ES2374470B1 - HIERARCHICALLY ORGANIZED CATALYSTS THROUGH DRY ROAD NANODISPERSION. - Google Patents

Abstract

Hierarchically organized catalysts by dry nanodispersion. # The present invention relates to a process for obtaining catalysts by nanodispersion and anchoring of nanoparticles or nanoparticulate clusters smaller than 100 nm on submicron or micrometric supports using a dispersion process on track Low energy dry. Catalysts prepared at room temperature are characterized by presenting new nanoparticle support intercalates capable of generating new reactive surfaces that favor high activity and catalytic selectivity. The heat treatment of these catalytic systems causes the formation of stable crystalline species generating catalytically inactive interfaces by decreasing the number of free active sites.

Description

Hierarchically organized catalysts by dry nanodispersion.

State of the art

Glycerin is a renewable chemical raw material, the use of which depends on its efficient conversion to products with high added value. However, glycerin reactivity provides too much chemical versatility, leading to a wide distribution of products that normally prevents its application [1-4]. The use of co-reactants to reduce the distribution of products is a particularly effective approach, for example, the use of ammonia to obtain acrylonitrile, both in the vapor phase and in the liquid phase, yields 40% to acrylonitrile with 90% selectivity [5 -7]. Like acrylonitrile, glycerin carbonate is also a product with high added value. Glycerin carbonate is one of the derivatives of glycerin that have more scientific and industrial interest thanks to the potential of its final uses. The search for routes to efficiently produce glycerin carbonate from renewable raw materials is a fundamental issue for the different production areas since it is possible to obtain compounds that are competitive with those obtained from petroleum derivatives [8-10]. For this reaction, carbon dioxide is used as a carbonylation agent under supercritical conditions [11], however, severe experimental conditions are employed. Other carbonizing agents are dimethyl carbonate [12, 13]; or dialkyl carbonates [14]. Urea is a suggestive carbonylation agent, so in the year 2000, Mouloungui et al [15] patented the synthesis of glycerol carbonate by carbonylation of glycerol with urea using heterogeneous zinc catalysts such as zinc sulfate, organosulfate of zinc and ion exchange resins containing zinc. The calcined zinc sulfate showed the best results by reaction with urea (yields of 86% glycerine carbonate in 2 hours) at 150 ° C and 40 mbar, eliminating the ammonia formed during the reaction. However, zinc sulfate is soluble in glycerin, so it is a homogeneous catalysis reaction, the catalyst being partially recovered after the reaction. Heterogeneous catalysts are particularly effective in the reaction of glycerin carbonylation with urea [16, 17], since they allow more moderate reaction conditions and good yields. There is therefore a great strategic and environmental benefit in the development of a heterogeneous catalyst for this process. Thus Climent and collaborators [17] have recently published glycerin carbonylation (yields of 72% glycerine carbonate in 5 h) with urea at 145 ° C using heterogeneous catalysts, such as basic oxides (MgO and CaO) and mixed oxides (Al / Mg, Al / Li) hydrotalcite derivatives with effective pairs of acid-base centers [17].

The reactions described above have a great environmental and sustainable value; The development of environmentally acceptable catalytic processes requires heterogeneous catalysts. In this way the process of preparing a catalyst is a key component as far as its environmental value is concerned.

The reactions described above have a significant environmental and sustainable value, thus the development of environmentally friendly catalytic processes requires heterogeneous catalysts. The process of obtaining and preparing these catalysts is a key component both in the environmental value of the catalyst and in the development of a high catalytic activity (selectivity and conversion of the reactions involved).

Under these premises we have recently developed a novel method of nanodispersion, free of residues and without organic solvents for the design of hierarchically nanodispersed catalysts. In this procedure nanoparticles are dispersed on the surface of micrometric scale supports [18, 19]. This nanodispersion method opens a wide range of opportunities to obtain nano-micro-supported nested systems with extraordinary properties, made by mixing oxides of different nature.

The intercares created after the partial reaction by exposing both oxides generate the appearance of novel and interesting properties due to the proximity and diffusion effects of the materials involved [20, 21], which acquire a greater relevance at the nanometric level. Thus, we have shown that the appearance of ferrimagnetism in the ZnO / Co3O4 system is related to intercara phenomena, although the constituent oxides of the system have diamagnetic and paramagnetic properties at room temperature, respectively [22, 23].

