases: MoO3 and NiMoO4; the species with m close to 1 are mainly composed of normal nickel molybdate; the species with m . 1 are mixtures of three phases: nickel oxide and normal and nonstoichiometric nickel molybdates.[78] However, for m . 1.6, only nickel oxide and the high temperature phase were detected.[26] This identication of the phases that are present in Mo- or Ni-rich catalysts was subsequently conrmed.[35] While in the stoichiometric catalyst, at room temperature, only the low temperature phase was detected (with Mo in octahedral coordination), in Ni-rich catalysts (Ni : Mo 1.01.3) a solid solution of nickel and both phases (high and low temperature) were found, and the presence of nickel oxide was not detected in the x-ray diffractograms or in the IR spectra. Therefore, the b-phase is stabilized at room temperature due to the excess of nickel in the crystalline lattice of the molybdate. In catalysts where Mo : Ni . 1, both the low temperature phase and MoO3 are present. For example, the compound [(NH4)4H6NiMo6O24], prepared in well-dened conditions (see Fig. 1), at the drying temperature presents very well-dened XRD diffraction patterns but at the thermal activation temperature (5508C), only the a-NiMoO4 and MoO3 peaks were identied.[31] For catalysts with excess nickel, in 1958 Corbet et al.[79] observed that, after heating to 5008C the precursor obtained by precipitation of the solution containing Ni2 and Mo6
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ions at pH higher than 6, a new phase was formed. This phase, then called the N-phase with Ni : Mo . 1, according to Di Renzo et al.[46] corresponds to the high temperature phase (b-NiMoO4), whose stabilization at room temperature is achieved by insertion of excess Ni in the NiMoO4 lattice. The formation of the nickel-rich solid solution (NiO in b-NiMoO4) entails an increase in the lattice parameters and leads to an increase in the reducibility of the system. In fact, a catalyst with composition Ni : Mo . 1.40 is more easily reduced than NiMoO4, which agrees with some results that will be described later concerning the reducibility of this system. The formation of the solid solution of NiO in NiMoO4 is demonstrated by the stabilization of the b-phase at room temperature when the nickel-rich samples are activated at temperatures around 550 7508C. The XRD data indicate that the solid solution is responsible for the enlargement of the lattice parameters of the structure of the b-NiMoO4 phase compared with the parameters of the stoichiometric phase.[46] The Ni-rich samples prepared by coprecipitation, when heated to 5508C, mainly showed the high temperature phase (b-NiMoO4), even when cooled to room temperature. The longer this treatment lasts, the higher the percentage of that phase, and the smaller the amount of crystalline NiO. However, when the temperature was increased, the percentage of b-phase stabilizing at room temperature decreased and the proportion of NiO increased. At very high temperatures the solid solution separates. Indeed, x-ray data showed that NiO precipitation reached a signicant rate at 8008C, contraction of the b-NiMoO4 cell occurred at 9008C, and that after heating to 10008C the sample was composed, at room temperature, only of a-NiMoO4 and NiO. This was conrmed by the results of diffuse reectance spectroscopy: the sample activated at 5508C showed the characteristic band of the tetrahedral coordination of molybdenum (b-NiMoO4 phase) at 35,500 cm21, while when activated at 9008C it presented the spectrum characteristic of stoichiometric NiMoO4 with a band at 30,000 cm21 (typical of the octahedral coordination of molybdenum in the a-phase) with the additional band of NiO at 14,000 cm21.[46]
4.2. 4.2.1.
Other Physicochemical Characterizations
Stoichiometric Nickel Molybdate
Stoichiometric nickel molybdate has been characterized by several research groups. Usually the bulk composition of the catalyst is determined by inductively coupled plasma spectroscopy, for molybdenum, and atomic absorption, for nickel. A typical BET surface area for the stoichiometric catalyst is 44.1 m2/g.[59] Since the material is crystalline, XRD analysis (including high temperature XRD) has often been used to study its structure. A typical diffractogram for both phases is presented in Fig. 4, which shows the characteristic peak of the a-phase located at 2u 28.78 (JCPDS powder diffraction le card no. 33-948) and of the b-phase at 26.48. The structure of the solid has also frequently been analyzed by infrared spectroscopy because it provides useful information regarding, for instance, the stoichiometry of the material. The Fourier transform infrared (FTIR) spectra of a-NiMoO4 (Ni : Mo 1.00) is shown in Fig. 5, which is in good agreement with others found in the literature.[26,37] It is characterized by bands at 608, 934, and 958 cm21. When, through stabilization, the b-phase is also present, the spectrum at room temperature reveals a band at 950 cm21, and
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Figure 4. X-ray diffraction patterns of a-NiMoO4 at 218C (A) and b-NiMoO4 at 7108C (B). (Adapted from Ref.[80], with the kind permission of Elsevier Science.)
two new characteristic bands are also visible at 800 and 880 cm21 as a consequence of the change in the Mo coordination from 6 to 4. This is an important feature in order to ensure that the obtained nickel molybdate has a well-dened octahedral structure. Moreover, the absence in the FTIR spectra of the characteristic MoO3 bands (at 980 cm21attributed to the vibration of the Mo O bondand at 870 and 812 cm21attributed to the Mo O bond),[37] and the absence of those characteristic of the b-phase, are a good indication that the prepared nickel molybdate does not contain excess of either Mo or Ni. Regarding the electrical conductivity (s) of the solid, it is known that a-NiMoO4 is an n-type semiconductor when prepared in quasistoichiometric conditions.[37,81] Studies performed with this catalyst have shown that when the oxygen partial pressure in the gas phase is lowered, at sufciently high temperatures, the electrical conductivity increases according to s / PO221/5.8.[37] The value of the exponent is close to 21/6, thus demonstrating that the main surface defects are compatible with the model of doubly ionized vacancies,[82] whose formation can be described by the following equilibria: 1 (OO )s ! O2 (g) VO 2 VO !Vo e O Vo O !Voo O e
(6) (7) (8)
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Figure 5. The FTIR spectra of a-NiMoO4. (Adapted from Ref.[60], with the kind permission of Academic Press, Inc.)
where (OO)s surface anion; VO anionic vacancy with the two electrons trapped (neutral entity); Vo and Voo singly and doubly ionized anionic vacancies, respectively. O O From the equilibria of Eqs. (6) (8), and taking into account that the corresponding equilibrium constants follow Vant Hoffs law [Ki Koi exp (2DH i/RT)], it can be easily deduced (e.g., Ref.[83]) that:
s A e A 2Ko6 Ko7 Ko8 e(DH6 DH7 DH8 )=3RT P1=6 O2
(9)
Thus, the exponent 21/6 affecting the oxygen partial pressure is indicative of the existence of doubly ionized anionic vacancies for a-NiMoO4, whose overall enthalpy of formation is DH DH6 DH7 DH8 3Ec. Mazzocchia et al.[37] found a value of 134 kJ/mol for Ec (DH 402 kJ/mol), while Madeira et al. recorded an activation energy of 124.5 kJ/mol.[83] Steinbrunn et al. also reported a value for Ec of 125.4 kJ/mol (at temperatures in the range 4506508C), but unlike the previous authors, they found that the a-phase has two conduction regimes: (1) in the range 4506508C it is a p-type semiconductor; (2) at higher temperatures (6507008C) it is a n-type semiconductor with a higher activation energy of conduction (Ec 182.4 kJ/mol).[73] Other studies concerning the electrical conductivity of the NiMoO system can be found in the literature (e.g., Ref.[81,84 86]). Due to the use of nickel molybdenum catalysts in the hydrodesulfurization of petroleum, the reducibility of nickel molybdate has been the subject of several studies. In Table 1 some of them are summarized, which clearly illustrates that the mechanism of
70
Table 1. Mechanisms and intermediate products of NiMoO4 reduction by hydrogen. 2nd step MoO2 ! Mo
(7008C)
1st step
Reference [29]
NiMoO4 ! Ni Ni-Mo alloys MoO2 intermetallics
(4758C)
(e.g., Ni4 Mo Amorphous molybdenum lower oxide phase ! MoO2 [28, 88] NiMox alloy MoO2 ! Mo Ni3 Mo Ni Mo2 O3 Intermetallide of Ni and Mo !
(7008C) N2 (6008C)
ORDER
(400 5008C)
NiMoO4 ! Ni-Mo alloy amorphous molybdenum lower oxide
[87]
NiMoO4 ! Ni MoO2
(300 4508C)
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NiMoO4 ! NiMox alloy MoO2
(300 5008C)
[22] [89]
NiMoO4 ! Ni Mo2 O3
(500 6008C)
Source: Ref.
[87]
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NiMoO4 reduction is far from being unambiguously established. More recently, Madeira et al.[90] used the temperature-programmed reduction (TPR) technique followed by XRD analysis in order to clarify the mechanism of NiMoO4 reduction by hydrogen. The TPR prole is shown in Fig. 6 and is similar to those found in the literature,[9,11,22,29,46] with two maxima at 5458C and 7258C. It was proposed that nickel molybdate reduction starts at low temperatures (3008C), leading to metals (Ni and probably Ni4Mo) and amorphous MoO2 . Ni2, after being reduced to metallic nickel, activates molecular hydrogen, thus favoring Mo6 reduction. The amount of MoO2 formed becomes signicant only at ca. 6208C. In this way, the peak at lower temperatures can be attributed to reduction of all Ni2 to metallic nickel and of Mo6 to Mo4 or to Ni4Mo. The second TPR peak would be due to Mo4 reduction. Metallic nickel activates hydrogen and induces molybdenum reduction with formation of metallic Mo and an Ni Mo alloy. Finally, at temperatures higher than 7258C, a mixture of Mo, Ni Mo alloy, and intermetallic Ni3Mo was found.[90] Other techniques have also been applied for the characterization of NiMoO4, as will be seen in the following sections. The use of surface techniques such as electron spin resonance (ESR) and x-ray photoelectron spectroscopy (XPS) also deserves special mention, since they have been very useful for identication of the active sites of the NiMoO catalytic system for selective oxidation reactions. This will be dealt with in Section 5.3.
4.2.2.
Catalysts with Excess Molybdenum or Nickel
Nickel molybdates with excess molybdenum have been characterized in detail by Ozkan and Schrader,[45] who have particularly established that Mo in excess appears as a new phase: MoO3. The solids were carefully characterized by several techniques,
Figure 6. The TPR prole of a-NiMoO4 with 5% H2 in argon. (Adapted from Ref.[90], with the kind permission of Elsevier Science.)
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including BET surface area, Raman spectroscopy, XRD, x-ray uorescence, photoelectronic spectroscopy, and scanning electron microscopy. Curiously, an association of particles was found, with crystallites of MoO3 covered supercially by NiMoO4 particles. Other important results of this study were as follows:[45] The BET surface areas of the catalysts decrease when the percentage of MoO3 excess increases, varying between 37 m2/g for pure NiMoO4 and 3 m2/g for MoO3. The percentage of MoO3 in the nal product increases with the acidity of the medium during precipitation (conrmed by x-ray uorescence).
Two forms of crystallites, an irregular, round and porous form, attributed to NiMoO4, and a hexagonal form, due to MoO3 were identied. NiMo catalysts with an atomic ratio of Mo : Ni . 1 are suitably characterized by FTIR and FT Raman because new bands appear, typical of MoO3. As stated above, the infrared spectrum exhibits additional bands at about 810, 860, and 990 cm21,[35] while the Raman peaks, characteristic of MoO3, also become evident (shown in Table 2). This new phase is also clearly visible in x-ray diffractograms. For instance, Fig. 7 shows the XRD patterns at room temperature of nickel molybdates with different Ni : Mo ratios. It was found that all the NiMoO catalysts show the diffraction patterns of the a-phase, and the x-ray diffractograms are practically identical for Ni : Mo 0.92 or 1.00.[68] On the other hand, the strong peaks corresponding to the MoO3 phase are found in the diffraction patterns of samples with Ni : Mo 0.38. Surface-sensitive techniques have also been used in order to investigate possible variations in the oxidation states of samples with nonstoichiometric compositions. Ozkan and Schrader[45] found that the band positions and bandwidths are identical for NiMoO4 samples containing excess MoO3, independently of the preparation technique used. Table 3 lists the observed binding energies (+0.2 eV) for such samples, showing that the Mo 3d binding energies for NiMoO4 samples are identical to those of MoO3, while the Ni 2p band positions are also very similar for the Ni Mo O catalysts, but entirely different from those of NiO.[45] These results are important for demonstrating that the oxidation states of molybdenum and nickel do not change in samples with different Mo : Ni ratios, and that there is no NiO present in the observed samples. Furthermore, they can also exclude the possibility of an entirely new compound in samples with excess MoO3. All the precursors and corresponding catalysts presented in Fig. 1 were characterized in detail by Mazzocchia et al. The E precursor, which contains excess Mo, deserved special attention given the excellent catalytic properties revealed in the oxidation of 1-butene to maleic anhydride.[30] In this case, the presence of excess molybdenum of the MoO3 type was revealed by the bands at 995, 865, 820, and 370 cm21 in the infrared spectrum, and by the corresponding reections at d 6.96, 3.82, 3.47, and 3.26 A in the
Table 2. Sample NiMoO4 MoO3 963vs 998s Raman bands (cm21) of NiMoO4 and MoO3. 709s 670s 494m 381m 420m 339m 389m 293m 373m 285s 179m 160m
916s 822vs
Source: Ref.[45].
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Figure 7. The XRD diffraction patterns of nickel molybdates with various Ni : Mo atomic ratios. (From Ref.[68], with the kind permission of Elsevier Science.)
