Title of Invention

A PROCESS FOR THE MANUFACTURE OF MESOPOROUS ZIRCONIUM COMPOUND.

Abstract

Process for the manufacture of mesoporous Zirconium compounds and in particular to the manufacture of cost effective mesoporous zirconia-silica composite and mesoporous zirconium phosphate involving cost effective inorganic ingredients. The process basically involves using a selective zirconium complex using a water soluble zirconium compound; providing a gel/ precipitation for phosphate from sald zirconium complex in the presence of a surfactant and selectively atleast one source of water soluble silicate and phosphate source; allowing the gel/ precipitation for phosphate to age; and obtalning therefrom the mesoporous compound. The process is commercially viable and favour cost effective and large scale production of such zirconium composites. Importantly the mesoporous zirconium composite of the invention is directed for application / use in catalyst bed and as mesoporous molecular sieve.

Full Text

FIELD OF THE INVENTION The present invention relates to the manufacture of mesoporous Zirconium compounds and in particular to the manufacture of cost effective mesoporous zirconia-silica composite and mesoporous zirconium phosphate involving cost effective inorganic ingredients. The process is commercially viable and favour cost effective and large scale production of such zirconium composites. Importantly the mesoporous zirconium composite of the invention is directed for application / use in catalyst bed and as mesoporous molecular sieve. BACKGROUND ART It is well known to provide mesoporous zirconium composites involving silicate and phosphate material with selective porosity for variety of end use / application including chemical, optical, biological and electronic industry. In providing such mesoporous composites it is an important consideration that fictionalization is enhanced for its variety of end use/applications. Usually in the synthesis of mesoporous zirconia-silica composite and mesoporous zirconium phosphates generally metal alkoxides are used which are however very costly and therefore synthesis routes involving the same are not commercial viable. It is also known to synthesis mesoporous SIO2 - ZrO2 composite through sol-gel method using TEOS as a source of silica and also the gelling agent. In such process Zlrconyl nitrate dihydrate is used as a zirconium source. In this method, after preparation of the gel through add catalyzed reaction, the gel obtalned was aged. Subsequently mesoporous SiO2 - ZrO2 was obtalned after super critical gel drying. The use of tetraethoxysilane and zirconium n - propoxfde, mesoporous SiO2 - ZrO2 composite is also reported. As a further variety synthesis of mesoporous zirconium phosphate through sol-gel technique using zirconium alkoxide as precursor is also known. In this process, hydrolyzing of the alkoxide in the presence of ortho-phosphoric add and cationic surfactant to produce a solid mass which on leaching / caldning formed mesoporous zirconium phosphate is also known. While the above reveals the avallable knowledge in the art to produce the mesoporous composites, such process however are found to be either complex and/or cost extensive- It should thus be apparent that there is considerable advancement by ways to fictionalize mesoporous silicate structures. One of the major concerns in such manufacture of mesoporous composites Is the need to provide selected, functional sites in a number of locations within the structural network. Moreover, the flctlonalizatlon processes should be generally compatible with avallable techniques for making such mesoporous structures. For example, they should not add excessive cost to the overall manufacturing operations. Furthermore, it would be helpful if the new processes generally malntalned the physical integrity of the mesoporous structure. The pore size distribution obtalned from surface area analysis was comparable with alkoxides route indicating very good quality of the materials. In general such characteristics are hardly obtalned by such cost effective procedure. Importantly while the commercial source of mesoporous zirconia is zirconyl oxychloride which is a cost effective source to produce mesoporous zirconia with broad range of pore size distribution through precipitation, it has been difficult to produce mesoporous zirconium composites involving such cost effective sources. This is because in case of mesoporous SIO2 - ZrO2 composite, if sodium silicate and zirconyl oxychloride are used, instantaneous inhomogeneous precipitation takes place which hinder the formation of mesoporous compound or decreased its quality. In contrast with these traditional techniques, the solution sol-gel method (SSG) allows excellent control of the properties of the products. The SSG method, comprised of controlled hydrolysis and subsequent condensation of metal alkoxides, normally yield a homogeneous distribution of all the components at a molecular level, high surface area and adjustable pore size distribution. The same problem is experienced for zirconium Phosphate also. Though precipitation occurs here but the process is very slow and the homogeneity of the retalned compared to other non sol-gel methods. Thus in spite of the well known wide applications /uses of mesoporous composites the reliance on cost extensive sources of its manufacture make its obtalning commercially not viable to the desired extent There is thus a continuing need in the art to develop methods of producing such mesoporous composites cost effectively involving cost-effective sources. SUMMARY OF THE INVENTION It is thus the basic object of the present invention to provide for a method of manufacture of mesoporous zirconium composite such as mesoporous zirconium phosphate and ZrO2-SiO2 -composite involving cost effective inorganic