Title of Invention

"COMPOSITION COMPRISING A SUPPORT PAHSE AND HETEROPOLYACID PHASE OF FORMULA III"

Abstract

Composition suitable for use as a catalyst, comprising: a support phase comprising one or more of dioxides of titanium, zirconium, or a mixture thereof; and at least one heteropolyacid phase of formula III H3ψΔ12O40, in which ψ represents one or more of the following atoms or entities: P, As, Sb, HSi, HGe, H2B; and Δ represents one or more of the following atoms or entities: W, Mo, HV, or mixtures thereof; in which Δ is a mixture of at least two atoms or entities and Δ has a W:Mo atomic ratio at least equal to 1:12, advantageously 1:4, preferably 1:3, or optionally Δ has a V:(W+Mo+V) atomic ratio at least equal to 1:12, wherein the heteropolyacid can optionally be at least partially neutralized by a cationic entity of formula (II) [AaBb], wherein A represents at least one of hydrogen ion, monovalent alkali metal cation, ammonium ion and phosphonium ion; B represents at least one of VO2+, VO3+, an ion of an alkaline-earth metal, and anion of a metal from groups VII A, VIII, I B, IV B and V B of the periodic table; and wherein the relative amounts of the support phase and the heteropolyacid phase are such that the atomic ratio (C+E)/metallic element of the support is between 0.1 and 30%, wherein C represents Mo and/or W and E represents vanadium.