XRD patterns. When activated at 7608C the excess MoO3 is eliminated, and the resulting pattern is characteristic of stoichiometric molybdate.[30] Still using catalysts with excess Mo, but obtained from different precursors, Mazzocchia et al. observed that in spite of an identical global atomic composition, the physical chemical properties of the solids and their catalytic behavior in propene oxidation were completely different.[44] The differences in the electrical conductivities suggested the existence of different phases in the two typical samples used. The sample obtained by decomposition of the heteropolymolybdate presented a smaller activation energy of conduction, a well-dened exothermal peak between 310 4308C in the differential thermal analysis, due to the crystallization of MoO3; and the MoO3 showed a preferential orientation of the crystalline planes in the (010) direction, compared with the sample obtained by the dry mixture of NiMoO4 and MoO3. Subsequently, several solids presenting more signicant amounts of molybdenum than the original product (in which Mo : Ni 0.98) were investigated. The materials exhibited different concentrations of defects whose nature could be explained by electrical conductivity measures and thermoluminescence experiments.[47,84] The Mo concentration varied between
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74 Table 3. Sample MoO3 NiMoO4 NiO NiMoO4 with 15% excess MoO3 (precipitation) NiMoO4 with 15% excess MoO3 (impregnation)
Madeira, Portela, and Mazzocchia Photoelectron spectra binding energies for pure compounds and catalysts (eV). Mo 3d5/2 232.7 232.6 232.7 232.7 Mo 3d3/2 235.8 235.7 235.8 235.9 Ni 2p3/2 855.7 853.3 855.8 855.7 Ni 2p1/2 873.3 871.3 873.4 873.4
Source: Ref.[45].
1% and 10% of the total number of Mo atoms in the initial product (a-NiMoO4). The electrical conductivity measurements showed that the original product, containing nickel vacancies, presents p-type conductivity. A small addition of Mo lls those vacancies. However, at higher loads the Mo atoms occupy an interstitial position and free electrons appear in the solid, responsible for the n-type conductivity. The recorded thermoluminescence emission was attributed to some of the atoms being in interstitial position.[84] It should also be stressed that in catalysts containing excess Mo (or even Ni), Vagin et al. found that the samples with the largest surface areas were those in which the dominant phase was NiMoO4, with values varying between 22.0 and 29.4 m2/g.[28] When the NiO, and particularly the MoO3 content is increased, the surface area decreases. Later Brito et al. investigated the reducibility of nickel and molybdenum catalysts, but supported over g-Al2O3, and analyzed the effects of Ni concentration and calcination temperature in the TPR proles.[53] The acid character of these catalysts is noteworthy (demonstrated by ammonia adsorption), especially when enriched in molybdenum, due to the higher acidity of Mo6 oxides compared to the alumina support. Characterization of the catalysts showed a supercial interaction between Ni and Mo in catalysts calcined at temperatures lower than 8008C, probably with formation of NiMoO phases. However, the metastable phase (b-NiMoO4) was detected in diffractograms at room temperature of the catalysts calcined at 8008C (characteristic line at 2u 26.88), which suggests that the support plays a part in the stabilization of this phase. Regarding the reducibility of the catalysts, the existence of a synergetic effect between Ni and Mo should be noted since the reduction of any of the species is facilitated by the presence of the other.[53] Quite recently, Kaddouri et al. have also studied the reduction behavior of Ni Mo O catalysts, and analyzed the effect of MoO3 (as well as the effect of tellurium and phosphorous compounds) on the reducibility of NiMoO4 catalysts.[67] It is noteworthy that when excess MoO3 is present, specically above 0.5 (Mo : catalyst ratio by weight), oxygen depletion from the solid decreases. When the MoO3 load is limited, the overall reduction rate increases, compared to the stoichiometric NiMoO4 catalyst. It was found that the 0.5 MoO3 NiMoO4 catalyst has the highest reduction rate.[67] For catalysts with excess nickel, and particularly for Ni : Mo 1.7, Mazzocchia et al. found that the thermal analyses did not show the exothermal peak that results from NiMoO4 crystallization and, in addition, the XRD patterns showed that the degree of crystallinity of the catalyst is lower, due to the formation of a NiMoO4 solid solution with excess NiO.[31] It is known that excess Ni allows the stabilization of the b-phase at room
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temperature, which is conrmed by XRD (Ib/Ia I3.33/I3.09) and IR (presence of the b-phase characteristic bands at 880 and 800 cm21) data.[31] For Ni-enriched catalysts, a p-type semiconductor behavior has also been reported.[47] The possibility of distinguishing the beta stoichiometric phase from the NiMoO4dNiO phase, which is a solid solution, may lead to confusion in distinguishing the catalytic properties of the NiMoO4 phases. Mazzocchia et al. considered this possibility and came to the conclusion that there are indeed reasons to confuse the solid solution and the bNiMoO4 phase. One of these reasons is that an excess of NiO, even if very small, involves the formation of an Ni11MoO41 solid solution, which is not very active for propane ODH.[32 34] Another reason depends on how the thermal cycles were performed in order to obtain the b-phase. If both the time and the temperature to which the catalyst is brought are not strictly controlled, a loss of xMoO3 may occur with the consequent formation of an Ni1xMo12xO423x solid solution. 4.2.3. Catalysts Prepared Using Organic Precursors and Sol Gel Methods
The agents that control pH in the synthesis of precursors of mixed oxides must be easily eliminated from the precipitate. From this point of view, ammonia is usually adopted instead of, for instance, alkaline or alkaline-earth hydroxides. However, the ease of ammonia oxidation necessitates careful control of the conditions used for precursor activation in order to avoid hot spots that induce heterogeneity in the properties of the nal oxide. In this context, the role of ammonium ions in the thermal activation of several precursors of nickel molybdates, with Ni : Mo ratios smaller or larger than 1, has been the subject of study by thermal and gravimetric analyses. Particularly, the different processes (endothermal and exothermal) that occur in the activation of each precursor were clearly dened.[33,91] It should be noted that elimination of ammonium ions can follow two different pathways: ammonia removal or oxidation. The competition between the two mechanisms depends on the oxygen partial pressure, kinetic factors, and on the heating rate and the material of the cell. This last factor is related to the catalytic role of metals in ammonia oxidation. While the decomposition of NH4NO3 in air is endothermal in alumina cells, it becomes exothermal with metallic cells and occurs at a high rate if platinum is used, which is also able to oxidize NH3 at temperatures of the order of 1508C.[91] Later, Mazzocchia et al. decided to prepare an oxalic precursor, because organic precursors have the advantage of crystallizing at lower temperatures, particularly the oxalic precursor compared with ammonia.[34] The analyses performed revealed the following processes in the precursor decomposition (when heated in O2): MoOC2 O4 4H2 O ! MoOC2 O4 4H2 O NiC2 O4 2H2 O ! NiC2 O4 2H2 O 1 2808C MoOC2 O4 O2 ! MoO2 2CO2 2 1 .2808C MoO2 O2 ! MoO3 2 1 3508C NiC2 O4 O2 ! NiO 2CO2 2 .4508C NiO MoO3 ! b-NiMoO4
2108C 1008C
(10) (11) (12) (13) (14) (15)
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The endothermal processes recorded are due to the loss of water and to oxalate decomposition. The strong exothermal effect found was attributed to molybdenum oxidation and to crystallization of MoO3. The nal exothermal peak observed corresponds to NiMoO4 crystallization. It should be stressed that the nal composition of the catalyst depends on the thermal treatment applied, and particularly on the heating rate and time. For instance, to obtain NiMoO4 it is necessary to decompose the oxalate as quickly as possible, usually introducing the precursor directly in a preheated oven at 5508C. It is noteworthy that the catalyst obtained presented considerable stabilization of the b-phase at room temperature.[34] More recently, Anouchinsky et al. prepared several catalysts by the sol gel method, applying different thermal activations to the dry powder.[40] X-ray analysis indicated that the dry gel is already a partially crystallized compound, several peaks of the a- and b-phases of NiMoO4 were identied. Neither NiO nor MoO3 were found in the samples, which conrms that the homogeneous dispersion of Ni and Mo ions in the precursor has specically led to the formation of the NiMoO4 phases, whose crystallization occurs at temperatures lower than with precursors prepared by coprecipitation. Indeed, the main exothermal effect recorded in the thermal analyses occurs at slightly over 2008C (either in air or in nitrogen), and corresponds to the elimination of volatile compounds and to a degree of crystallization of NiMoO4, concluded at 4708C. Water elimination is the predominant phenomenon during thermal activation and the composition of phases of the formed oxide varies as follows: fast heating (by direct introduction into the previously warmed oven) favors b-NiMoO4 stabilization at room temperature, while slow heating leads to the preferential formation of the more stable a-phase. This behavior was explained based on the availability of Ni ions to form the solid solution with the b-NiMoO4 phase, because when the sample is heated slowly, and therefore crystallization occurs more slowly, the availability of Ni ions is reduced.[40] 4.2.4. Doped and Supported Nickel Molybdates
Alkali and alkali-earth metals have been widely and successfully used as promoters of mixed oxides. In several works published by Portela et al. the effects of either alkali[59,80,83,90] or alkaline-earth[60] promoters in the physical chemical properties of the stoichiometric nickel molybdate were analyzed. As already mentioned, these catalysts were prepared by wet impregnation. In spite of the high metal content of the treating solutions, in the bulk of the solids only traces of promoters were found when using alkali metal salts. Consequently, they remain only on the catalyst surface, curiously in the overall expected concentration, mainly affecting the NiMoO4 surface properties. The surface promoter content was quantied by XPS, and will be herein denoted as X% (X is the nominal metal/Mo atomic ratio in solution, which is equal to the surface content for alkali-doped nickel molybdate). For alkali-earth elements (Ca, Sr, or Ba), the nominal promoter content was found in the catalyst bulk.[60] The above-mentioned promoters, particularly alkali metals, affect the NiMoO4 BET surface area. It was found that higher promoter loadings lead to a greater decrease in SBET and that for a given loading of promoter the surface area decreases with increasing promoter ionic radius. Surface areas as low as 26.7 and 26.6 m2/g were found for 6% Cs-a-NiMoO4[59] and 12% Ba-a-NiMoO4,[60] respectively. However, the binding energies recorded for nickel and molybdenum showed no major changes after promoter
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addition (as compared to a-NiMoO4), demonstrating that the oxidation state of the catalysts may remain unchanged.[59] The use of cesium (Cs) deserved special attention because of its high selectivity in the ODH of n-butane.[59,80] It is particularly noteworthy that Cs-doping does not affect the nickel molybdate structure at room temperature (neither does Li, Na, or K), as revealed by FTIR or XRD, but strongly affects the a- to b-phase transition. Indeed, high temperature x-ray diffraction (HTXRD) analyses have shown that with a surface cesium loading of 3% or 6% (atomic ratio Cs : Mo), the transition of phases at 7108C is only ca. 50%.[80] In our opinion this behavior is probably related to the size of the promoter, which has an ionic radius (r) of 1.67 A, because with either K or Ba (r 1.33 and r 1.34 A, respectively), the a ! b transition is complete, even when using higher promoter loadings.[60] The reason for the choice of these kinds of promoters concerns the importance of the adsorption bond strength of hydrocarbons to the surface in ODH reactions. It has been proposed that for the selective oxidation of alkanes into alkenes, which are considered to be nucleophilic molecules, a basic surface is crucial for obtaining higher selectivities because it signicantly decreases the chances of further oxidation into carbon oxides. This led to doping NiMoO4 with basic promoters and using carbon dioxide as the probe molecule in order to characterize the basicity of the surface of some Cs-doped catalysts through temperature-programed desorption (TPD).[80] Figure 8 shows the TPD proles for a-NiMoO4 doped with different Cs loadings. It should be noted that Cs-doping signicantly increases the surface basicity, shown particularly by the area of the rst peak, with a maximum for a surface Cs loading of 3% (atomic ratio Cs : Mo). However, an overdoping effect was recorded for the 6% Cs-NiMoO4 sample. Such an overdoping effect was also noted in the electrical conductivity data recorded for the same catalysts by Madeira et al.[83] (Fig. 9). It was found that cesium-doped catalysts are much more conductive than unpromoted a-NiMoO4 due to surface Cs ions
Figure 8. The TPD proles of CO2 adsorbed at 308C for a-Ni : MoO4 doped with different Cs loadings. (Adapted from Ref.[80], with the kind permission of Elsevier Science.)
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Figure 9. Change of electrical conductivity at 3908C (B) and 4508C (W) as a function of surface cesium contents on a-NiMoO4. (From Ref.[83], with the kind permission of Elsevier Science.)