ingredients as an effective alternative to cost extensive alkoxide presently in use for such synthesis. The maln object of the present invention is to prepare good quality mesostructured compounds with narrow pore size distribution and with high surface area through cheapest way. Another object of the present invention is directed to provide mesoporous composites such as ZrO2 -SiO2 composite, zirconium phosphate composite which would be commercially viable and favour its large scale production and wide ranging industrial applications. It is another object of the present invention to provide for the manufacture/ synthesis of mesoporous zirconium compound by way of cost effective and commercially viable process for advantageous cost -effective end uses of the same in catalyst beds and / or as mesoporous molecular sieves. It further object of the present invention is directed to avoid the problems experienced in use of cost effective inorganic sources such as zirconyl oxydoride in the manufacture of mesoporous zirconium composites such as ZrO2 -SiO2 and/or zirconium phosphate composite thereby facilitating advantageous use of such cost effective sources in the manufacture of mesoporous composite. Yet further object of the present invention is directed to provide for a simple and cost effective mesoporous composite with superior physiochemical property such as thermal and chemical satiability better mechanical strength catalyzing activity and strong surface acidity. Yet another object of the present invention is to provide for zirconium composite Involving simple and cost effective zirconium source which can be used for variety of end use / application such as ceramic toughening, alkaline resistance glass, solid super add and heterogeneous catalysis. Thus according the basic aspect of the present invention there is provided a process for the manufacture of mesoporous zirconium compound comprising: providing a selective zirconium complex using a water soluble zirconium compound ; providing a gel/ precipitation for phosphate from sald zirconium complex in the presence of a surfactant and selectively atleast one source of water soluble silicate and phosphate source; allowing the gel/ precipitation for phosphate to age at 80-100°C for 2-7 days; filtering, washing/ calcining and obtalning therefrom the mesoporous compound after drying. In the above process of the invention the sald zirconium complex is obtalned such as to be stable at alkaline pH. The sald complex of zirconium is ammoniuim zirconium carbonate complex preferably which is stable at pH 8.5. The water soluble zirconium compound is preferably selected from zirconium oxychloride and othere water soluble zirconium compounds comprising nitrates, sulphates, formate, perchlorate, sulfamate, bromide, organic sulfonates. The water soluble source of silicate comprise sodium or potassium silicate preferably sodium metasilicate solution. The water soluble source of phosphate used comprise diammonium hydrogen phosphate, disodum hydrogen phosphate and dipotassium hydrogen phosphate malntalning a pH in the alkaline range. In accordance with an aspect of the invention when disodium hydrogen phosphate and dipotassium hydrogen phosphate are used, sodium and potassium ions are washed off after gel ageing. Preferably, the water soluble zirconium compound used is zirconium oxychloride, the source of silicate is sodium silicate and sald source of phosphate is diammonium hydrogen phosphate. The selected anionic surfactant is sodium dodecyi sulphate (SOS). Other suitable anionic surfactants are Sodium-7-ethyl-2-methyl-4-undecyt-sulphate, linear alkylbenzene sulfonate /dodecyibenzene sulfonate, potassium lauryl phosphate, potassium monododecyl phosphate. Cetytrimethylammonium bromide (CTMABr) is selected as a suitable cationic surfactants from Cetytrimethylammonium bromide, Cetytrimethylammonium chloride, chloride or bromide of cetytpyridinium cation, dodecyltrlmethylammonium vation, dodecyttriethyl ammonium catlon,cetyltriethylammonium cation, though all other also give the similar results. In accordance with an aspect in the preparation of zirconia-silica mesocomposite the composition in moles of ingredients comprise Zirconium carbonate complex: Sodium silicate: sodium dodecyl sulphate;Water = 1:1-2:0.25-0.4:725-1000.Deflne SDS In accordance with another aspect in the preparation of mesoporous Zirconium phosphate the composition in moles comprise Zirconium carbonate complex : Phospahte: Cetytrimethylammonium bromide: water =1:1.5-2.5:0.25-0.35:175- 225.Define CTMABr In the above process of the invention the gel is aged at 80-100°C for 2-7 days in a Teflon lined autoclave and thereafter it is filtered, washed with water and finally methanol followed by drying at room temperature. In accordance with a preferred aspect for zirconia-sillca mesocomposite the composition in moles used comprise Zirconium carbonate complexrsodium silicate: sodium dodecyl sulphate: Water*l:2:0.3:1000;the gel is aged at about 80°C for 5 days and 100°C for 1day in Teflon lined autoclave and thereafter filtered, washed with water and finally methanol followed by drying at room temperature. The final product can also be obtalned by direct calcinations of the residue after filtration at 540°C for 6h. In accordance with another preferred aspect of the invention for mesoporous zirconium phosphate the composition in moles used comprise Zirconium carbonate complex:Phosphate: Cetytrimethylammonium bromide: Water=l:3:0.3:200;the gel is aged at about 80°C for 5 days and 100°C for 1 day in Teflon lined autoclave and thereafter ffltered,washed with water , dried and dispersed into methanol followed by drying at room temperature. The final product can also be obtalned by direct calcinations of the residue after filtration at 550°C for 8h. Examples: The detalls of the