Full Text

The present invention relates to a process for the controlled oxidation of electron-depleted substrates, in the presence of. a catalyst whose active phase is obtained from one or more heteropolyacids. It more particularly concerns the controlled oxidation of a substrate having a methylene to which an electronwithdrawing group or functional group is attached/ The present invention furthermore relates to a composition obtained from certain specific heteropolyacids and titanium dioxide as a support, as well as to a catalyst comprising the said composition as its active phase. By convention, the term heteropolyacid (or HPA) will be used in this text to denote compounds corresponding to the Keggin structure, both heteropolyacids and polyoxometallates. In this field, as regards the nature of the Keggin structure, reference may be made to two articles published in "the catalyst review newsletter"; the one published in October 1993 concerning "solid acid '93 meeting, Houston Texas" on page 9, and the one in volume 4 No. 7 on page 12. Obtaining a carbon-oxygen bond, in particular a single one, from a >CH- unit (in general methyl) of which at least one of the bonds is linked to an electron-withdrawing group, by controlled oxidation of the said unit, has the advantage of using a raw material whose cost is very competitive compared to those employed in existing technologies. However, to the knowledge of the Applicant Company, no process of this type has been described to date. A process of this type would be of particular interest for synthesizing carbon derivatives which contain both oxygen and halogens, above all fluorine. As an example of the problem to be solved, mention may be made of the cases in which the electron-withdrawing group or groups are selected from fluorine atoms and radicals whose attachment carbon tthat is to say the one linked to the said >CH-) is monofluorinated, and advantageously difluorinated. As electron-withdrawing group, particular mention should be made of perfluoroalcoyls and, in particular, trifluoromethyl. This is why one of the objects of the present invention is to provide a controlled oxidation process which makes it possible to treat electron-depleted substrates. Another object of the present invention is to provide a process of the above type which makes it possible to form one or more carbon-oxygen bonds. Another object of the present invention is to provide a process of the above type which makes it possible to form one or more ether, ester and/or acid f \inc t i ona 1 group s . Another object of the present invention is to provide a process of the above type which makes it possible to form one or more ether, ester and/or acid functional groups from a methylated perfluoroalkane, and in particular 1,1,1-trifluoroethane. These objects, and others which will become apparent below, are achieved by means of a process for the controlled oxidation of a substituted hydrocarbon substrate, in which the said substituted hydrocarbon substrate is brought into contact with an oxygen source in the presence of at least one catalyst selected from those whose active phase is obtained from a heteropolyacid of formula (I): Hf [CcDdEeOj in which: C represents Mo and/or W; D represents phosphorus, arsenic, antimony, silicon, germanium and/or boron; E represents an element selected from vanadium optionally in combination with at least one metal from groups VA, VIIA, VIII or chromium; it being possible for the said acid to be partially or even completely neutralized by a cationic entity of formula (II) [AaBb] substituting for H£: x being the number of oxygens needed to accommodate the highest valencies of C, D and E; from hydrogen, an alkali metal, or an ammonium or phosphonium ion; B represents VO2+, VO3+, an ion of an alkaline-earth metal or of a metal from groups VII A, VIII, IB, IV B and V B of the periodic table; = a + ab with a being the charge of the ion B, i.e. equal to 2, 3 or 4; c varies between 5 and 20-e inclusive; d varies between 1 and 5 inclusive; e varies between 1 and 9 inclusive; and in that the said substrate has a (>CH-) unit, advantageously methylene (CH2) , to which at least one electron-withdrawing group (or atom) is attached, f/d is on one hand at least equal to 1 and on the other hand at most equal to 12, advantageously to 8, preferably to 8. x is equal to (f+cy+d6+ee)/2 where the greek letters represent the highest valence of the elements represented by the corresponding capital latin letters. Here, and throughout the description, the references made to the periodic table of the elements pertain to the one published in the supplement to the Bulletin de la Socigte Chimique de France (No. I - January 1966). The invention also relates to a composition obtained from titanium dioxide as the support and a heteropolyacid of formula (I). In what follows, the terms titanium dioxide and titanium oxide have the same meaning. Thus, the process according to the invention consists in employing a catalyst whose active phase is obtained from a heteropolyacid of the aforementioned formula (I) . More particularly, the element B is selected from the ions VO2+, VO3+, Cu2+, Fe3+, Co2+, Ag+, Ni2+, Mn2+, Mg2+, The element B is advantageously selected from the ions V02+ and V03+ ; preferably the ion V02+. As regards the element E, if other than vanadium, it is more particularly selected from chromium, manganese, iron, cobalt and nickel. According to a preferred variant of the invention, the heteropolyacid involved in the preparation of the active phase corresponds to the formula (I) in which D is phosphorus, E is vanadium, d is equal to 1, c is between 1 and 3 and the sum of c + e is equal to 12. According to a particular embodiment, the catalyst which is employed has an active phase that furthermore comprises a support. By way of a support which is suitable for this particular embodiment, mention may for example be made of the dioxides of titanium, silicon, zirconium, cerium, tin, alumina and silica-alumina, it being possible for these made of the dioxides of titanium, silicon, zirconium, cerium, tin, alumina and silica-alumina, it being possible for these compounds to be used individually or as a mixture. The support is preferably selected from the dioxides of titanium or zirconium, the former being preferred. According to a variant of this embodiment, the active phase of the catalyst has an atomic ratio, (C + E)/metallic element of the support, of between 0.1 and 30%. The term metallic element of the support is intended to mean titanium, zirconium, cerium, etc. The aforementioned atomic ratio is preferably between 5 and 20%. In the case when the active phase comprises a support, the distribution