and associated oxygen species (ionic conductivity) and also exhibit smaller activation energies of conduction (Ec), with values in the range 83 94 kJ/mol.[83] As noted above, for the nickel molybdate catalyst the value obtained was Ec 124.5 kJ/mol, very close to that obtained by other authors (Ec 134 kJ/mol).[37] This was, at the time, the main evidence that led Madeira et al. to assume that under similar conditions the catalyst exhibits the same electrical behavior with the same type of defects as those suggested by Mazzocchia et al.,[37] i.e., doubly ionized anionic vacancies [cf. Eqs. (6) (9)]. Such n-type conductivity was conrmed subsequently by in situ electrical conductivity runs under different atmospheres.[92] Another interesting effect resulting from Cs-doping was the increase of the resistance of nickel molybdate to reduction,[90] similarly to the effects recorded when doping molybdenum catalysts with Li, Na, or K[93] or vanadium oxide with Cs.[94] Although the TPR prole (cf. Fig. 6) was almost unaffected by the addition of Cs to the catalyst, an increase in the temperature of onset of reduction was recorded when the surface Cs loading was increased, with a value of 3008C for undoped a-NiMoO4 and 3508C for 6% Cs-NiMoO4.[90] Concerning the characterization of alkali earth-doped a-NiMoO4, particularly noteworthy is the formation of new oxygen species, detected as oxide and peroxide compounds through XRD, FTIR, and FT Raman analyses.[60] In addition, CO2-TPD results also showed an increase in the basicity of barium (Ba)-doped catalysts with promoter loading, with an overdoping effect for Ba concentrations higher than 9%.[60] Similar results were also recently reported by Liu et al. when doping an Ni0.9MoO4 catalyst with various barium loadings (molar ratio of Ba/Mo between 1% and 15%).[95] In this paper, the XRD patterns and IR spectra demonstrate the formation of BaO2, the concentration of which increases with barium loading up to 9%, decreasing for Ba contents in the range 9 15% due to formation of BaMoO4.
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The deposition of coke over nickel molybdate has also been the subject of study and has revealed interesting features, particularly the stabilization of the high temperature b-phase at room temperature, as shown by XRD and FTIR analyses.[96] The role of coke in this stabilization was demonstrated by completely eliminating it from the catalyst. After this gasication, the solid again shows the typical a-phase structure at room temperature, thus demonstrating the instability of the b-phase in the absence of coke. As mentioned below, catalyst deactivation was not found after such forced coke deposition. On the contrary, the effect of b-phase stabilization markedly improved catalyst performance, particularly its selectivity for oxydehydrogenation of n-butane.[96] The stabilization of b-NiMoO4 at low temperatures is very important because there is much evidence that, for some reactions, and particularly for ODH of light alkanes, this phase shows more interesting catalytic properties than the a-phase, especially selectivity to dehydrogenation products. Thus, special reference should also be made to recent studies that showed stabilization of b-NiMoO4, even at room temperature, when using TiO2[48] or SiO2[49] as supports. Moreover, this effect was found both when preparing the catalysts through precipitation[48,49] and through sol gel routes.[50,51] The formation and stabilization of this phase was also found over PNiMo : Al2O3 catalysts,[97] but in this case it turned out to be a disadvantage because these catalysts are used in hydrodesulfurization reactions in which the b-phase is much less active. Published data on oxidic Ni-Mo : Al2O3 also point to a role of the alumina support in stabilizing b-NiMoO4.[98] The acid base properties of SiO2-supported nickel molybdate catalysts were also evaluated and compared with those of unsupported stoichiometric NiMoO4.[52,99] Temperature-programed desorption experiments of NH3 and CO2 have showed that supported catalysts with ca. one monolayer of the active phase are less acidic than the unsupported nickel molybdate, but acidity increases with the number of monolayers. The use of Ni Mo-supported catalysts is widely reported in the literature, mainly for applications in petroleum hydrotreatment processes, and so there are many examples of interesting works in which the characterization of such materials is mentioned. A simple example is the combination of TPR and ESR techniques, which have helped to clarify that in Al2O3-supported Ni Mo catalysts the good catalytic properties in the hydrodenitrogenation reaction of pyridine can be attributed to the improvement in the reducibility of Mo, the formation of an Ni Mo O phase, and the creation of more anionic vacancies when using Ni or W as promoters.[100,101] For the interested reader, other references are provided, merely illustrative, to show that different supports have been used and the catalytic systems characterized, namely alumina,[97] titania-alumina mixed oxides,[14,56] alumina-magnesia mixed oxides,[13] activated-carbon,[15,16] and zirconia.[58]
4.3.
Characterization of the High Temperature b-Phase
It is well known that the XRD signal at interplanar spacing around 3.33 A is [98] considered to be characteristic of b-NiMoO4 in Ni Mo catalysts. Thus, the use of a heating camera has enabled several researchers, including the present authors, to record the XRD patterns of both a- and b-phases of NiMoO4 at different temperatures, as well as to study the transition of phases and their stability.[37,80] For instance, from Fig. 4 it is clear that the a ! b transformation is practically complete after 10 min at 7108C in air, as
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shown by the relative intensities of the characteristic peaks (2uI2100 28.78 and 2uI2100 26.48, for a and b-phase, respectively). The HTXRD data have also provided evidence that the a-phase is stable up to at least 6258C and that the b-phase is stable down to at least 4258C,[80] the range of temperatures typical for ODH reactions. The characterization of the b-phase through other techniques is not easy due to its instability at low temperatures. The BET surface area, for instance, is estimated to be of the same order of magnitude as the value obtained with the a-phase after thermal treatment (e.g., 15 min at 7008C), followed by quenching to room temperature. Mazzocchia et al. obtained specic surface areas for the a- and b-phases of 40 and 15 m2/g, respectively,[32,37] very close to those obtained by Martin-Aranda et al. (44.1 vs. 16.0 m2/g).[59] Regarding electrical conductivity (s), it has been observed that the b-phase is also a semiconductor of the n-type, like the a-phase, and it therefore obeys the same law (for PO2 . 19.7 kPa): DHa 1=n s so exp (16) PO 2 RT with a conduction enthalpy (DHa) of 125.4 kJ/mol.[37] For the b-phase the exponent n is close to 4, demonstrating that the main surface defects are singly ionized anionic vacancies, while with a-NiMoO4 a value close to 6 was obtained, indicative of doubly ionized anionic vacancies [cf. Eqs. (6) (8)].[37] Steinbrunn et al. also found that the electrical transport for both nickel molybdate phases takes place via a classical intrinsic band conduction mechanism, but they concluded that the b-phase behaves as a p-type semiconductor in the temperature range 450 6508C, with an activation energy of 125.4 kJ/mol.[73] Another property of the high temperature phase that was studied by Mazzocchia et al. was its reduction rate by H2. A signicant increase was reported in the reduction rate of b-NiMoO4 phase compared to the a-phase.[31,67] Among several results obtained by Brito et al.,[11] it should be noted that the BET surface area of a-NiMoO4 (38 m2/g)obtained by calcination of the hydrated precursor at 5508Calso decreases considerably after cooling b-NiMoO4 to room temperature (26 m2/g). However, the TPR proles show clear differences in the reducibility of both phases, with higher reduction temperatures for the b-phase due to the greater difculty in reducing Mo6 in tetrahedral than in octahedral coordination.
5.
Applications of Ni Mo O Catalysts
The multifunctional character of the Ni Mo O system is demonstrated by the wide variety of reactions in which it is applied and through the great diversity of products obtained with a given reactant. An example is butane oxidation, in which the possible reactions involved include dehydrogenation, isomerization, oxidation with oxygen insertion, partial oxidation with rupture of carbon carbon bonds, and total oxidation.[35] Nickel molybdenum-based catalysts have been used in several reactions. As already mentioned, this review essentially concerns oxidation reactions, and particularly ODH of light alkanes. However, their use in reactions such as hydrogenation and hydrogenolysis of toluene,[22] hydrodesulfurization of thiophene,[8 15] hydrodenitrogenation of
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pyridine,[16,17] water gas shift,[18] steam reforming of hydrocarbons,[19] oxidative coupling of methane,[20] COx hydrogenation,[55] and in other important hydrogenation and hydrotreating reactions[8,21,23,24] should also be mentioned.
5.1.
Oxidation of Hydrocarbons
According to Ozkan and Schrader,[45] there is strong evidence that the presence of excess MoO3 is a key factor that determines the catalytic behavior of simple molybdates in selective oxidation reactions. In this context, they decided to prepare nickel molybdates with excess MoO3 through several techniques (see Section 2), and used these catalysts in the conversion of some C4 hydrocarbons into maleic anhydride. The hydrocarbons used were 1-butene,[102] butadiene, and furan.[103] The results recorded show that specic concentrations of MoO3 are necessary in order to obtain high selectivities to maleic anhydride (with a maximum for 15% molar excess of MoO3), and that pure NiMoO4 and MoO3 are not selective. The most selective prepared catalyst for maleic anhydride production was an MoO3 phase supercially covered with NiMoO4, which exhibited stability in reaction conditions for 200 hr. Characterization of the catalysts used after such long runs did not reveal any chemical or structural alteration, with no change in the oxidation states of Mo 3d and Ni 2p (as found by XPS), but only a change of color (from yellow to dark gray) due to carbon deposition on the surface.[102] Regarding the role of each phase, it was clearly established that selectivity for maleic anhydride is determined by competition between the processes of carbon oxides and maleic anhydride formation, both occurring at different MoO3 sites. NiMoO4 is the component responsible for 1-butene ODH, and moreover this phase selectively blocks the MoO3 sites that lead to total oxidation, thus favoring selectivity to maleic anhydride.[103] Zou and Schrader then decided to develop a technique to prepare thin lms (150 300 A) of NiMoO4 on the surface of (0 1 0) MoO3 previously deposited over a support.[38] The catalysts thus prepared revealed excellent catalytic behaviors in the oxidation of 1-butene to furan and maleic anhydride. It is noteworthy that when only NiMoO4 was deposited a high selectivity to butadiene was obtained, with yields of about 48%, which was attributed to the presence of defects, probably in Ni O Mo sites.[38] A synergetic effect between the a-phases of NiMoO4 and MoO3 was also detected in 1997 by Magaud et al. during propane oxidation.[104] Indeed, activity and selectivity to acetic acid and acrylic acid are maxima when the ratio a-MoO3/(a-NiMoO4 a-MoO3) is close to 0.25, due to a specic arrangement of the two species, especially a reciprocal covering. Mazzocchia et al. have also frequently used the Ni Mo O system in hydrocarbons oxidation reactions. In a pioneering work, 1-butene oxidation to maleic anhydride was studied with several catalysts.[30] Once again, the catalyst with excess Mo, relative to the stoichiometric one (precursor E in Fig. 1), was shown to be particularly active and selective. Moreover, pulsed-feed experiments have shown that ODH to butadiene is possible due to the intervention of reticular oxygen (through a redox mechanism), while the formation of partial and total oxidation products involves different forms of adsorbed oxygen. In the conditions studied, the greatest selectivity to maleic anhydride was 64%, which was attributed to the presence of Mo(V) sites that are able to activate the oxygen molecule and that exist in catalysts with MoO3 present in an NiMoO4 matrix.
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The oxidation of propene has also been the subject of study, in particular the inuence of the Mo : Ni ratio on the behavior of the catalysts.[31] While all the catalysts tested have produced acrolein, only catalysts with excess MoO3 enabled acrylic acid to be obtained. In any case, the maximum yield was always obtained with catalysts containing excess MoO3, which increases the supercial acidity of the catalyst and thus favors formation of acrylic acid. In addition, the b-phase of NiMoO4 enabled propene to be converted into acrylic acid and also oxidized acrolein into acrylic acid, while the NiMoO4 a-phase is practically inactive in both reactions. From the above-mentioned results it is clear that excess MoO3 is crucial in oxidation reactions, the same being true for propene oxidation. However, the method of preparation of the precursor signicantly affects the catalytic behavior. Preparation of precursors with identical atomic composition, but through different methods, leads to catalysts with quite different properties.[44] For instance, the catalyst prepared by coprecipitation presents a smaller electrical conduction activation energy and is catalytically more active than the one prepared by a simple mixture of NiMoO4 and MoO3. The former is also more selective to acrolein and to acrylic acid and presents a preferential orientation of the MoO3 crystalline planes in the (0 1 0) direction.[44] Oxidation of propene with Ni Mo-based catalysts has also been the subject of some patents. For instance, US Patent No. 4,388,223, by Ferlazzo et al.,[70] describes the preparation of a complex molybdenum-based catalytic system, which is formed of one or two crystalline phases and at least one promoter element. When one of the phases involves beta-nickel molybdate, runs performed using propene as the unsaturated hydrocarbon resulted in a conversion of 95.3%, with a selectivity of 95.6% for the acrolein and acrylic acid produced (feed containing the following percent volume composition: propene/oxygen/steam 6.64/12.5/34.0, with a contact time of 2.3 sec at 3708C).[70] Finally, Umemura et al. reported a yield to acrolein as high as 91.5% using an Mo Co Ni Bi Fe Al Ti O type catalyst, which also has an excellent crushing strength.[105] The great interest in oxidizing propene directly to acrylic acid led Mazzocchia et al. to study this reaction further. After determination of the optimum proportion between MoO3 and NiMoO4 in the binary system, i.e., NiMoO4 . 2MoO3, the catalyst was promoted with Te (Te2MoO7), which considerably increased the performance of the solid. This catalyst was then used in a preliminary kinetic study.[106] As regards the effects of each oxide, molybdic anhydride by itself dramatically increased the selectivity (and also activity) of NiMoO4, while the presence of tellurium, in spite of decreasing conversion, increased the selectivity to acrylic acid. It is possible that the decrease in conversion results from the fact that tellurium molybdate accelerates the a ! b-NiMoO4 transformation,[107] that leads to a less active catalyst. The synergistic effect between MoO3 and a-NiMoO4 was related to the large amount of Ni found by XPS on the surface of the catalyst, which was in agreement with the above-mentioned results obtained by Ozkan and Schrader[45] that demonstrated the presence of NiMoO4 on the surface of MoO3 crystals. With regard to the effect of tellurium, it was considered that this promoter keeps Ni and Mo in high oxidation states (e.g., Mo5 Te4 ! Mo6 Te3), necessary for easy desorption of acrolein, whose formation probably represents the rate-determining step.[106] More recently, the partial oxidation of propene was carried out with Ni Mo Te O ternary catalysts by Kaddouri et al.[67] It was concluded that the catalytic behavior is governed by both the synergetic effect generated by combining NiMoO4 with Mo- and