Therefore, the present invention assesses the effects in the process of preparing the Co3O4 / ZnO mixtures obtained by nanodispersion in the dry path. In addition, the process of preparing the family of catalysts modifies the structure and morphology of the Co3O4 / ZnO system. In this way, the catalytic properties (activity / selectivity) are modified and regulated due to the intercares generated in the system, since it has been tested in the reaction of carbonylation of glycerin with urea.

Description of the invention

In a first aspect, the present invention relates to a process for obtaining catalysts comprising the dry dispersion of nanoparticles or nanoparticulate clusters smaller than 100 nm on a support formed by micrometric particles.

In a preferred embodiment, in the described process the nanoparticles or nanoparticulate clusters are oxides

or metal hydroxides that are selected from the list comprising oxides of aluminum, cobalt, copper, tin, nickel, silicon, titanium, zinc, cerium, vanadium, niobium, tantalum, chromium, molybdenum, tungsten, phosphorus, antimony, iron, zirconium

or any of its combinations.

Preferably, the nanoparticles or nanoparticulate clusters are of cobalt oxides and more preferably of Co3O4.

In another preferred embodiment, in the described process the particles that form the support are metal oxides or hydroxides, preferably aluminum oxides, zinc, silicon, titanium, zirconium, cerium, niobium or combinations thereof and more preferably ZnO.

In another preferred embodiment, the nanoparticles or nanoparticulate clusters are added to the dispersion in a percentage between 0.5 to 15 by weight with respect to the particles of the support.

In another preferred embodiment, the precursor materials of the nanoparticles and the support are subjected to a drying treatment.

In another preferred embodiment, Method according to any of the preceding claims wherein the catalysts obtained are subjected to a heat treatment.

Another aspect of the invention relates to a catalyst obtainable by the process as described above.

Another aspect of the invention relates to the use of the catalyst described for the carbonylation of glycerin with urea.

Description of the fi gures

Figure 1. Micrograph of raw materials, (a) ZnO microparticles and (b) nanoparticulate Co3O4 agglomerates. The insert shows a detail of the spherical Co3O4 nanoparticles obtained by Transmission Electron Microscopy. Micrograph, FE-SEM, of the ZnO particles coated by Co3O4 nanoparticles adhered to the surface after the dry nanodispersion process. (c) ZnO mixture with 10% by weight of nanoparticulate Co3O4 nanoparticles; (d) Detail of the micrograph obtained by TEM of Co3O4 nanoparticles dispersed in a ZnO microparticle with prismatic morphology observed in mixtures with Co3O4 in concentrations greater than 5% by weight.

Figure 2. X-ray diffractograms corresponding to raw materials, Co3O4 / ZnO mixtures at room temperature and heat treated at 500ºC / 36 h depending on the concentration of Co3O4.

Figure 3. (a) Raman spectra of the raw materials, of the Co3O4 / ZnO mixtures and also of the Co3O4 / ZnO mixtures heat treated at 500 ° C for 36 h depending on the Co3O4 content. (b) Magnification of the Raman spectra in the range between 640 and 760 cm -1 of the heat treated Co3O4 / ZnO mixtures. Figure 3 (b) presents the deconvolution through a Lorentzian function adjusted to the Raman mode associated with the appearance of the spinel phase (ZnCo2O4).

Figure 4. Development of the catalytic activity of Co3O4 / ZnO systems for the synthesis of glycerin carbonate at 145 ° C for 4 h.

Figure 5. Schematic representation of the binding of the nanoparticles to the surface of the micrometric ZnO obtained by the dry nanodispersion method, (a) Co3O4 / ZnO system before and (b) after the dry nanodispersion process. (c) Magnification of the ZnO surface hierarchically coated with Co3O4 nanoparticles, where Co3O4-ZnO interleaves can be observed. (d) Schematic representation of the formation of the spinel phase after heat treatment at 500 ° C / 36 h.

Figure 6. Mechanism of the reaction between glycerol and urea. Reaction products: A urethane glycerol; B glycerol carbonate; C 5- (hydroxymethyl) -oxazolidin-2-one; D (2-methyl oxo-1,3-dioxolan-4-yl) carbamate.