between the two constituents of the active phase is such that the heteropolyacid of formula (I) is more particularly dispersed at the surface of the said support. According to a first embodiment, the catalyst is employed in bulk form, that is to say a catalyst comprising only the active phase obtained from the heteropolyacid and, where applicable, the support. According to a second embodiment, the catalyst is employed in dilute form, that is to say the aforementioned active phase is mixed with an inert material. In the latter case, the active phase may either be deposited on the inert material, or coated or else mixed with it. By way of materials which may be used as inert materials, mention may be made of: sintered clay, magnesia, magnesium silicate, diatomaceous earth. These types of inert materials may be used in porous or nonporous form. The respective inert material is preferably used in non-porous form. If necessary, it may be enamelled to render it non-porous. Ceramic materials, such as cordierite, mullite, porcelain, nitrides of silicon and of boron, and silicon carbide may also be used as the inert material. The catalyst employed in the process according to the invention, which may or may not be diluted, is in the form of particles or a monolith. If the catalyst consists of particles, their size will depend on the way in which the catalyst is used. It can therefore vary in wide limits, in particular between a few micrometres and about ten millimetres. More particularly, by way of indication, a catalyst used as a fixed bed has a particle size distribution of generally between 0.5 and 6 mm. The size of the particles of a catalyst used as a fluidized or mobile bed is usually between 5 and 700 microns, and preferably between 5 and 200 microns for 80% of the particles. If the catalyst consists of particles, any shape will be suitable for implementing the invention. Thus, the catalyst may for example be in the form of balls or rings. The term rings is used to denote hollow objects whose cross-section is circular, parallelepipedal, ellipsoidal or the like. Any other type of complex structure may likewise be envisaged, for example one obtained by extruding the inert material (cross, star, etc.). In the conventional way, the quantity of inert material involved in the composition of the catalyst varies in wide limits, most of the time depending on the way in which the catalyst is formed. Thus, catalysts obtained by coating or depositing the active phase on the inert material have a quantity of active phase which usually varies between 0.1 and 30%, and preferably between 2 and 20% of the total weight of catalyst (active phase + inert material). In the cases when the catalyst comprises the active phase dispersed in an inert material, the quantity of active phase is between 1 and 90% of the total weight of catalyst. According to a preferred embodiment of the invention, the active phase of the catalyst coats the inert material which is present. The catalyst may be prepared using any simple and reproducible conventional technique, and this constitutes an additional advantage of the invention. Heteropolyacids are known compounds, and the person skilled in the art may refer to the relevant publications in order to prepare them. As more particularly concerns heteropolyacids, that is to say compounds for which A represents a hydrogen atom, two types of process may in particular be employed. According to a first method, more particularly suitable for the preparation of heteropolyacids in which b is equal to 0 and d is equal to 1, a mixture comprising the constituent elements of the heteropolyacid, preferably in the form of oxides, is refluxed in water for 24 h. Another method of obtaining the heteropolyacids of the same type as above, for which the value c is between 6 and 12, consists in preparing a solution of the constituent elements of the HPA, which are present in the form of alkali or alkalineearth metal salts. This solution is obtained by dissolving the said compounds in water. Once the solution has been obtained, it is neutralized by adding an inorganic acid such as, in particular, hydrochloric acid. The resulting product is extracted from the medium with ether, then brought into contact with distilled water in order to obtain an aqueous solution, from which the heteropolyacid can be crystallized. After each of these two methods, it is possible to obtain the desired heteropolyacid by evaporation or crystallization. This heteropolyacid may be used directly as a catalyst in the reaction according to the invention, optionally after having been subjected to a calcining step which will be described below. In the conventional way, and in the case when the catalyst employed comprises a support, the heteropolyacid is brought into contact with the said support by means, for example, of dry impregnation, although other ways are not a priori ruled out. In this regard, mention may be made of mixing the various constituents, heteropolyacid and support, in a solid form for example. According to the impregnation method, the support as defined above is brought into contact with a heteropolyacid solution in a quantity such that the atomic ratio, (C + E)/metallic element of the support, is between 0.1 and 30%, and preferably between 5 and 20%. The resulting suspension is then dried. This drying step may advantageously be carried out in two steps: the first consisting in evaporating the solvent or dispersant of the mixture, more particularly water, to dryness, and the second in drying the paste thus obtained. The first step is generally carried out at a temperature varying from 20 to 100°C, optionally under vacuum, for the time needed to obtain a paste. The evaporation is usually carried out while stirring. The paste obtained is then dried, in a second step, under a preferably non-reducing atmosphere, such as oxygen or air for example, for an average time of 15 h. The drying temperature is usually between 100 and 150°C. It should be noted that other drying methods may be envisaged, for example spray-drying the suspension in any suitable type of equipment, and under conditions known to the person skilled in the art. The dried product is then subjected to a calcining step. This is carried out, in the conventional way, under a non-reducing atmosphere. Air is advantageously used, but oxygen could equally well be employed. The calcining temperature is usually between 200 and 500°C. The duration of the operation generally varies between 1 and 24 h. Before and/or after the calcining step, the dried product may be subjected to a desegregation step. In the case when the catalyst employed in the process according to the invention comprises an inert