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Te-oxides and by the oxygen partial pressure rather than lattice oxygen. Indeed, Te-doped Ni Mo O catalysts have a high potential for partial propene oxidation, which is linked also to the increase in catalyst reducibility induced by the presence of tellurium, although the reaction seems to be governed by the molecular oxygen partial pressure. This was concluded after a preliminary kinetic study, in which a power-law rate expression of the form r kPm2PC3Hn showed a reaction order with respect to oxygen, m, of 0.39, 0.23, and O 6 0.48 for CO, CO2, and acrolein formation, respectively. The order with respect to propene, n, was 0.43, 0.49, and 0.32.[67] Thus, a conventional redox mechanism does not seem to operate, and the yield of acrolein can be improved by lowering propene and increasing oxygen partial pressures. Even more interesting than the direct oxidation of propene to acrylic acid is the direct use of propane, for which the Ni Mo Te O system doped with P has been successfully tested.[66] It was found that the catalytic system provides a wide product distribution, leading to propene, acrolein, and acrylic acid formation according to a reaction pathway as shown in Sch. 1. However, the reported yields were low, as compared to the more promising study published by Fujikawa et al.[68] Sautel et al. also tested nickel molybdenum catalysts for such a reaction and compared the results obtained by the almost stoichiometric catalyst (Mo : Ni 0.98) with another one 5% enriched in Mo.[84] It was found that at 500 or 5308C, and with any phase, propene and acrolein formation rates were higher with the Mo-enriched sample, while the CO2 formation rate was much lower. Therefore, the Mo-enriched compound was a better catalyst for both conversion and selectivity, and this behavior was attributed to Mo atoms in interstitial positions (demonstrated by electrical conductivity and thermoluminescence measurements). While the higher conversion was attributed to increased propane adsorption, the lower rate of CO2 formation was explained on the basis of smaller availability of lattice oxygen due to the formation of interstitial Mo atoms.[84] Investigating the oxidation of butane to butadiene and maleic anhydride, Mazzocchia et al. found that signicantly different results were obtained with respect to product distribution by changing contact time, temperature, or the butane : oxygen ratio.[35] It was also interesting that an excess of MoO3 is responsible for higher activity, despite reducing selectivity to dehydrogenation products and increasing formation of carbon oxides. The fact that practically the same yield in butenes was observed when the number of pure butane pulses was increased suggested that butane dehydrogenation occurs without the intervention of lattice oxygen. On the other hand, maleic anhydride formation is related to the activation of gaseous oxygen in sites that disappear with strong reduction and that cannot be regenerated by reoxidation. Such sites probably correspond to Mo(V)
Scheme 1. Reaction pathway proposed for propane oxidation with Ni Mo O based systems. (From Ref.[66], with the kind permission of Elsevier Science.)
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sites.[35] The nickel molybdate catalysts used were prepared by coprecipitation and exhibited low hydrocarbon conversions: at 4758C, 19% conversion of n-butane was recorded with low selectivity to maleic anhydride.[35] The great interest in producing maleic anhydride is due to its use as raw material for products ranging from agricultural chemicals, paints, paper sizing, and food additives to synthetic resins. To meet the high demand for this valuable chemical, a variety of commercial processes and efcient catalysts have been developed, particularly from n-butane oxidation. With this goal in mind, Cherry et al.[69] announced the preparation of a catalyst composition useful for the vapor phase oxidation of butane to maleic anhydride. The catalytic system usedan oxide composition containing Sn Ni Mowas found to be highly selective, stable, and long-lasting, providing selectivities for the desired maleic anhydride in the range of about 25 35%. Surprisingly it was found that these catalysts are more effective when unsupported. Table 4 shows some typical results obtained with Ni Mo catalysts, undoped or doped with antimony. For the Sb : Ni : Mo catalytic system, the constant selectivity recorded with increasing conversion up to 70% is particularly noteworthy, while with nickel molybdate the selectivity for maleic anhydride decreases markedly above about 50 60% conversion. In the United States patent by Kourtakis and Sullivan, several molybdenumcontaining oxides (including nickel molybdenum-based materials) are described, which can be used in a wider context for catalyzing other C4 oxidation processes.[108] They state that such catalysts can be used advantageously with regard to conversion and selectivity in a wide variety of conventional techniques and reactor congurations (i.e., xed or uidized bed reactors or recirculating solids reactors) to perform the oxidation of C4 hydrocarbons to maleic anhydride.[108] Other important oxidation processes in which Ni Mo containing catalysts have been successfully used include: (i) the oxidation of toluene, where a 70% yield of benzaldehyde
Table 4. Catalytic system Sb/Ni/Moa
Catalytic data of oxidation of butane to maleic anhydride. Contact time (sec) 0.32 0.46 0.83 0.98 0.09 0.13 0.24 0.23 0.46 0.86 1.51 2.10 Conversion (%) 29 39 58 68 37 48 65 70 36 52 70 81 Selectivity (%) 33 31 27 25 27 26 29 26 27 29 21 17 Yield (%) 10 12 16 17 10 13 19 18 10 15 15 14
T (8C) 400 403 400 400 450 450 450 453 500 506 500 499
Ni/Mob
Atomic ratio 1 : 0.24 : 0.14. Experimental conditions: butane/air 0.8/99.2 (mol%); W 29 g. Experimental conditions: butane/air 0.9/99.1 (mol%); W 18.4 g. Source: Ref.[69].
b
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per pass was achieved in a xed bed reactor with NiMoO4 activated at 4508C;[109] (ii) the conversion of alcohols to aldehydes with an Ni Mo catalyst containing a complex iron molybdate;[110] (iii) methacrolein production by catalytic oxidation of isobutene;[105] and (iv) the ammoxidation of olens to unsaturated nitriles, notably acrylonitrile and methacrylonitrile production, using propene and isobutene as olen reactants, respectively.[111]
5.2.
Oxidative Dehydrogenation of Light Alkanes
5.2.1.
Undoped Ni Mo Catalysts
The search for catalysts with good performance in butadiene production has been studied for a long time because of its use as a monomer in the production of synthetic rubber. Although references exist since the 1960s on the use of the nickel molybdenum catalytic system in n-butane to butadiene ODH,[112] it was only after 1974 that a considerable number of studies began to appear on this subjects. One of the pioneering patents is that of Bertus et al., in which a stationary bed of nickel molybdate provided a yield of butadiene of 4.2 13.5% by weight, with a selectivity of about 33% (at a temperature within the range 550 5908C, a space velocity of the butane supply of 50 500 hr21 and at a molar ratio n-butane : oxygen : steam of 1 : 1 : 20).[113] Around the same time, Pilipenko et al.[114] investigated the effect of the composition of the nickel molybdenum system in that reaction. n-Butane conversion at 6008C was about 30 40% in samples with Ni : Mo atomic ratios m 17.3 0.48, drastically decreasing when the MoO3 concentration was increased, reaching values lower than 0.6% with the pure oxide. The pure nickel oxide is not also interesting for this ODH reaction because its selectivity to butadiene was practically nil, although conversion is high. The data obtained show that catalysts with compositions in the range m 1.92 1.28 present the highest selectivities and yields butadiene, with values up to 54% and 17.1%, respectively, decreasing strongly when the MoO3 loading is increased. Therefore, catalysts with three phases, normal nickel molybdate, nickel oxide, and nonstoichiometric nickel molybdate (phase N, now called b-phase), are the most efcient in butane to butadiene ODH. The authors have proposed that an oxygenated nickel compound, which may exist in several forms, is responsible for the catalytic activity. Finally, by performing some runs from 1-butene and butadiene, they have suggested that nickel oxide is the species responsible for the butane to butenes conversion step.[114] The assignment of the active component of this system caused some controversy. Two years later Itenberg et al. again studied this reaction with nickel molybdenum catalysts.[115] Although catalytic tests with the individual oxides have shown that molybdenum trioxide and nickel oxide are active in n-butane ODH, the low recorded conversions and selectivities to butadiene led them to conclude that they were not the agents responsible for the catalytic activity of the NiO MoO3 system. Then they performed some runs with catalysts of different compositions and found that the maximum selectivity (to butenes or butadiene), at equal butane conversion levels, was obtained with samples with Ni : Mo atomic ratios between 1.0 and 1.2. A study of the composition of phases led them to conclude that the active component was nickel molybdate or a solid solution of nickel oxide in the molybdate lattice. A shift of the ratio for m . 1.2 or m , 1.0 led to a decrease in selectivity, apparently due to the presence of the individual
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oxides. It was also reported that both nickel molybdate modications (P and N, where Mo presents octahedral and tetrahedral coordination, respectively) presented practically the same activity and selectivity. That is, the crystalline structure of the nickel molybdate lattice would not affect the behavior in butane ODH. Similar conclusions were also ` presented by Cavani and Triro,[116] who reported that both crystalline forms of the molybdate (now called a and b) present similar catalytic behaviors in butane ODH (for T 5008C, butane conversion 12%, yield to butadiene 4.2%, yield to butenes 4.8%). In addition, they reported that in the presence of excess MoO3 or NiO relative to the stoichiometric molybdate, activity increases but selectivity decreases considerably.[116] The claim that a- and b-phases of NiMoO4 exhibit similar performances in ODH is another subject of controversy. Indeed, neither the results obtained by Mazzocchia et al. (mentioned in Table 5) nor those obtained by Madeira and Portela seem to support this. For instance, in the rst study reported by these authors it was reported that the a-phase is more active (see Fig. 10) while the b-phase is much more selective for dehydrogenation products at comparable conversions and similar temperatures.[59] Most papers published on ODH reactions with undoped NiMoO catalysts concern propane conversion. For catalysts with Mo : Ni ratios .1/1, Lezla et al. considered the a-phase as the active one.[41] The addition of molybdenum oxide to nickel molybdate signicantly improved the behavior of the catalyst and the most effective composition found had a Mo : Ni ratio 1.27/1, with which a selectivity to propene of 63% was obtained, at a propane conversion level of 22% (at 5008C, t 3.8 sec, C3/O2/H2O/N2 20/10/30/ 40).[41] They found that interfacial synergetic effects exist between the planes (0 1 0) of aNiMoO4 and (1 0 2) of MoO3, as already noticed in some oxidation reactions. Thomas et al.[47] also tested nickel molybdates with different Ni : Mo ratios in propane oxydehydrogenation. It was noticed that selectivity to propene is enhanced for Mo-rich catalysts, which also have better catalytic activity as measured by reaction rates; although, the surface areas were lower than those of Ni-rich products. Mo-rich catalysts were ve times more efcient than Ni-rich products and the high kinetic constants for propene formation shown in Fig. 11 counterbalance the low values of their surface areas. This effect was attributed to the existence of Mo atoms in interstitial positions, revealed by electrical conductivity and thermoluminescence measurements.[47,84]
Table 5. Catalyst
Catalytic data of oxidative dehydrogenation of propane.a Conversion of propane (%) 23.3 37.1 16.8 29.0 37.2 34.0 Selectivity to propene (%) 50.6 33.8 80.3 62.5 28.6 18.5 Yield to propene (%) 11.8 12.5 13.5 18.1 10.6 6.3
T (8C) 560 600 560 600 600 600
a-NiMoO4 a-NiMoO4 b-NiMoO4 b-NiMoO4 NiMo1.5O5.5 Ni1.5MoO4.5