Examples

Nanodispersion procedure of Co3O4 / ZnO mixtures

Compositions with 0.5, 1, 5 and 10% by weight of Co3O4 nanoparticles (hereinafter referred to as ZCo0.5-Nps, ZCo1 Nps, ZCo5 Nps and ZCo10 Nps, respectively) were prepared by incorporating the amounts appropriate of the Co3O4 nanoparticles and ZnO microparticles by a previously described method of dry nanodispersion [18]. The process consists of dispersing the Co3O4 / ZnO mixtures, with ZrO2 balls of 1 mm in diameter in a 60 cm3 nylon container for 5 min at 50 rpm by means of a turbula-type mixer. The pure oxides ZnO and Co3O4 have also been exposed to the same mixing process to ensure that contributions from the structural disorder produced by the mixing process are not introduced. The raw materials used in this study are Cobalt oxide Co3O4 (99.99%) and ZnO (99.99%) of analytical grade which were dried at 110 ° C for 2 hours before dry nanodispersion.

Morphology Characterization

The particle size and morphology of the powders were evaluated using a Scanning Electron Microscope with field emission, FE-SEM (Hitachi S-4700) and using Transmission Electron Microscopy (MET, Hitachi H-7100 175) with a voltage 120 kV acceleration. The samples analyzed by MET were suspended in isopropanol.

Structural Characterization

The crystalline structure was determined by X-ray diffraction analysis (DRX, Siemens D5000, Munich, Germany, CuKα radiation). Raman spectra were obtained in the air atmosphere at room temperature, with an Ar + laser radiation of 514 nm. The signal is collected by a Raman spectrometer equipped with a microscope (Micro-Raman Renishaw System 1000) and a measuring window between 100 cm − 1 and 1100 cm − 1.

TABLE 1

Main Raman modes observed in ZnO and Co3O4 phases. The intensity of the peaks is tabulated from very low to very intense, (b: low, m: medium; f: strong, v: very)

Reaction procedure in the carbonylation of glycerin with urea

The reaction procedure characteristic of this work consisted of mixing in a 10 ml round bottom flask, glycerin and urea in equimolar amounts. Before adding the catalyst, this mixture was stirred for five minutes at 300 rpm in a batch reactor in a silicone bath heated to 140-145 ° C. After this type, the catalyst was added and the reaction began. This process was carried out in the absence of solvents at atmospheric pressure by eliminating the ammonia formed during the reaction by passing a flow of air over the reaction mixture. The amount of catalyst used was 6% by weight with respect to the initial amount of glycerin used. After four hours of reaction, the sample was taken using water for dilution and extracting the catalyst by filtration. The catalyst was washed with acetone several times and dried at room temperature for 24 hours to be used later in a new reaction cycle. The reaction was then followed by gas chromatography using an HP5890 gas chromatograph provided with an Ultra 2-5% capillary column of phenyl methyl siloxane (50 m) and flame detector (FID).

Morphology of Co3O / ZnO mixtures

The morphology of the raw materials ZnO and Co3O4 is shown in Figure 1 (a-b). The FE-SEM micrograph, Figure 1 (a), shows the typical morphology of the ZnO consisting mainly of elongated prismatic particles and almost cubic particles, with sizes of 0.2-1.0 μm, and an average particle size of 0.5 μm. The morphology of the Co3O4 nanoparticles is spherical with a size of 40-50 nm [see insert of Fig. 1 (b)] that form globular agglomerates of sizes between 0.5 to 4 μm Fig. 1 (b). On the other hand, the FE-SEM image of the ZnO mixture with 10% by weight of Co3O4 nanoparticles can be observed in the figure. 1 C). The micrographs show that most of the Co3O4 agglomerates disappear and the individual nanoparticles are attached to the surface of the ZnO, Fig. 1 (d). The dispersion and adhesion of the nanoparticles could indicate the appearance of Co3O4 / ZnO interleaves at room temperature, due to the high initial reactivity of Co3O4 and ZnO. All individual nanoparticles disperse below 10% by weight of Co3O4, but some agglomerates can be observed for high concentrations of Co3O4. This means that for concentrations ≥ 10% by weight, the dispersion limit of the nanoparticles on the ZnO microparticles has been reached. It is characteristic of the process that the morphology of the ZnO particles remains unchanged as a result of the low energy used during the dispersion process. The TEM micrograph, fi gure. 1 (d), again confirms the presence of the ZnO-Co3O4 interleaves after the dry dispersion process.