material, the coating method is preferably employed. Thus, the inert material, preferably in the form of rough particles, and the active phase are brought into contact in a high-shear mixer (LODIGE type machine) or in a granulation machine (drum or disc granulators) . The operation is in general carried out at a temperature varying between 20 and 150°C for the time needed to coat the inert material with the desired quantity of active phase, more particularly under air, for at least 30 min. The particles thus obtained are usually calcined at a temperature of between 300 and 500°C. The calcining generally lasts at least 3 h. Of course, all these ways of preparing the heteropolyacid, and bringing the said HPA into contact with the support and/or inert material, have been given solely by way of indication and can in no way constitute an exhaustive list. As mentioned above, the process according to the invention consists in carrying out controlled oxidation of the substrate with an oxygen source, in the presence of a catalyst as described above. The said methylene unit is preferably a methyl. It is desirable if the said electronwithdrawing group (or atom) is not readily oxidizable. Advantageously/ the said electron-withdrawing group(s) (or atom(s)) have at least one halogen atom, advantageously fluorine. As mentioned in the introduction, the results are of particular benefit when the bond between the said group and the said >CH- unit is attached to a carbon to which at least two halogen atoms are attached, advantageously at least one, and preferably at least two, of which are fluorine. The said electron-withdrawing group is an Rf group, and in particular the said group is selected from the trihalomethyl, tetrahaloethyl and pentahaloethyl groups. It is desirable that at least half of the said halogens are advantageously fluorine, and preferably the said group is selected from the trifluoromethyl, tetrafluoroethyl and pentafluoroethyl groups. As is evident from the description above, the said CH- unit has an alcoyl radical, a second (or even a third) electron-withdrawing group or, preferably, a hydrogen attached to it. The said methylene group (CH2) has a second electron-withdrawing group attached to it, which is linked to the first electron-withdrawing group to form a ring. The said CH- unit may have an acrylic unit attached to it. The said CH- unit may advantageously be a methylene group (CH2) , to which a hydrogen is preferably attached in order to form a methyl radical. Returning to the composition of the catalyst, it may be reiterated that, according to an advantageous variant of the present invention, the reaction is advantageously carried out in the presence of a catalyst whose active phase is obtained from a heteropolyacid of formula (I) in which D is phosphorus, E is vanadium, e is between 1 and 3 inclusive, d is equal to 1, the sum of c + e is equal to 12 and x = 40. The reaction is advantageously carried out in the presence of a catalyst whose said active phase is deposited on a support. In particular, the reaction is carried out in the presence of a catalyst whose said active phase is deposited on a support, and the support is selected from the dioxides of titanium, silicon, zirconium, cerium and tin, alumina, silica-alumina, or mixtures thereof. According to a particularly advantageous embodiment of the present invention, the reaction is carried out with a gas mixture comprising from 0.1 to 99.9 mol% of substrate, and more particularly between 0.1 and 3% or between 10 and 99 mol% of substrate, and air, oxygen or nitrogen monoxide is preferably used as the oxygen source . Furthermore, the reaction is carried out with a gas mixture comprising from 0.1 to 99.9 mol% of oxygen, and more particularly comprising between 1 and 90% or between 97 and 99.9 mol% of oxygen. Advantageously, use is made of a gas mixture having a substrate/oxygen molar ratio of less than 20 and more particularly between 0.01 and 0.2 or between 0.6 and 18. According to an advantageous variant of the present invention, the reaction is carried out in the presence of a diluent selected from water, or the inert gases, or recycled gases from the reaction, individually or as a mixture and more particularly a gas mixture comprising 0.1 to 70 mol% of water, and preferably comprising from 1 to 20 mol% of water. According to a particularly advantageous embodiment of the present invention, the heteropolyacid of formula (I) satisfies the empirical formula (III) : H3 with: *¥ representing the following atoms or entities: P, As, Sb, HSi, HGe, H2B; A representing the following atoms or entities: W, Mo, HV and mixtures thereof . ¥ represents pentavalent entity (or atom) Advantageously, as mentionned before, *F represents; P, As and preferably Phosphorus. A represents hexavalent entity (or atom). It is desirable that when A represents a mixture the atomic ration (Mo + W) / (W + Mo + HV) est at least equal to 0,5. It is desirable that the heteropolyacid of formula (III) has a so-called Keggin structure. According to the present invention, the role of delta is important for the level of oxidation obtained (see below). Thus, the heteropolyacid of formula (III) may be such that A is a mixture of at least two atoms or entities. :v According to one option, the heteropolyacid of formula (III) is such that A has a W/Mo atomic ratio at least equal to 1/2, advantageously 1, preferably 2. According to a variant, the heteropolyacid of formula (III) is such that A has a V/(W + Mo + V) atomic ratio at least equal to 1/12, advantageously 1/6, preferably 1/4. More precisely, if it is desired for the substrate to be oxidized to form a carboxylic acid (essentially in the case when the said >CH- unit is methyl) it will be preferable if the heteropolyacid of formula (III) and the cationic entity of formula II are such that the atomic ratio between the total number of hydrogens present and *F is at least equal to 3, advantageously 4, preferably 5. If it is desired for the substrate to be oxidized to the average state II (for example to form an ester or a ketone), it will be preferred that the heteropolyacid of formula (III) and the cationic entity of formula II are such that the atomic ratio between the total number of hydrogens present and *F is at least equal to 2, and at most equal to 3. If it is desired for the substrate to be oxidized to form an ether, it will be preferred that the heteropolyacid of formula (III) and the cationic entity of formula II are such that the atomic ratio between the total number of hydrogens present and *F is at most equal to 3, advantageously 2, preferably 1. The present invention thus also relates to a composition which includes a support phase selected