a
Experimental conditions: Qt 15 LPTN/hr (25% propane, propane/O2 molar ratio 0.9); W 0.5 g. Source: Ref.[32].
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Figure 10. Conversion and selectivity for n-butane ODH with the a (A) and b (B) phases of NiMoO4. Experimental conditions: W 0.5 g; C4H10/O2/N2 molar ratio 4/9/87; W/F 20 gcat hr/molbutane. (Adapted from Ref.[59], with the kind permission of Elsevier Science.)
In another very interesting work the possibility of using nickel molybdate in circulating bed reactors for propane ODH was tested.[117] In these reactors the catalyst is regenerated by oxygen (in a regeneration zone) after leaving the reaction zone where it oxidizes the hydrocarbon. The maximum amount of oxygen that can be reversibly removed from a catalyst is a parameter that determines its applicability in these reactors. In the case of NiMoO4 it corresponds to 2% of the total oxygen content, excessive reduction leads to the irreversible transformation into MoO2 and Ni (NiO).[117] More recently, Stern and Grasselli[72] have also studied propane to propene conversion with several molybdates supported over SiO2. The results showed that the
Figure 11. Change of the kinetic constant for the formation of propene during propane ODH with the atomic composition in NiMoO catalysts. Experimental conditions: W 0.25 g; T 5008C; C3H8/ O2/He% 15/18/67; QT 15 L/hr. (From Ref.[47], with the kind permission of Elsevier Science.)
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reaction is catalytic and is not initiated with formation of radicals in the gas phase, the rate controlling step being the breaking of the C H bond with abstraction of a hydrogen from a methylene group of the propane molecule. Among the simple molybdates tested of the type AMoO4 (with A Ni, Co, Mg, Mn, or Zn), the nickel one presented the greatest activity, even when normalized per unit of surface area (which was the highest: 39 m2/g). The molybdenum oxygen bond, which is inuenced by the nature of the adjacent metal, A, is probably responsible for propane activation and, consequently, bonds of the type Ni O Mo O are the most active. It is noteworthy that at equal conversion levels, the highest selectivity was also found with the NiMoO4 catalyst (60% for propene at a conversion of 27%). Mazzocchia et al. have also studied the ODH of propane to propene with catalysts containing Ni : Mo ratios below and above 1, as well as the behavior of the two NiMoO4 phases.[32] In Table 5 some of the data are presented. It is clear that the two phases of the Ni Mo O system exhibit quite different catalytic behaviors. Further investigation conrmed that although the a-phase is slightly more active, the b-phase is almost twice as selective to propene at comparable conversions and identical temperatures.[37] This selectivity difference was accounted for on the basis of the different types of oxygen bonds at the active sites. Since the presence of M5 bonds is usually associated with the 5O formation of oxygen-containing products, and because in the b-phase the character of this bond is weaker than in the a-phase (band at lower frequencies in the infrared spectrum), the high temperature phase should be more selective to dehydrogenation products. This different behavior of the two phases was very recently attributed by Kaddouri et al. to the different reducibility of the two phases.[67] In fact, a relationship was found between the reducibility of the catalysts and the catalytic behavior in propane ODH, demonstrating that lattice oxygen plays an important role in the reaction, i.e., the process is governed by a redox or Mars van Krevelen mechanism.[118] The formation of propene by reaction of propane with supercial O22 anions was proposed, leading to the formation of anionic vacancies (Voo) shown by electrical O conductivity measurements [Eq. (17)].[37] Regeneration of the oxygen species active in propane ODH occurs through spontaneous reoxidation of the surface by gaseous O2 [Eq. (18)] according to a Mars van Krevelen mechanism: ! C3 H8 O2 C3 H6 H2 O Voo 2e s O 1 oo 2 O2 (g) VO 2e Os ! 2 (17) (18)
The fact that the b-phase is more selective than the a-phase led Mazzocchia et al.[33] to try to prepare the former phase at lower temperatures than those generally used (about 7008C) in order to avoid sintering, which drastically reduces the surface area. It would also be convenient to stabilize this phase but without excess NiO, because the precursor with excess nickel (green), which stabilizes the b-phase at room temperature, does not exhibit good performance in propane ODH. It was found that when calcining the yellow precursor of stoichiometric nickel molybdate in situ, after thermal decomposition at 5008C, the bphase of NiMoO4 crystallizes.[33] The catalytic runs were quite interesting because the precursor calcined in the reactor at 5508C showed a selectivity to propene at 5308C, which was almost as high as the b-phase (65.7% against 78.5%), which had been obtained starting from a-NiMoO4 and heating from 258C to 7008C, then cooling later to the
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reaction temperature. Furthermore, the rst catalyst presented a higher level of propane conversion (18.3% against 10.0%), leading to a larger yield to propene (12.0% against 7.8%). The previous situation still presented a technical problem because the reactor had to be continuously heated to keep the catalyst as the more selective b-phase for a long period, and it could not be cooled to room temperature in order to prevent transition to the a-phase. To overcome this drawback, an oxalic precursor was prepared which, after thermal activation, led to stabilization of the NiMoO4 b-phase at room temperature.[34] In this way the need for continuous heating of the reactor is avoided in possible industrial applications. Moreover, the catalyst presented a specic surface area of 34 m2/g, similar to that of a-NiMoO4 (32 m2/g).[34] Later Anouchinsky et al. immobilized the Ni and Mo ions inside an organic gel (agaragar), which led to NiMoO4 crystallization at lower temperatures and to possible stabilization of the b-phase at room temperature, depending on the thermal treatment applied in the precursor activation.[40] Such stabilization may be due to the presence of organic residues because, as mentioned above, stabilization of the b-phase at room temperature was also found after forced coke deposition over NiMoO4.[96] The catalyst obtained starting from the gel presented selectivity to propene similar to that obtained with the pure b-phase, but it was less active.[40] Propene productivities (in mmol/hr) at 5008C were the following: 4.7 (a-NiMoO4), 2.5 (b-NiMoO4), and 1.9 (a b NiMoO4, obtained from the gel). The catalytic results in propane ODH do not appear very promising, although the preparation method has not yet been completely optimized. 5.2.2. Doped and Supported Catalysts
Due to the great industrial interest in butadiene, butenes have also been converted into this product by ODH using Ni Mo doped catalysts. Some interesting results are shown in Table 6, obtained with catalysts claimed by Bertus in one of the pioneering patents dated 1978.[64] The effective conversion and yield of butadiene with both catalytic systems is noteworthy, and it is also apparent that contact times must be short. The use of promoted Ni Mo catalysts in n-butane oxydehydrogenation is not recent. For instance, US Patent No. 4,094,819 of 1978[64] presents good results using several Ni Mo doped-catalysts, those obtained with arsenic being particularly interesting (Table 7). Even more efcient was a catalyst of oxides of molybdenum, cobalt, and nickel, which provided a conversion of butane of about 20%, with a selectivity for n-butenes of about 26% and of about 35% for butadiene, thus providing a total yield for C4s of 12.2%.[119] Some studies on the use of promoted Ni Mo catalysts for n-butane ODH have been published by Madeira and Portela. In a preliminary study it was shown that all the alkali metals studied (Li, Na, K, or Cs) signicantly improve the selectivity of the NiMoO4 catalyst,[59] when promoting either the a- or b-phase. As shown in Fig. 12, this effect increases in the sequence unpromoted , Li-doped , Na-doped , K-doped , Cs-doped, the b-phase of this catalyst providing a yield to C4 products of 14.5% (for a conversion level of 28.2%).[59] The fact that higher selectivities were obtained with Cs-doped nickel molybdate led the authors to study the effect of this promoter in more detail.[80,83] The effect of doping with alkali metals, i.e., the increase of selectivity to ODH products, can be easily understood if one takes into account their basic nature. Thus, the
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Madeira, Portela, and Mazzocchia Catalytic data of oxidative dehydrogenation of butenes to butadiene. T (8C) 538 538 538 482 482 482 538 538 538 Contact time (min) 15 60 180 15 60 180 15 60 180 Conversion (%) 38.8 36.0 35.7 26.3 25.5 24.2 28.3 19.1 16.2 Selectivity (%) 72.2 74.8 74.0 82.8 77.4 74.0 83.0 92.2 94.3 Yield (%) 28.0 27.0 26.4 21.8 19.7 17.9 23.5 17.6 15.3
Ni/Mo/Sbb
Catalyst composition 38.3/26.1/5.3 (wt%). Experimental conditions: butene/oxygen/steam feed rate 300/264/5780 GHSV. b Catalyst composition 35.7/24.3/15.2 (wt%). Experimental conditions: butene/oxygen/steam feed rate 300/264/5400 GHSV. Source: Ref.[64].
more basic surface facilitates desorption of the nucleophilic olens/di-olens from the catalyst surface (butenes and butadiene that have high electron densities at the p bonds), thus avoiding their overoxidation into carbon oxides. Indeed, a good correlation was recorded between surface basicity, measured by CO2-TPD experiments, and selectivity for C4 products as shown in Fig. 13,[80] in which an overdoping effect is also visible. Alkali-earth metals, namely Ca, Sr, and Ba, were also used by Madeira et al. as promoters of the NiMoO4 catalyst in n-butane ODH.[60] In this case, and due to the moderate basicity of such promoters (as compared with alkali metals and revealed by CO2-TPD), a less pronounced increase in selectivity to C4s was recorded. However, and because there is much interest in obtaining butadiene directly from butane, this tuned basicity seems to be very interesting because a very high selectivity to butadiene was achieved. In fact, alkali-earth doped catalysts were almost twice as selective to butadiene as was undoped NiMoO4. Nonetheless, an overdoping effect was also detected
Table 7. Catalytic system Ni/Mo/Bib Ni/Mo/Sbc Ni/Mo/Asd
a b
Catalytic data of oxidative dehydrogenation of n-butane to butenes and butadiene.a Conversion (%) 10.0 15.0 15.9 Total selectivity (%) 33.6 23.0 59.0 Yield C4H8 (%) 1.7 3.6 6.0 Yield C4H6 (%) 1.6 0.3 3.4 Total yield (%) 3.3 3.9 9.4
Experimental conditions: butane/oxygen/steam feed rate 50/50/500 GHSV; temperature 5668C Composition 36.0/24.4/15.8 (wt%). c Composition 35.7/24.3/15.2 (wt%). d Composition 35.7/24.3/13.8 (wt%). Source: Ref.[64].
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Figure 12. Effect of different alkali promoters (1% loading, surface atomic ratio metal/ molybdenum) on the catalytic behavior of a- and b-phases of NiMoO4 for n-butane ODH. Experimental conditions as in Fig. 10. (Adapted from Ref.[59], with the kind permission of Elsevier Science.)
for barium-doped catalysts that exhibit a maximum of selectivity (as well as a maximum of basicity) at a 9% promoter loading (atomic ratio Ba : Mo).[60] Similar conclusions were also recently reported by Liu et al. for propane oxydehydrogenation.[95] They found that selectivity to propene increased with the barium load from 1% to 9%, but decreased with the increase of its content from 12% to 15%, i.e., a maximum was found once again for a molar ratio Ba : Mo of 9%. The 9% Ba Ni0.9MoO4 catalyst is thus the most interesting one, with a very good yield to propene of 30.5%.[95] Although alkali (and also alkaline-earth) metals improve selectivity in n-butane ODH, the conversion level usually decreases, and this becomes more pronounced as the promoter loading (or size) increases. This effect results mainly from the decrease in the BET surface area after doping.[59,60] Stern and Grasselli[72] have tested some nickel-containing binary molybdates with the formulas Ni0.5A0.5MoO4 (with A Co, Mg, Mn, or Zn) in propane ODH. Although these catalysts have not shown better performance than NiMoO4, the most active and selective one (Ni0.5Co0.5MoO4) was used as a reference to investigate in more detail the Ni Co Mo O system due to its great ease of preparation. With this catalyst a kinetic study was then performed and a mechanism proposed for propane ODH,[120] as mentioned below. These authors decided to study in detail the following systems in propane ODH: Ni12xCoxMoO4 (with x between 0 and 1), AMo1+xOy (where A Ni or Co and x is between 0 and 0.1), and promoted Ni0.5Co0.5MoOx.[72] It is worth noting that the results of the variation of molybdenum content (x) between 0.9 and 1.1 in catalysts of the type NiMoxOy have shown that catalytic activity to partial oxidation products is strongly sensitive to Mo content. The catalyst of stoichiometric composition, NiMoO4, presented
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Figure 13. Selectivity to dehydrogenation products (at an n-butane conversion level of 5%) as a function of catalyst surface basicity (amount of adsorbed CO2 at 308C) for unpromoted and Cs-promoted a-NiMoO4 catalysts. (Adapted from Ref.[83], with the kind permission of Elsevier Science.)
by far the greatest activity and the highest yield, both activity and yield signicantly decreasing with increasing or decreasing Mo content. Mazzocchia et al. have also used doped-nickel molybdate catalysts in ODH reactions, namely K-, Ca-, and P-doped for propane[61 63] or isobutane conversion.[62] It is particularly noteworthy that with calcium and potassium addition, propane conversion decreases but selectivity to propene increases, showing once again that basic sites (assessed by catalytic decomposition of isopropanol in the absence of oxygen) are crucial to the oxydehydrogenation process. On the other hand, promotion with phosphorous (a typical acidic element) has led to enhancement of propane conversion, which was ascribed to an increase in alkane adsorption on the more acid catalyst surface.[61,63] Similarly, to previous results obtained by Madeira et al.,[90] it was found that these promoters signicantly increase the reduction resistance of nickel molybdate, indicating that the mobility of the lattice oxygen has become less important.[61,63] It seems that the catalytic activity of Ni Mo O-based catalysts for ODH of light alkanes is related to catalyst reducibility, while selectivity to dehydrogenation products depends mainly on the acid base character of the catalyst surface. However, Kaddouri et al. concluded that selectivity also depends on the degree of catalyst reduction, since propene formation is improved with the pulse period in a periodic-ow reactor operation.[61] With regard to isobutane conversion, it was found that the catalytic performances of stoichiometric nickel molybdate, in terms of selectivity for isobutene, can be improved by the addition of potassium oxide, which avoids subsequent overoxidation of the reactive isobutene formed. However, methacrolein formation is negatively affected (see Table 8). The great interest in producing methacrolein, which is widely used to produce methacrylic
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Table 8. Typical results of oxidative dehydrogenation of isobutane to isobutene and methacrolein, at 8% conversion level.a Selectivity Catalysts i-C4H8 25.5 44.4 52.2 41.3 66.0 69.2 60.1 69.1 CH25 5CCH3CHO 12.5 11.5 9.5 15.5 6.4 6.3 8.4 11.0 CO 27.7 14.7 11.8 17.9 5.7 6.2 8.3 7.2 CO2 34.3 27.8 24.6 22.7 20.9 12.6 22.6 12.1 (CH3)2CO 0.0 1.6 1.9 2.6 1.0 5.7 0.6 0.5 Surface area (m2/g) 32.2 30.7 29.4 13.1 10.6 9.8 10.6 9.8
a-NiMoO4 a-NiMoO4/0.20%K a-NiMoO4/0.25%K b-NiMoO4 b-NiMoO4/0.20%K b-NiMoO4/0.25%K a0 -NiMoO4/0.20%Kb a0 -NiMoO4/0.25%Kb