Structural characterization of the Co3O4 / ZnO system

X-ray diffraction spectra of raw materials and mixtures of Co3O4 / ZnO are shown in the Figure. 2, can be indexed based on a phase mixture consisting of a majority phase of ZnO and a minority of Co3O4. As expected, the intensity of the diffraction peaks of the Co3O4 phase becomes increasingly intense with increasing Co3O4 concentration.

In order to verify the effect of the heat treatment temperature on the phase structure, the mixtures were heat treated at 500 ° C for 36 hours. No changes in the X-ray diffraction spectrum are observed after heat treatment as seen in Figure 2.

There is no evidence of metallic Co, CoO or any additional phase other than ZnO, Co3O4 within the resolution provided by the X-ray diffraction technique. The expected reaction between Co3O4 and ZnO is the formation of a solid solution Zn1 − xCoxO with structure Wurtzite type, which has the same network parameters as those of ZnO. This would explain the fact that only ZnO diffraction peaks are observed at 500 ° C. There is little difference between the ionic radii of Co + 2 (0.058 nm) and Zn + 2 (0.060 nm) and, therefore, a small change in the value of the c axis could be expected due to the replacement of Co + 2 in ZnO. At higher temperatures, the formation of the ZnCo2O4 spinel phase is similarly possible, but this phase is isostructural with Co3O4, and therefore X-ray diffraction patterns cannot differentiate between both spinels.

The Co3O4 / ZnO mixtures prepared by the nanodispersion method at room temperature and heat treated at 500 ° C have also been characterized by Raman spectroscopy and the resulting spectra are shown in the Figure. 3 (a). The ZnO has a wurtzite-like structure, with two formulas per unit cell and C3ν symmetry. For this structure, group theory predicts the following active Raman modes A1 + E1 + 2E2 [24, 25]. These different active Raman modes of the ZnO can be seen in Table I, together with the proposed assignment. On the other hand, Table I also identifies the main Raman modes of Co3O4, which can be observed in the Raman spectra of the fi gure. 3 (a). Given that the spinel structures belong to the space group Fd3m (Oh7), five active Raman modes (A1g + Eg + 3F2g) could be expected. Pure cobalt oxide exhibits the five Raman modes theoretically predicted in the spectral range: A1g (689 cm -1); F2g (619, 521 and 191 cm − 1) and Eg (481 cm − 1). The high frequency mode, A1g, has been assigned to vibrations related to the movement of oxygen atoms within the octahedral unit of the spinel structure (for example, CoO6 in Co3O4). Its width is related to the length of the anion-cation bonds, as well as to the distortions of the polyhedron that occur in the network of the spinel structure [26], while the F2g and Eg modes combine the vibration of the spinel tetrahedron (by example, CoO4 in Co3O4) and octahedral sites [27]. The Raman spectra of ZnO and Co3O4 as raw materials and of the Co3O4 / ZnO mixtures are represented in the Figure. 3 (a), can be indexed based on a mixture consisting of two phases, ZnO and Co3O4. After heat treatment of the Co3O4 / ZnO mixtures at 500 ° C, the Raman bands of cobalt oxide show changes. The possible diffusion of Zn + 2 in the crystalline spinel network slightly modifies the frequencies of the vibrations as seen in the figure. 3 (b), moving them slightly towards blue. The Raman band associated with the movement of oxygen atoms within the octahedral unit, A1g, enelCo3O4 is the most intense for any Co3O4 concentration. On the other hand, the nanodispersion of Co3O4 produces a slight widening of the Raman A1g mode and the appearance of a double band for thermal treatments of 500ºC. The second band can be attributed to the appearance of the ZnCo2O4 spinel phase at 14714 cm − 1 that emerges concomitantly, Figure 3 (b). Actually, for Co3O4 concentrations as low as 0.5% by weight, the formation of the ZnCo2O4 spinel is clearly observed. The spinel formation requires a wide diffusion of the Zn + 2 atoms and therefore is favored by the long calcination time to which the mixtures are subjected, 36 hours. Recently, the formation of the spinel phase at low temperature ∼400 ° C [28] has been described in this system, which could be related to the phenomena of diffusion of Zn + 2 cations.