invention, its objects and advantages are explalned hereunder in greater detall in relation to non-limiting exemplary methods of manufacture of the mesoporous composites as hereunder: Example 1. Under this example a manner of manufacture of zlrconla - silica mesoporous composite is discussed. The preparation of zirconium carbonate complex was carried out as detalled hereunder: Pure zirconium carbonate complex was obtalned from commercially avallable zirconium oxychloride. Zirconium oxychloride was first dissolved in water. Ammonium carbonate solution is then added to it dropwise. White precipitate of zirconium carbonate appeared. It is then washed with distilled water to remove chloride ions. The precipitate was then dissolved into excess ammonium carbonate solution to prepare zirconium carbonate complex. The zirconium carbonate complex obtalned as above was next used to obtaln a get involving zirconia silica mesoporous composite composition (in moles) of the ingredients comprising: Zirconium Carbonate Complex : Sodium Silicate : Sodium Dodecyl Sulphate (SDS) : water in amounts of 1 : 2 : 0.3 : 1000. The gel thus obtalned was aged at 80 ° centigrade for 5 days and 100 ° centigrade for 1 day in a Teflon lined autoclave. After that it is filtered, washed with water and finally methanol .Thereafter the product was dried at room temperature . The BET surface of the composite obtalned was found to be 401.65 sq.m / g. while the pore size distribution was found to be 70% pore in the range of 4 - 6 nm. EDS analysis of the product revealed 40.82 atomic % Zr. And 59.18 atomic % Si. Example 2 Under this example the manner of manufacture of mesoporous zirconium phosphote was carried out as detalled hereunder: The zirconium carbonate complex In this process was obtalned as hereunder: Pure zirconium carbonate complex was obtalned from commercially avallable zirconium oxychloride. Zirconium oxychloride was first dissolved in water. Ammonium carbonate solution is then added to it dropwise. White precipitate of zirconium carbonate appeared. It is then washed with distilled water to remove chloride ions. The precipitate was then dissolved into excess ammonium carbonate solution to prepare zirconium carbonate complex. The above obtalned zirconium carbonate complex was used to obtalned a gel involving this zirconium carbonate complex : Phosphate : Cetytrimethylammonium bromide (CTMABr) : water in amounts of 1:3:0.3:200. Thus obtalned gel was next aged at 80Pc centigrade for 2 days and 100°C centigrade for 2 days in a Teflon lined autoclave. After that it was filtered, washed with water .Next ft was dried and dispersed into methanol adjusting the pH to 3 using HCL and thereafter stirred well followed by filtration and washing with methanol .Finally the composite was dried. The BET surface area of the composite was found to be 215.68 sq.m/g and 55% pores of the composite were found to lie between 5 to 20 nm. The EDS analysis of the composite showed 34.20 atomic % Zr and 65.80 atomic % P. The detalled result of BET surface area & pore volume distribution, low angle XRD, FTXR data, EDS analysis carried out on the composites obtaln the Example 1 above is provided in accompanying figures 1A, IB, 1C, and ID while the results of BET surface area & pore volume distribution, low angle XRD, FTIR data, EDS analysis carried out of the composite obtaln the Example 2 are provided in accompanying figures 2A, 2B, 2C and 2D respectively. It is thus possible by way of the above invention to provide for a cost-effective manner of manufacture of mesoporous composite in particular mesoporous zirconium phosphate and ZrO2 -SiO2 involving cost effective inorganic sources. Importantly, the inorganic sources used in the process are readily avallable and cost effective and the process is thus industrially viable and commercial beneficial in favour of large scale manufacture of such mesoporous compound composites. The cost effective composite of the invention should have beneficial use / application including as catalyst bed and mesoporous molecular sieves. The composites are suppose to have superior physicochemical properties such as high thermal and chemical stability, better mechanical strength catalytic activities and strong surface acidity. Importantly also the composites actively benefit wide variety of applications such as ceramic toughening, alkaline resistant glass, solid super add and heterogeneous catalysis and the like. Importantly the property / end characteristic of the composite can be varied depending upon the purpose and desired end use /application thereby imparting the provision for generating tallor made mesoporous zirconium composites for selective and cost-effective beneficial use. The mesoporous composite of the invention can thus serve as a promising cost effective catalyst and support material. WE CLAIM: 1. A process for the manufacture of mesoporous zirconium compound, comprising providing zirconium carbonate complex using a water soluble zirconium compound selected from zirconium oxychloride and other water soluble zirconium compounds comprising nitrates, sulphates, formate, perchlorate, sulfamate, bromide, organic sulfonates ; and obtalning a gel from sald zirconium carbonate complex using a surfactant and at least one source of water soluble silicate and phosphate source; subjecting the gel to aging at 80°C-100°C for 2-7 days; filtering, washing and finally drying at room temperature for obtalning therefrom the mesoporous zirconium compound. 2. A process for the manufacture of mesoporous zirconium compound as clalmed in clalm 1 wherein sald zirconium carbonate complex is obtalned such as to be metastable at alkaline pH. 3. A process for the manufacture of mesoporous zirconium compound as clalmed in anyone of clalms 1 to 2 sald water soluble source of silicate comprise sodium or potassium silicate preferably sodium metasilicate solution. 