a
Experimental conditions: W 0.5 g; %i-C4H10 15; 4 , %O2 , 7; 4208C , T , 4808C; 10 , F , 20 L/hr. b 0 a -NiMoO4 is obtained after cooling the b phase to room temperature. Source: Ref.[62].
acid for the polymer industry, led Kaddouri et al. to try to avoid this negative effect.[62] This was achieved by using low oxygen partial pressure in the feed, which also increases isobutene selectivity, due to a decrease in formation of carbon oxides. The use of supported catalysts in the oxydehydrogenation of light alkanes is uncommon. Recent studies have been performed on isobutane ODH, using TiO2[48] or SiO2[49,52] as supports. Such catalysts have been shown to be more selective to isobutene than unsupported NiMoO4, which was attributed to the acid base properties of the surface[52] or to b-phase stabilization at low temperature.[48,49] This is very important because the b-phase is metastable at room temperature and, in industrial practice, it is not practical to keep reactor operation above 2508C to avoid the transition to the a-phase. Furthermore, incorporation of excess nickel to stabilize the b-phase at low temperatures favors competitive side reactions. Silica-supported nickel molybdate catalysts, prepared through sol gel procedures, were also tested in isobutane ODH,[50,51] but no signicant yields were obtained. A special mention should be made of the unexpected effects found after coke deposition on nickel molybdate catalyst.[96] First, and surprisingly, it was observed that, with this deposition, deactivation was not found during n-butane ODH. On the contrary, conversion increased (more than 40%), as well as selectivity to dehydrogenation products, and particularly to butadiene. These effects were attributed to the stabilization of the more selective b-phase at low temperatures and to the presence of catalytically active coke.[96] 5.2.3. Kinetics and Mechanism
One of the few kinetic and mechanistic studies found in the literature performed with Ni Mo O catalysts for propane oxydehydrogenation was published by Stern and Grasselli.[120] It was carried out with the above-mentioned Ni0.5Co0.5MoO4/SiO2 catalyst and the results showed that the reaction proceeds through ODH, propene being formed as
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the primary and exclusive product. Formed propene is rst oxidized to acrolein, which is then oxidized to carbon oxides and acrylic acid. However, small amounts of COx are also formed directly from propene. The selective oxidations of propane to propene and of propene to acrolein are both zero-order in oxygen (a common behavior found in the oxidation of hydrocarbons over metallic oxides and consistent with the redox mechanism of Mars and van Krevelen)[118] and rst-order with respect to the hydrocarbon (consistent with a rate-limiting reaction between the hydrocarbon and an active site on the catalyst surface). The deep oxidation of propane into CO and CO2 has an order of 1/2 in oxygen and is of rst-order with respect to propane, while the deep propene oxidation shows dependence on the hydrocarbon concentration of the type r / kx/(1 Kx), that is, the rate-limiting step involves a surface species that is in adsorption equilibrium with the gas phase and is also of order 1/2 in oxygen. To conclude, the work by Stern and Grasselli[120] showed that the partial and deep oxidation of the hydrocarbons on the Ni Co Mo O system occurs through two different mechanisms. The partial oxidation of propane to propene and of this product to acrolein can be described by the Mars van Krevelen mechanism,[118] in which the adsorbed hydrocarbon reacts with the lattice oxygen (nucleophilic). On the other hand, deep oxidation of propene to COx can be described by a Langmuir Hinshelwood mechanism in which the adsorbed hydrocarbon reacts with adsorbed and dissociated oxygen (electrophilic). Finally, it should be noted that isotopic studies in propane and propene activation have revealed that hydrogen abstraction from a methylene group and in allylic position (a-hydrogen) are the respective rate-controlling steps.[120] The greater selectivity presented by the b-phase in some oxydehydrogenation reactions was the reason that impelled Sautel et al. to perform a detailed kinetic study on propane to propene ODH, trying likewise to clarify some important aspects of the reaction mechanism.[121] For the conditions used, it was found that the propene formation rate presents partial orders to propane and to oxygen close to one and zero, more precisely 0.95 + 0.01 and 0.03 + 0.02, respectively (see Fig. 14), and therefore gaseous oxygen is not directly responsible for the ODH reaction. This is indicative of a Mars van Krevelen type mechanism. Over a-NiMoO4, Del Rosso et al. also found that a change in the oxygen partial pressure does not affect propene formation, which is instead dependent on the propane partial pressure. Indeed, for the propene formation rate partial orders with respect to propane and oxygen of 1.2 + 0.01 and 0.04 + 0.01, respectively, were found.[122] The involvement of lattice oxygen was then conrmed using continuous, transient, and periodic operating systems.[122] For the more selective b-NiMoO4, it was proposed that the global reaction: 1 C3 H8 O2 ! C3 H6 H2 O 2 (19)
can be written in six steps:[121] (1) propane adsorption on the catalyst surface; (2) oxidation of the adsorbed propane by the oxygen of the NiMoO4 lattice; (3) and (4) desorption of the products (propene and water); (5) and (6) oxygen adsorption on the catalyst surface and lling of the oxygen vacancies in the solid. Assuming a rate-determining step and that the others are at near-equilibrium conditions, the theoretical rate equations were deduced and were compared with the experimental data. It was possible to conclude that the rate-limiting step that controls the overall reaction rate can be either propane adsorption
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Figure 14. Evolution of the rate of formation of propene with the partial pressure of propane (for PO2 18 103 Pa) and oxygen (for Ppropane 15 103 Pa) introduced with b-NiMoO4. (From Ref.[121], with the kind permission of Elsevier Science.)
(step 1) or the reaction between adsorbed propane and the oxygen of the NiMoO4 lattice (step 2).[121] A kinetic study with b-phase nickel molybdate was also reported for ethane ODH, in which interesting and even uncommon results were obtained.[123] First, it was found that in ethane oxydehydrogenation the a-phase is not only more active but also more selective than the b-phase, therefore behaving differently from the case of propane ODH. Secondly, it was found that for the b-phase the overall rate of ethane conversion can be described by: r C2 H 6 d(C2 H6 ) k(C2 H6 )1:15 (O2 )0:21 dt (20)
with a reaction order of 0.16 for C2H4 formation with respect to oxygen. In addition, tests performed under continuous ow in the absence of gas phase oxygen have led to the conclusion that no ethylene is formed. Thus, and unlike the case of propane ODH, lattice oxygen does not seem to guide the reaction towards dehydrogenation. For this case, a mechanism that considers the intervention of surface O2 species was proposed, in which the activation of ethane involves hydrogen abstraction by these species to give ethyl radicals.[123] Regarding butane conversion, a kinetic study of the selective oxidation and degradation of n-butane over undoped and cesium-doped nickel molybdates was recently reported, covering a wide range of experimental conditions.[90] The rate data were tted to power-law rate equations, i.e.: ri kPn1 Pn22 butane O (21)
The computed reaction orders n1 and n2 showed that Cs doping only affects the partial order with respect to butane, which increases for dehydrogenation products and decreases for CO and CO2. The partial order with respect to oxygen is almost unaffected, in both cases, i.e. with undoped or Cs-doped NiMoO4, showing zero-order dependence for formation of C4s, which suggested the existence of a Mars van Krevelen process.[90] In a Mars van Krevelen (or redox) model[118] it is assumed that hydrocarbon reacts with the lattice oxygen of an oxidation catalyst, which becomes reduced. The reduced catalyst then reacts with molecular oxygen from the gas phase to complete the catalytic cycle.
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A generalized Mars van Krevelen model was applied by Madeira and Portela[124,125] to the results of the above-mentioned kinetic study of the selective oxidation and degradation of n-butane over undoped and cesium-doped nickel molybdates. By nonlinear regression analysis, the following rate equations were obtained: ri ko kr Pbutane ko akr Pbutane (22)
for the products of selective butane conversion (butenes and butadiene)[124] and
ri
ko kr P1=2 P2 O2 butane ko P1=2 akr P2 O2 butane
(23)
for the degradation products of butane (CO and CO2), over the pure NiMoO4 catalyst,[125] where ri butane conversion rate to specied products; ko, kr kinetic constants for the reoxidation and reduction steps, respectively; PO2, Pbutane oxygen and butane partial pressure, respectively; a stoichiometric number of oxygen moles required in the reaction. Other studies performed with nickel molybdate catalysts also supported a Mars van Krevelen mechanism for n-butane ODH. Evidence for such a mechanism includes: (i) the zero-order dependence on the oxygen partial pressure for C4 formation,[90] (ii) the relationship between catalytic activity and reducibility (inferred by the temperature of onset of reduction) of several Cs-doped catalysts,[90] (iii) the similar apparent activation energies for butane conversion with and without gas phase oxygen,[126] (iv) the fact that no oxygen adsorption was observed by O2-TPD,[124] and (v) catalytic tests without O2 in the feed, which showed that butane can be converted to C4 products with high selectivity even without gas phase oxygen.[126] The tests performed in the absence of oxygen showed that lattice oxygen plays a crucial role in selectivity during butane conversion, as is also the case for propane ODH.[122] In addition, the very low butane conversion levels achieved (typically below 1% as compared to runs with oxygen in the gas phasebetween 2.9% and 7.9%),[126] indicate that alkane conversion is limited by the reducibility of the catalyst or by lattice oxygen availability and mobility. However, such low conversion levels (,1%) are typically consistent with an oxygen consumption that corresponds to a small percentage of the mobile oxygen content of the catalyst monolayer, as shown by Del Rosso et al.[122] Therefore, the reaction seems to be controlled by the reducibility of the catalyst (or by the oxygen diffusion within the solid). More recently, the existence of a redox mechanism in n-butane ODH over nickel molybdate catalysts was further supported by an in situ study of the catalysts electrical conductivity.[92] When the catalysts were subjected to a sequence of gaseous atmospheres of the type: oxygen butane oxygen-reaction mixture, a reversible redox process was observed, for both undoped and Cs-doped NiMoO4 (Fig. 15). The sharp increase in the electrical conductivity (s) recorded when pure butane is introduced in the cell is attributed to the release of electrons into the conduction band during surface reduction: C4 H10 (OO )S C4 H8 H2 O Voo 2e ! O (24)
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Figure 15. Kinetics of the changes in electrical conductivity of unpromoted and Cs-promoted a-NiMoO4 catalysts under different atmospheres (at 3758C). (From Ref.[92], with the kind permission of Elsevier Science.)
When oxygen is reintroduced, s reversibly decreases and practically returns to its initial value, this process corresponding to the lling of the vacancies by gas phase oxygen in accordance with the following equation: 1 Voo 2e O2 (g) (OO )S ! O 2 (25)
In the steady state, the electrical conductivity of the NiMoO4 catalyst under the reaction mixture is much closer to that of the oxidized state than to that of the reduced one (see Fig. 15), which agrees with the faster reoxidation as compared to reduction of the catalyst.[92] The n-type semiconductor behavior of nickel molybdate was also demonstrated, because (@s/@t)O 2 , 0 and (@s/@t)C4H10 . 0. The kinetics and mechanism of isobutane ODH over nickel molybdate were also recently investigated.[127] It was concluded that isobutene is formed via a redox mechanism with the participation of lattice oxygen, while the formation of carbon oxides occurs with the participation of chemisorbed oxygen.
5.3.
Nature of Active Sites
The nature of the active sites in the selective oxidation of hydrocarbons has been widely investigated for molybdenum-containing catalysts,[7] and the use of surfacesensitive techniques has made a crucial contribution. We should mention, for instance, the very recent study by Watson and Ozkan,[128] in which ESR was used to investigate changes in Mo(V) species upon contact with propane.
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The role of Mo5 as an active species is well recognized by several authors. For instance, Abello et al.[129,130] suggest the involvement of Mo5 species (for Mg Mo O catalysts) in propane ODH. Characterization by several techniques, particularly XPS and EPR, gave clues that the active site would be a coordinatively unsaturated form of Mo5, which could be generated on the surface by propane reduction. Khan and Somorjai[131] proposed that the active sites in molybdenum-based catalysts are coupled pairs of Mo(V) and Mo(VI) species, which are responsible for the redox mechanism. More recently, the importance of the Mo(V)/Mo(VI) redox pair in propane ODH over molybdenum phosphates was also pointed out.[132] Although some consensus seems to exist regarding the active species for molybdenumcontaining catalysts, other active species are also suggested. For instance, Harlin et al. claim that the oxidation state of molybdenum active in the dehydrogenation of n-butane is either Mo5 or MO4, which upon reduction to lower oxidation states leads to a catalyst responsible for increased selectivity to cracking and coke formation.[133] Other authors found instead that catalyst performance (MgMoO and CoMoO systems) during propane ODH increases in parallel with the increase of surface weak acid sites, suggesting that these sites are involved in propane activation.[134] An excess of octahedral molybdenum, partially covering the surface, seems to be responsible for the weak acid sites. For Ni Mo O catalysts, it is also generally accepted that the active site involves Mo5 species. Mazzocchia et al., while investigating butane to butadiene and maleic anhydride oxidation, found practically the same yield of butenes when the number of butane pulses was increased, suggesting that butane dehydrogenation occurs without the intervention of lattice oxygen.[35] Moreover, maleic anhydride formation is related to gaseous oxygen activation over sites that disappear by deep reduction and that cannot be regenerated by reoxidation. Such sites probably correspond to Mo(V) sites. Although no unequivocal and denitive proof exists that establishes the nature of the active and/or selective sites involved in selective oxidation reactions, other authors also seem to agree that the redox couple Mo6/Mo5 is necessary for the ODH step, particularly for propane conversion.[41] However, further research using surface sensitive techniques for characterization of NiMoO4 catalysts, of which there have so far been rather few, is urgent.