In summary, Raman spectroscopy evidences a progressively intercalating reaction in Co3O4 / ZnO mixtures, which is produced by the effective dispersion of nanoparticles on the surface of ZnO. Prolonged thermal treatments at low temperature allow the diffusion of Zn cations and therefore the formation of new spinel-like structures, ZnCo2O4. Zn cations are active at temperatures close to 400 ° C due to the thermal desorption of interstitial Zinc (Zni +) and the formation of surface oxygen vacancies (Vo) s. This behavior facilitates the volatilization of the Zn cations of the crystalline network of wurtzite and the diffusion of zinc in the nearest particles, in this particular case Co3O4, thus promoting the solid state reaction during heat treatment [22, 29] .

Activity measures of the Co3O4 / ZnO catalytic system

According to the studies carried out so far on the carbonylation reaction of glycerin with urea, urea reacts with glycerin when the mixture is heated in the presence of a catalyst. The proposed reaction mechanism follows four possible steps: (I) carbamoylation of glycerin to glycerolurethane (A), (II) carbonylation of glycerolurethane to glycerin carbonate (4-hydroxymethyl-1,3-dioxolan-2-one) (B) With ammonia abstraction or (III) carbonylation of glycerolurethane at 5- (hydroxymethyl) oxazolidin-2-one (C) without ammonia abstraction and (IV) glycerin carbonate can react with another urea molecule to give (2-) carbamate oxo-1,3-dioxolan-4-yl) methyl (D), decreasing glycerin carbonate selectivity [15, 17], see Fig 6.

Figure 4 shows the activity results obtained during the carbonylation of glycerin using as catalysts the pure oxides of Co3O4 and ZnO, the Co3O4 / ZnO catalytic system prepared by nanodispersion dry at room temperature and heat treated at 500 ° C / 36 h. Pure ZnO was not much more active than the reaction without catalyst, which is in agreement with the results published in the literature [30]. However, pure Co3O4 oxide proved to be more active and selective. The mixture of both oxides shows catalytic activity depending on the preparation procedure and treatment temperature. The catalytic activity increases considerably with the amount of cobalt oxide dispersed over zinc oxide in samples prepared at room temperature, however it increases slightly for the series of samples calcined at 500 ° C (Figure 4). This shows that the calcination of the samples decreases their catalytic activity. The series of samples of 1% by weight of Co3O4 dispersed in ZnO at room temperature showed 100% selectivity to glycerin carbonate but were only slightly more active than the white reaction without catalyst; for higher concentrations of Co3O4 dispersed on ZnO (10% by weight) the conversion reaches 69% and 97% selectivity to glycerin carbonate in 4 hours of reaction. The behavior of this series differs from others previously studied [17], where total conversion and selectivities of around 75% to glycerin carbonate were shown in 5 hours of reaction. On the other hand, the calcination of the Co3O4 / ZnO series at 500ºC does not improve its catalytic activity with respect to the Co3O4 / ZnO series.

When the Co3O4 nanoparticles are dispersed in the ZnO microparticles, the Co3O4 / ZnO systems were catalytically more active since the nanodispersion preparation method leaves the free active centers Co3O4 dispersed in the system. With the calcination of the samples the phenomenon that takes place can be explained as follows: ZnO microparticles can interact with Co3O4 nanoparticles and form inactive species such as ZnCo2O4, which is confirmed by Raman Spectroscopy, decreasing in the system the number of active centers free of Co3O4. The cobalt and zinc oxide spinel, ZnCo2O4, shows very little catalytic activity due to the restriction of active cobalt species in their tetrahedral structure. An increase in the amount of cobalt oxide in the system (from 1 to 10% by weight) leads to an increase in catalytic activity, said increase being less significant in the case of calcined samples since the main phase present in its composition It is the inactive spinel type phase. Finally, the ZnCo2O4 / ZnO catalytic system proved to be fully recoverable and reusable up to three times without showing significant loss of activity and selectivity in the glycerin carbonylation reaction.

To conclude, Co3O4 / ZnO systems prepared by dry nanodispersion at room temperature showed the best results compared to pure starting oxides and Co3O4 / ZnO systems calcined at 500ºC / 36 h. Specifically, samples with high concentrations of Co3O4 (10% by weight) showed the best activity (above 69% conversion and 97% selectivity to glycerin carbonate) demonstrating that a good dispersion of the active catalytic centers of Co3O4 in the System interface, plays a crucial role during the reaction. The results highlight the importance of the synthesis method used in the preparation of this heterogeneous catalytic system.