from the dioxides of titanium, zirconium and a mixture thereof, and at least one heteropolyacid phase of formula III in which A has a W/Mo atomic ratio at least equal to 1/12, advantageously 1/4, preferably 1/3. It also relates to a composition in which the heteropolyacid of formula (III) and the cationic entity of formula II are such that the atomic ratio between the total number of hydrogens present and *F is at most equal to 3, advantageously 2, preferably 1. It also relates to a composition in which the heteropolyacid of formula (III) and the cationic entity of formula II are such that the atomic ratio between the total number of hydrogens present and *¥ is at least equal to 3, advantageously 4, preferably 5. According to an advantageous variant of the present invention, the heteropolyacid of formula (III) and the cationic entity of formula II are such that the atomic ratio between the total number of hydrogens present and *F is at least equal to 2, and at most equal to 3. Advantageously, the heteropolyacid of formula (III) has a so-called Keggin structure. Preferably, the heteropolyacid of formula (III) is such that A is a mixture1of at least two atoms or entities. It is beneficial if the heteropolyacid has a formula (III) such that A corresponds to a W/Mo atomic ratio at least equal to 1/2, advantageously 1, preferably 2. It may also be advantageous if the heteropolyacid has a formula (III) such that A corresponds to a V/(W + Mo + V) atomic ratio at least equal to 1/12, advantageously 1/6, preferably 1/4. The following non-limiting examples illustrate the invention. Catalysts A dry run was carried out, that is to say a test of the TiO2 support at 250°C for seven hours. It was found that this solid has weak activity (3 to combustion (COX Sel. = 95%). Three groups of catalysts may be identified: Selectivity with respect to Selectivity with respect to ether (VO)HPMol20«o Pressure Reactants Operating conditions Sample mass: 1 gram of powdered catalyst (diluted to 3 ml in silicon carbide), 1 bar absolute, F143a/02/H20/inert material = 15.6/15.6/7.8/61 mol% Inert material: He: 55.9 and N2: 5.1 mol%, between 175°C and 250°C. : Temperature : Optimal : Conversion ratio : Selectivity expressed in mol% CO2 + CO Temperature - T - opt. - CR - Sel. - Ether : (CF3CH2)20 - TFA : Trifluoroacetic acid The model test lasts two days and includes two parts. 1.1 Test at variable temperature Effluent gases are analysed with a temperature increment of 25°C between 175 and 250°C, that is to say four analyses separated by an interval of 1 h 15 each. The results are analysed and used to determine the optimum temperature for the operating point in the second part. Catalysts selective with respect to TFA (trifluoroacetic acid) 1.2 Test at optimum temperature This is the temperature at which the best compromise is obtained between the overall conversion ratio for F143a and the total selectivity with respect to controlled-oxidation products (apart from combustion: CO2 and CO) . This temperature is either 225°C or 250°C. On the basis of this temperature's being kept constant, one analysis per hour is made in order to monitor the variation in the performance as a function of time. The study time varied from 5 h 3 0 to 46 h 00, according to: The stability of the values observed, The possible decrease in the conversion ratio for the initial F143a. Catalysts selective with respect to TFA 2. Preparation and characteristics of the catalysts The HPAs were dry-impregnated on the TiO2 support using the procedure described above. The TiO2 support has a specific surface area of 86 m2/kg, and a pore volume measured with water equal to 0.94 ml/g. The impregnation was carried out on 10 g of support and calculated so as to obtain a theoretical monolayer of HPA on it, such that: total metals/Ti = 0.167 by atom. The mass of HPA was dissolved in 9.4 ml of deionized water at 40°C. The support was then impregnated with the clear solution at room temperature. In some cases, two successive impregnation operations were needed, with drying at 120°C in between, in order to dissolve the requisite mass of HPA. The solids were dried at 110°C and tested as such. The following table summarizes the preparations which were made. We claim: 1. Composition suitable for use as a catalyst, comprising: a support phase comprising one or more of dioxides of titanium, zirconium, or a mixture thereof; and at least one heteropolyacid phase of formula III: (Formula Removed) in which Ψ represents one or more of the following atoms or entities: P, As, Sb, HSi, HGe, H2B; and Δ represents one or more of the following atoms or entities: W, Mo, HV, or mixtures thereof; in which Δ is a mixture of at least two atoms or entities and Δ has a W:Mo atomic ratio at least equal to 1:12, advantageously 1:4, preferably 1:3, or optionally Δ has a V:(W+Mo+V) atomic ratio at least equal to 1:12, wherein the heteropolyacid can optionally be at least partially neutralized by a cationic entity of formula (II) [AaBb], wherein - A represents at least one of hydrogen ion, monovalent alkali metal cation, ammonium ion and phosphonium ion; - B represents at least one of VO2+, VO3+, an ion of an alkaline-earth metal, and anion of a metal from groups VII A, VIII, I B, IV B and V B of the periodic table; and wherein the relative amounts of the support phase and the heteropolyacid phase are such that the atomic ratio (C+E)/metallic element of the support is between 0.1 and 30%, wherein C represents Mo and/or W and E represents vanadium. 2. Composition as claimed in Claim 1, in which the heteropolyacid of formula (III) and a cationic entity of formula II are such that the atomic ratio between the total number of hydrogens present and Ψ is at most equal to 3:1, advantageously 2:1, preferably 1:1. 3. Composition as claimed in Claim 1, in which the heteropolyacid of formula (III) and a cationic entity of formula II are such that the atomic ratio between the total number of hydrogens present and Ψ is at least equal to 3:1, advantageously 4:1, preferably 5:1. 4. Composition as claimed in Claim 1, in which the heteropolyacid of formula (III) and a cationic entity of formula II are such that the atomic ratio between the total number of hydrogens present and Ψ from 2:1 to 3:1 inclusive. 5. Composition as claimed in any of Claims 1 to 4, in which, in the heteropolyacid of formula (III), Δ has a W:Mo atomic ratio at least equal to 1:2, advantageously 1:1 preferably 2:1. 6. Composition as claimed in any of Claims 1 to 5, in which, in the heteropolyacid of formula (III), Δ has a V:(W + Mo + V) atomic ratio at least equal to 1:6, preferably 1:4. 7. Composition substantially as herein described with reference to any of the examples.