6.
CONCLUSIONS AND FUTURE TRENDS
In this paper, the main scientic publications regarding the Ni Mo O catalytic system and its applications for the selective oxidation of hydrocarbons were reviewed. Particular attention was also dedicated to the preparation techniques that have been used and to the main physical chemical characterization data. With regard to the preparation techniques, most studies found in the literature have focused on the use of the coprecipitation method. These techniques have been progressively rened considering that their preparation involves a sequence of unit operations, each requiring the optimization of its specic parameters. In this context it is important to note the work of Mazzocchia et al., which led to signicant scientic and technical results detailed in Refs.[32,37,106,121,135,136]. At the same time the application of increasingly sophisticated characterization techniques was essential for fundamental results contributing to the optimization and applicability of the prepared catalysts.[33,91,137]
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The use of supported Ni Mo O catalysts is now the subject of more investigation,[48,49] particularly catalysts prepared by sol gel techniques.[50,51] This is a topic that, in our opinion, should be further explored because interesting results have already been obtained, particularly the stabilization of the high temperature b-phase at room temperature. Since products obtained by sol gel techniques depend strongly on all experimental conditions, which play an important role in determining their physicochemical characteristics and consequently their catalytic behavior, further fundamental research on this subject is required. Mixed Ni Mg molybdates were also recently synthesized by Soares et al.[65] via the sol gel technique and revealed interesting catalytic behavior in n-butane ODH. C4 yields were signicantly improved using mixed molybdates, particularly for an Mg/Ni atomic ratio of 0.31. But this behavior has not been fully claried. Nanosized materials are another promising eld for research. It is known that the catalytic properties of mixed metal oxides are largely dependent on their microstructure. In the nanoparticle phase, the surface to volume ratio increases drastically and the surface atoms include an increasing fraction of the total particulate volume with high defect structures. Thus, they may exhibit interesting new or improved catalytic properties. Nanocrystalline NiMoO4, with particle size of about 20 nm, has been prepared,[42,43] but no catalytic data have been reported. Regarding the application of Ni Mo O catalysts in oxidation reactions, the direct oxidation of propane deserves special mention. It is known that the most important industrial process for synthesis of acrylic acid involves two steps, the rst one being oxidation of propene to acrolein, which is further oxidized in the second stage to acrylic acid. The most promising route would be the direct oxidation of propane to acrylic acid in a single step. This was successfully tested by Kaddouri et al.[66] but their yields were not sufcient for industrial application. More recently, Fujikawa et al.[68] found that nickel molybdates modied with telluromolybdate are good catalysts for this reaction, with a maximum yield of 20% (acrylic acid and acrolein). However, because of the instability and toxicity of tellurium compounds, other catalysts should be tested in the future. Several nickel molybdenum-based catalytic formulations have already proved promising for hydrocarbon oxidation reactions. The continuous screening of new classes of catalytic materials and their optimization has been a great challenge, but it is very time consuming. However, high-throughput experimentation methodology has been successfully used for other applications,[138] and is an important approach to be considered for accelerated catalyst design, evaluation, and development. Besides, this technique is particularly promising for the development of novel multicomponent mixed metal oxide catalysts through rapid microscale synthesis and catalytic screening, using combinatorial methods. Although the data found in the literature for ODH reactions with NiMoO catalysts do not point to very high levels of parafn conversion, it seems that these oxides can operate at low conversions, at which selectivity to dehydrogenation is quite favorable. Indeed, ` according to Cavani and Triro,[116] the various molybdates (among them nickel) present a common feature in ODH reactions, which is a decrease of selectivity to olens when the hydrocarbon conversion level increases (e.g., n-butane). For this reason these catalysts need to operate at low conversions, with recycling of the nonconverted parafn. But among the required properties for heterogeneous oxidation catalysts (activity, selectivity, and stability), selectivity to desired product(s) is crucial since the production of undesirable products
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increases costs at the industrial level.[5] Therefore, many authors have investigated the applicability of nickel molybdates in such reactions and, among other aspects, have tried to increase the selectivity of the catalyst to the desired oxidation products, particularly by the use of promoters. Promising results have been achieved, but for very low hydrocarbon conversion levels, and the yields obtained do not yet recommend the use of such processes on an industrial scale, as an alternative to conventional dehydrogenation processes. Despite the large number of studies found in the literature concerning the use of Ni Mo O catalysts for the selective oxidation of hydrocarbons, and particularly for the ODH of light alkanes, some important aspects, such as the nature of the active sites, the hydrocarbon activation process, the kinetics and mechanism of the reaction, and the factors that determine selectivity, are not yet sufciently clear. It has been shown that nickelmolybdenum catalysts are efcient for several oxidation processes. Their use for isobutane conversion into isobutene is an application that should be explored further in the future. Isobutene is a key reactant for the production of methyl t-butyl ether (MTBE) and ethyl t-butyl ether (ETBE), which are used as lead-free octane boosters for gasoline.[139,140] The use of MTBE has given rise to signicant pollution problems not found with ETBE, which is now much in demand as a lead-free gasoline additive, improving the combustion process, and decreasing carbon monoxide emissions. So, to produce the amounts of ETBE required, additional sources of isobutene will be needed. Recently some studies have been performed using TiO2-[48] and SiO2-supported[49,52] NiMoO4 for the oxydehydrogenation of isobutane. Although these catalysts have proved to be more selective to isobutene than unsupported NiMoO4, which was attributed to b-phase stabilization at low temperature[48,49] and to the acidbase properties of the surface,[52] the yields obtained were not sufciently high and the formation of many undesirable products was reported, namely carbon oxides, products from cracking reactions (light alkanes), and heavy organic compounds that condense at the reactor outlet or remain on the catalyst surface (coke). Other studies have also been recently reported, but the isobutene yields attained were even lower.[50,51,62] This subject is worth further investigation to achieve higher performances in isobutane to isobutene conversion. In the ODH of light alkanes, some studies suggest that, in practice, it would be advantageous to operate with a high alkane/oxygen ratio in the gas-phase feed in order to favor selectivity for dehydrogenation products. This agrees with the fact that a higher partial order in oxygen was observed for formation of carbon oxides (CO and CO2) compared with that found for the desired selective oxidation process (see Refs.[62,90]). However, various groups have found difculties in this operation. For instance, Madeira et al.[90] found catalyst reduction and strong coke deposition when using high butane concentrations in the feed of a tubular reactor containing undoped a-NiMoO4. Similar problems were also found by Del Rosso et al. when operating a periodic ow reactor under severe conditions (i.e., high temperature, long pulse periods, high propane partial pressure, etc.) during propane ODH.[122,141] In this case, the deep reduction depleted more than the surface oxygen monolayer, leading to irreversible deactivation of the catalyst with formation of metallic nickel and coke laments. A possible way to avoid this drawback would be the use of promoters to inhibit such reduction, or the use of accelerators in the gas phase. For instance, it was recently reported that Cs partially inhibits NiMoO4 reduction under pure butane, but completely inhibits it under a reaction mixture containing butane and oxygen.[92] Thus, the promoter keeps the catalyst in a higher oxidation state, allowing the use of higher alkane concentrations. Cs-doped NiMoO4 catalysts, therefore,
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seem to be promising for reactor designs in which operation is achieved in the absence of gas-phase oxygen, with the consumed lattice oxygen periodically restored by exposure to an oxygen-containing gas, i.e., in a cyclical process similar to that proposed by Boutry et al.[142] This can be done in practice using multiple reactors or catalytic reactors with mobile or uidized beds. Concerning the use of accelerators in the gas phase, which are applied in some industrial processes, Dury et al.[143] found very recently that the addition of CO2 to the gas stream helps to maintain the catalytic surface of NiMoO4 in a high oxidation state, under conditions for which the catalyst undergoes reduction with consequent deactivation. In specic conditions it can also increase propene formation from propane, thus suggesting the possible utilization of CO2 in industrial applications. Some of the most important works concerning the ODH of alkanes have indicated the possibility of using riser reactors in order to obtain results of industrial interest to alkenes. The above-reviewed data have clearly demonstrated the redox properties of NiMoO4. Also, tests performed by the periodic operation technique have determined the degree of optimal reduction of NiMoO4 for its regeneration and also for the deposit conditions of coke. These results make it possible to propose technologies based on riser reactors. The mechanical properties of NiMoO4 catalytic systems are a fundamental factor for the success of these technologies. In fact for such technologies the mechanical properties of the catalyst are essential, since it has to resist both abrasion and circulation, because it has to be moved from the reaction reactor to the regeneration reactor and back to the reaction reactor. For the improvement of the mechanical properties of the catalysts there are some noteworthy works in which microwave technology has been used for unit operations of drying and calcination. The solids obtained after these operations, at the end of the microwave thermal treatments, have better mechanical properties than those that have undergone conventional thermal treatments.[144,145] For technologies based on riser reactors there are two steps requiring optimization of the reaction parameters: 1. During the rst step a reaction between the alkane and lattice oxygen takes place and, therefore, the contact time, temperature, and alkane/catalyst ratio have to be optimized in the reactor to ensure maximum reduction of the catalyst allowing both its reoxidation and optimal control of coke formation. During the second step catalyst reoxidation occurs and it is essential to establish the temperature, contact time, and oxygen partial pressure precisely, to prevent harmful structural and morphological changes during reoxidation.
2.
The use of catalytic membrane reactors (CMRs) is also a promising alternative since they enable control of oxygen distribution, maintaining its partial pressure sufciently low within the catalytic bed.[146] In addition, generated heat is also more regularly distributed along the bed, considerably decreasing hot-spot formation and leading to safer and more stable operation. The catalyst charge can also be increased in this way. The application of CMRs for oxidation reactions, particularly for partial oxidation of hydrocarbons, was very recently patented by Schwartz et al.[147] Their invention relates to the use of a gas-impermeable membrane for transport of oxygen anions, the membrane separating oxidation and reduction zones. An oxygen-containing gas is reduced at the membrane in the reduction zone (thus generating oxygen anions) while a species in a reactant gas is oxidized in the oxidation zone of the reactor. This technology is claimed to
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be useful for several reactions, including partial oxidation of hydrocarbons to oxygenated species and ODH of alkanes, using several catalysts and different congurations.[147] In this approach, Ni Mo O based catalysts could also be considered. But for successful industrial application, both catalyst development and process engineering, particularly reactor design, must be considered simultaneously.
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Nickel Molybdate Catalysts and Their Use in The Selective Oxidation of Hydrocarbons