The phenomenology described here can be interpreted as a simple model based on the formation of the Co3O4 / ZnO intercars at room temperature and the formation of new crystalline phases, ZnCo2O4, for low temperature thermal treatments, see Fig. 5. So both, Figure 5 (a) and (b) show a schematic representation of an individual ZnO particle hierarchically coated with Co3O4 nanoparticles by the dry nanodispersion method. The dispersion and adhesion of the nanoparticles may indicate that a spontaneous reaction occurs at room temperature, between these materials, due to the high initial reactivity of Co3O4 and ZnO [19]. Figure 5 (c) shows the magnification of the ZnO surface where it is possible to observe the formation of new interleaves between the ZnO microparticles and Co3O4 nanoparticles. The dry nanodispersion process performed to mix the ZnO and Co3O4 creates new reactive surfaces (as evidenced by FE-SEM and TEM) that can favor catalytic activity. This new form of nanoparticle deagglomeration has been applied in the reaction of glycerol carbonylation with urea producing new properties in the intercars with high activity and catalytic selectivity. The high reactivity of ZnO can promote greater availability of Zn cations to diffuse in the Co3O4 nanoparticles, and therefore form stable crystalline species with spinel structure, ZnCo2O4, when the Co3O4 / ZnO system was heat treated at 500 ° C for 36 h as can be seen in the figure. 5 d). The heat treatment causes the formation of catalytically inactive species such as ZnCo2O4 by decreasing the number of free active sites of Co3O4.

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Claims (13)

one.

Process for obtaining catalysts comprising the dry dispersion of nanoparticles or nanoparticulate clusters smaller than 100 nm on a support formed by micrometric particles.

2.

Process according to claim 1 wherein the nanoparticles or nanoparticulate clusters are metal oxides or hydroxides that are selected from the list comprising oxides or hydroxides of aluminum, cobalt, copper, tin, nickel, silicon, titanium, zinc, cerium, vanadium, niobium, tantalum, chromium, molybdenum, tungsten, phosphorus, antimony, iron, zirconium or any combination thereof.

3.

Method according to claim 2 wherein the nanoparticles or nanoparticulate clusters are of cobalt oxides.

4. Process according to claim 3 wherein the cobalt oxide is Co3O4.

5.

Process according to any of the preceding claims wherein the particles that form the support are metal oxides.

6.

Process according to claim 5 wherein the particles that form the support are of oxides or hydroxides of aluminum, zinc, silicon, titanium, zirconium, cerium, niobium, or combinations thereof.

7. Method according to claim 6 wherein the particles forming the support are ZnO.

8.

Method according to any of the preceding claims wherein the nanoparticles or nanoparticulate clusters are added to the dispersion in a percentage between 0.5 to 15 by weight with respect to the particles of the support.

9.

Process according to any of the preceding claims wherein the precursor materials of the nanoparticles and the support are subjected to a drying treatment.

10.

Process according to any of the preceding claims wherein the catalysts obtained are subjected to a heat treatment.

eleven.

Catalyst obtainable by the process according to any of the preceding claims.

12.

Use of the catalyst according to claim 10 for the carbonylation of glycerin with urea.

SPANISH OFFICE OF PATENTS AND BRANDS SPAIN REPORT ON THE STATE OF THE TECHNIQUE 51 Int. Cl. See Additional Sheet twenty-one Application no .: 201031234 22 Date of submission of the application: 06.08.2010 32 Date of priority: RELEVANT DOCUMENTS

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EN 2332079 A1 (SUPERIOR INVESTIGATION COUNCIL) 25.01.2010, 1-8

page 3, lines 31-51; page 4, lines 58-69; page 5, lines 4-24; page 6, lines 44-46;

Example 1.

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CHERNAVSKII, P.A. et al. "Size Distribution of Cobalt Particles in Catalysts for the Fischer eleven

Tropsch Synthesis "KINECTICS AND CATALYSIS, Vol. 44 no 5 2003 pages 718-723, abstract,

experimental.

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BARTHE, L et al. "Dry impregnation in fluidized bed: Drying and calcination effect on nanoparticles   

dispersion and location in a porous support ". CHEMICAL ENGINEERING RESEARCH AND  

DESIGN 2008 Vol. 86 pages 349-358, abstract.