Documents:

1860-DEL-2005-Abstract-(15-09-2008).pdf

1860-DEL-2005-Abstract-02-04-2008.pdf

1860-del-2005-abstract.pdf

1860-DEL-2005-Claims-(01-10-2008).pdf

1860-DEL-2005-Claims-(15-09-2008).pdf

1860-DEL-2005-Claims-02-04-2008.pdf

1860-del-2005-claims.pdf

1860-del-2005-complete specification (granded).pdf

1860-DEL-2005-Correspondence-Others-(16-09-2008).pdf

1860-DEL-2005-Correspondence-Others-(24-09-2008).pdf

1860-DEL-2005-Correspondence-Others-02-04-2008.pdf

1860-Del-2005-Correspondence-Others-28-03-2008.pdf

1860-del-2005-correspondence-others.pdf

1860-DEL-2005-Description (Complete)-(15-09-2008).pdf

1860-del-2005-description (complete)-01-10-2008.pdf

1860-del-2005-description (complete).pdf

1860-DEL-2005-Description (Complete)02-04-2008.pdf

1860-DEL-2005-Form--2-02-04-2008.pdf

1860-DEL-2005-Form-1-(15-09-2008).pdf

1860-del-2005-form-1.pdf

1860-del-2005-form-13.pdf

1860-del-2005-form-18.pdf

1860-DEL-2005-Form-2-(15-09-2008).pdf

1860-del-2005-form-2.pdf

1860-Del-2005-Form-3-28-03-2008.pdf

1860-del-2005-form-3.pdf

1860-del-2005-form-5.pdf

1860-DEL-2005-GPA-02-04-2008.pdf

1860-del-2005-gpa.pdf

1860-DEL-2005-Others-Document-(24-09-2008).pdf

1860-Del-2005-Petition-137-28-03-2008.pdf

1860-del-2005-petition-138.pdf

1860-DELNP-2005-Claims-22-04-2008.pdf

1860-DELNP-2005-Correspondence-Others-22-04-2008.pdf

1860-DELNP-2005-Others Docoment-22-04-2008.pdf