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Nickel Molybdate Catalysts and Their Use in The Selective Oxidation of Hydrocarbons

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Catalysis Reviews: Science and Engineering

CATALYSIS REVIEWS Vol. 46, No. 1, pp. 53110, 2004

Thermal ActivationTransition of Phases . . . . . . . . . . . . . . . . . 63 Characterization of Catalysts . . . . . . . . . . . . . . . . . . . . . . . . . 66

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Conclusions and Future Trends . . . . . . . . . . . . . . . . . . . . . . .

Nickel Molybdate Catalysts and Selective Oxidation of Hydrocarbons

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PREPARATION OF CATALYSTS 2.1. Coprecipitation Techniques

Madeira, Portela, and Mazzocchia

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Nickel Molybdate Catalysts and Selective Oxidation of Hydrocarbons

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Ni2 MoO2 (aq:) 4(aq:) !NiMoO4(s) Ni2 (aq:) Ni2 (aq:)

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Nickel Molybdate Catalysts and Selective Oxidation of Hydrocarbons

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Madeira, Portela, and Mazzocchia

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Nickel Molybdate Catalysts and Selective Oxidation of Hydrocarbons

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Supported and Doped Catalysts

Madeira, Portela, and Mazzocchia

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Nickel Molybdate Catalysts and Selective Oxidation of Hydrocarbons

THERMAL ACTIVATIONTRANSITION OF PHASES

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Madeira, Portela, and Mazzocchia

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Nickel Molybdate Catalysts and Selective Oxidation of Hydrocarbons

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Madeira, Portela, and Mazzocchia

Composition of Phases for Catalysts with Different Ni : Mo Ratios

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Nickel Molybdate Catalysts and Selective Oxidation of Hydrocarbons

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Other Physicochemical Characterizations

Stoichiometric Nickel Molybdate

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Nickel Molybdate Catalysts and Selective Oxidation of Hydrocarbons

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s A e A 2Ko6 Ko7 Ko8 e(DH6 DH7 DH8 )=3RT P1=6 O2

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NiMoO4 ! Ni Ni-Mo alloys MoO2 intermetallics

NiMoO4 ! Ni-Mo alloy amorphous molybdenum lower oxide

NiMoO4 ! NiMox alloy MoO2

Madeira, Portela, and Mazzocchia

Nickel Molybdate Catalysts and Selective Oxidation of Hydrocarbons

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Catalysts with Excess Molybdenum or Nickel

Madeira, Portela, and Mazzocchia

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Nickel Molybdate Catalysts and Selective Oxidation of Hydrocarbons

Downloaded by [UNAM Ciudad Universitaria] at 11:19 24 February 2012

Downloaded by [UNAM Ciudad Universitaria] at 11:19 24 February 2012

Nickel Molybdate Catalysts and Selective Oxidation of Hydrocarbons

Downloaded by [UNAM Ciudad Universitaria] at 11:19 24 February 2012

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