4. A process for the manufacture of mesoporous zirconium compound as clalmed in anyone of clalms 1 to 3 sald water soluble source of phosphate used comprise diammonium hydrogen phosphate, disodium hydrogen phosphate and dipotassium hydrogen phosphate malntalning a pH in the alkaline range. 5. A process for the manufacture of mesoporous zirconium compound as clalmed in clalm 4 wherein when disodium hydrogen phosphate and dipotassium hydrogen phosphate are used, sodium and potassium ions are washed off after gel ageing. 6. A process for the manufacture of mesoporous zirconium compound as clalmed in anyone of clalms 1 to 5 wherein preferably the water soluble zirconium compound used is zirconium oxychloride, the source of silicate is sodium silicate and sald source of phosphate is diammonium hydrogen phosphate. 7. A process for the manufacture of mesoporous zirconium compound as clalmed in anyone of clalms 1 to 6 wherein sald complex of zirconium comprise ammoniuim zirconium carbonate complex. 8. A process for the manufacture of mesoporous zirconium compound as clalmed in anyone of clalms 1 to 7 wherein sald anionic surfactant is selected from sodium dodecyl sulphate, Sodium-7-ethyl-2-methyl-4-undecyl-sulphate, linear alkylbenzene sulfonatest /dodecylbenzene sulfonate, potassium lauryl phosphate, potassium monododecyl phosphate preferably sodium dodecyl sulphate. 9. A process for the manufacture of mesoporous zirconium compound as clalmed in anyone of clalms 1 to 7 wherein sald surfactant used comprise a cationic surfactant selected from Cetytrimethylammonium bromide, Cetytrimethylammonium chloride ,chloride or bromide of cetylpyridinium cation, dodecyltrimethylammonium cation, dodecyltriethyl ammonium cation,cetyltriethylammonium cation. 10. A process for the manufacture of mesoporous zirconium compound as clalmed in anyone of clalms 1 to 7 wherein for preparation of zirconia-silica mesocomposite the composition in moles of ingredients comprise Zirconium carbonate complex: Sodium silicate:SDS;Water = 1:1-2:0.25-0.4:725-1000. 11. A process for the manufacture of mesoporous zirconium compound as clalmed in anyone of clalms 1 to 7 wherein for preparation of mesoporous Zirconium phosphate the composition in moles comprise Zirconium carbonate complex : Phospahte: CTMABr: water =1:1.5-2.5:0.25-0.35:175-225. 12. A process for the manufacture of mesoporous zirconium compound as clalmed in anyone of clalms 1 to 11 wherein the gel is aged at 80-100°C for 2-7 days in a Teflon lined autoclave and thereafter it is filtered, washed with water and finally methanol followed by drying at room temperature. 13. A process for the manufacture of mesoporous zirconium compound as clalmed in clalm 10 wherein for zirconia-silica mesocomposite the composition in moles used comprise Zirconium carbonate complex:sodium silicate:SDS: Water=l:2:0.3:1000;the gel is aged at about 80°C for 5 days and 100°C for 1 day in Teflon lined autoclave and thereafter filtered, washed with water and finally methanol followed by drying at room temperature. 14. A process for the manufacture of mesoporous zirconium compound as clalmed in clalm 13 wherein the composite comprise 40.82 % Zr and 59.18 atomic % Si in EDS analysis. 15. A process for the manufacture of mesoporous zirconium compound as clalmed in clalm 11 wherein for mesoporous zirconium phosphate the composition in moles used comprise Zirconium carbonate complex: Phosphate :CTMABr: Water=l:3:0.3:200;the gel is aged at about 80°C for 5 days and 100°C for 1 day in Teflon lined autoclave and thereafter filtered, washed with water , dried and dispersed into methanol followed by drying at room temperature. 16. A process for the manufacture of mesoporous zirconium compound as clalmed in clalm 15 wherein the composite comprise 34.20 atomic % Zr and 65.80 atomic % P in EDS analysis. 17. A process for the manufacture of mesoporous zirconium compound as clalmed in clalm 13 wherein the mesoporous composite synthesized is ZrO2 -SiO2 mesocomposite (1:2 molar ratio) having BET surface area of 401.65 sq.m / g. while the pore size distribution is found to be 70% pores in the range of 4 - 6 nm. 18. A process for the manufacture of mesoporous zirconium composite as clalmed in clalm 15 wherein the mesoporous composite synthesized is Zr-Phospahte mesocomposite (1:3 molar ratio) having BET surface area of 215.68 sq.m/g and 55% pores of the composite are found to lie between 5 to 20 nm. 19. A process for the manufacture of mesoporous zirconium composite as clalmed in anyone of clalms 1 to 18 wherein sald zirconium carbonate complex is obtalned by dissolving Zirconium oxychloride in water, adding dropwise Ammonium carbonate solution to form white precipitate of zirconium carbonate, washing to remove chloride ions and finally the precipitate was then dissolved into excess ammonium carbonate solution to obtaln zirconium carbonate complex. ABSTRACT Process for the manufacture of mesoporous Zirconium compounds and in particular to the manufacture of cost effective mesoporous zirconia-silica composite and mesoporous zirconium phosphate involving cost effective inorganic ingredients. The process basically involves using a selective zirconium complex using a water soluble zirconium compound; providing a gel/ precipitation for phosphate from sald zirconium complex in the presence of a surfactant and selectively atleast one source of water soluble silicate and phosphate source; allowing the gel/ precipitation for phosphate to age; and obtalning therefrom the mesoporous compound. The process is commercially viable and favour cost effective and large scale production of such zirconium composites. Importantly the mesoporous zirconium composite of the invention is directed for application / use in catalyst bed and as mesoporous molecular sieve.