  Category of the documents cited X: of particular relevance Y: of particular relevance combined with other / s of the same category A: reflects the state of the art O: refers to unwritten disclosure P: published between the priority date and the date of priority submission of the application E: previous document, but published after the date of submission of the application

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 Date of realization of the report 27.10.2011

 Examiner V. Balmaseda Valencia  Page 1/4

TECHNICAL STATUS REPORT Application number: 201031234 CLASSIFICATION OBJECT OF THE APPLICATION C04B35 / 00 (2006.01) B82Y30 / 00 (2011.01) B01J23 / 75 (2006.01) B01J21 / 06 (2006.01) B01F3 / 18 (2006.01) Minimum documentation sought (classification system followed by classification symbols) C04B, B82Y, B01J, B01F Electronic databases consulted during the search (name of the database and, if possible, search terms used) INVENES, EPODOC, WPI, XPESP, NPL, HCAPLUS State of the Art Report Page 2/4  WRITTEN OPINION Application number: 201031234 Date of Written Opinion: 27.10.2011 Statement

Novelty (Art. 6.1 LP 11/1986)

Claims 9,10,12 YES

Claims 1-8

NO

Inventive activity (Art. 8.1 LP11 / 1986)

Claims 12 YES

Claims 1-11

NO

The application is considered to comply with the industrial application requirement. This requirement was evaluated during the formal and technical examination phase of the application (Article 31.2 Law 11/1986).  Basis of Opinion.- This opinion has been made on the basis of the patent application as published. State of the Art Report Page 3/4  WRITTEN OPINION Application number: 201031234 1. Documents considered.- Below are the documents pertaining to the state of the art taken into consideration for the realization of this opinion.

Document

Publication or Identification Number Publication Date

D01

EN 2332079 A1 (RESEARCH SUPERIOR COUNCIL) 01.25.2010

D02

CHERNAVSKII, P.A. et al. "Size Distribution of Cobalt Particles in Catalysts for the Fischer-Tropsch Synthesis" KINECTICS AND CATALYSIS, Vo l. 44 No 5 2003 pages 718-723, abstract, experimental.

2. Statement motivated according to articles 29.6 and 29.7 of the Regulations for the execution of Law 11/1986, of March 20, on Patents on novelty and inventive activity; quotes and explanations in support of this statement The object of claims 1-8 and 11 is a process for obtaining catalysts based on dispersion via dry, as well as the resulting catalysts. Document D01 describes a procedure for the dispersion of nanoparticles, of the same or different morphology and / or nature, in which at least one of said types of nanoparticles has a size smaller than 100 nm. The dispersion is It performs on other support particles or on a substrate and includes dry agitation. Preferably, the nanoparticles of dispersed in a proportion less than 5%. In a preferred embodiment, the nanoparticles are selected from Al2O3, Co3O4, CuO, NiO, SiO2, SnO, TiO2, ZnO and the support particles between Al2O3, NiO or ZnO. In this way, the dispersions obtained can be used in various sectors of the industry, including catalysis. (page 3, lines 31 -51; page 4, lines 58 -69; page 5, lines 4 -24; page 6, lines 44-46 and example 1). In document D02 the dispersion of Co3O4 nanoparticles (6-10 nm) on Al2O3, SiO2 and ZrO2 supports is studied for use as catalysts, the proportion of Co3O3 being 10% by weight (abstract, experimental sections). Thus, the technical characteristics of claims 1-8 and 11 are known from documents D01-D02. Consequently, it is considered that the object of said claims lacks novelty and inventive activity in accordance establish Articles 6.1 and 8.1 of the L.P. The difference between lodged between documents D01-D02 and the object of claims 9-10 of this application lies in the drying treatment of the precursor materials and the thermal treatment of the catalysts obtained. Although these documents are not included in these treatments and the novelty of the procedure, it is not possible to recognize its inventive activity since, in the absence of technical elements that define the operating conditions, these treatments correspond to usual treatments known to the expert Matter in catalyst processing. Consequently, it is considered that the object of claims 9 and 10 lacks inventive activity (Article 8.1). None of documents D01-D02 discloses the use of a dispersed Co3O4 nanoparticle catalyst on a ZnO support for the carbonylation of glycerin with urea. In addition, it would not be obvious to an expert in the field such use from the cited documents. Consequently, the object of claim 12 is considered to be new and involves inventive activity in accordance with Articles 6.1 and 8.1 of the L.P. State of the Art Report Page 4/4