Documents:

632-KOL-2004-ABSTRACT.pdf

632-kol-2004-amanded claims-1.1.pdf

632-KOL-2004-AMENDE CLAIMS.pdf

632-KOL-2004-CANCELLED PAGES.pdf

632-KOL-2004-CLAIMS.pdf

632-KOL-2004-CORRESPONDENCE 1.2.pdf

632-kol-2004-correspondence-1.1.pdf

632-KOL-2004-CORRESPONDENCE.pdf

632-KOL-2004-DESCRIPTION (COMPLETE).pdf

632-KOL-2004-DRAWINGS.pdf

632-KOL-2004-EXAMINATION REPORT 1.1.pdf

632-kol-2004-examination report.pdf

632-KOL-2004-FORM 1.pdf

632-kol-2004-form 18.pdf

632-KOL-2004-FORM 2.pdf

632-kol-2004-form 3.pdf

632-KOL-2004-GRANTED-ABSTRACT.pdf

632-KOL-2004-GRANTED-CLAIMS.pdf

632-KOL-2004-GRANTED-DESCRIPTION (COMPLETE).pdf

632-KOL-2004-GRANTED-DRAWINGS.pdf

632-KOL-2004-GRANTED-FORM 1.pdf

632-KOL-2004-GRANTED-FORM 2.pdf

632-KOL-2004-GRANTED-SPECIFICATION.pdf

632-kol-2004-pa.pdf

632-KOL-2004-REPLY TO EXAMINATION REPORT.pdf

632-kol-2004-specification.pdf