Title of Invention

PROCESS FOR PREPARATION OF MESOPOROUS CLAY

Abstract

A process for preparation of mesoporous clay comprising 20 to 40 weight percent phosphate and 60 to 80 weight percent clay and having meso-pores in the range of 80-120 A for use as a catalyst for cracking lower bottoms in hydrocarbon conversion reactions and also as an active base to support conventional catalysts , said process comprising the step of: (a) preparing clay slurry having from 50 to 70 weight percent freshly ground and optionally calcined clay; (b) decreasing the pH of the clay slurry of step (a) to a level such as herein described which is conducive to formation of a viscous mass complex; (c) contacting the clay slurry of step (b) with a phosphate ion source for at least 4 hours, and; (d) drying the slurry of step (c) to produce the mesoporous clay particles comprising 20 to 40 weight percent phosphate and 60 to 80 weight percent clay and having meso-pores in the range of 80 to 120 A.

Full Text

FORM 2 THE PATENTS ACT, 1970 (39 of 1970) COMPLETE SPECIFICATION (See section 10) "PROCESS FOR PREPARATION OF MESOPOROUSLLAY INDIAN OIL CORPORATION LIMITED, a Public Limited Company, having its Head Office at G-9, AIi Yavar Jung Marg, Bandra (East), Mumbai 400 051, India. The following specification (particularly) describes the nature of the invention and the manner in which it is to be performed. GRANTED 11-2-2005 Field of the Invention: The present invention provides a process for preparing clay having meso pores (pore size in the range of 80 to 120 A) which comprises reacting phosphoric acid and clay and aging the reaction mixture for at least 4 hours to obtain clay having meso-pores while maintaining its surface area. The clay thus obtained can act both as a catalyst for cracking lower bottoms in hydrocarbon conversion reactions and also as an active base to support conventional catalysts used in cracking, hydrocracking, reforming, isomensation and other refining processes. The availability of pore sizes in the range of 80 to 120A is responsible for bottom cracking of heavy residues. The present invention also provides a novel catalyst system for hydrocarbon conversion reactions comprising an active clay support having meso pores (pore size in the range of 80-120 A) and a conventional zeolite catalyst. Background and Prior Art References: Certain types of clays are long known for their use in catalysis, especially in high temperature reactions like cracking, hydrocracking, etc. Prior to invention of zeolites, clays were widely used in cracking catalysis. The reasons for their use are many: they are cheap, abundantly available in relatively pure form, high temperature resistant and easy to handle. The clays were subjected to acid/base treatments before use. With the invention of zeolite with their magnificent acid properties, shape selectivity and reactivity, clays started to loose their importance as prime active component though, they continued to be used as diluents and heat reservoirs or heat sinks. The alternative roles, the clays played, were no less important. They were supposed to protect the active zeolite component from destruction during the course of reactions. During the last 50 years, clay is the dominant component for processes like Fluid Catalytic Cracking (FCC), Hydrocracking etc. The use of clay in the prior art can be described in the following areas, (1) Catalyst (2) Support and (3) Binder. Let us discuss the role of clay as perceived in these uses. Catalyst: Catalytic use was confined to earlier days prior to zeolite The limitations were many Reaction on clay catalysts was non -selective and life was limited. Support: During the last 50 years clay was mainly used as support but inactive support, while other components like silica-alumina, alumina etc are often used as active matrix. They take part in the primary reactions and subsequently the active component, i.e. zeolite takes over. The acid treated clay used in the earlier days was very non-selective and often generated more coke in the cracking reactions. There is a gap in the research domain regarding conscious use of clay as active support in cracking and other reactions. Binder: In the last decade, clay is finding increasing use as binder A cheap binder. Many researchers attempted to impart secondary properties in clay. However, binding remained the major area where considerable work is done. Gap areas: Let us consider clay as active support. Clay is an ideal material for cracking if suitable porosity is generated insitu. Which pores are important? Zeolite has a fixed pore size; it does not allow entry of molecules bigger than this size. Conventional alumina or silica alumina matrix has pore sizes ranging from 80-100 angstroms and above. Any attempt to synthesize pores in the post-zeolite range between 20-100 is difficult. These pores in a conventional silica alumina matrix is unstable and decomposes under hydrothermal conditions. Can meso pores of required sizes be created on clay itself, can support materials for catalyst be' prepared using this pore modified clay, will this clay remain active under severe hydro thermal conditions, these are a few of many unanswered questions which are bothering researchers in the field for quite some time. However while looking for solutions to these problems one has to take care of undesirable reactions which reactive clay may induce. It has been rightly pointed out in United States Patent 5,288,739 by Demmel that "independent catalytic activity has proved to be an advantage in catalyzing some chemical reactions, but a disadvantage in catalyzing many others ... many of these glue or binder materials also are chemically reactive with many of the different kinds of catalyst particles they are called upon to bind together. Such chemical reactivity between a given binder material and a given species of catalyst particle may be an advantage in some cases, but generally speaking it is not considered to be an advantage; and in many cases it may well constitute a serious detriment to the catalytic activity of a given species of catalyst". So while designing a pore modified active clay support it is necessary to see to it that this activity do not interfere with the primary activity of the major catalyst components. US patent 5,231,064 (Absil et al.) describes use of phosphate treated clays as a component for FCC catalyst formulation. Absil et al. envisages use of clay as a low cost component which ensures attrition resistance to the active zeolite catalyst and not as an active catalyst in itself. The object of the process of Absil et al. was to increase the attrition resistance of the catalyst. However, in the present invention, the main purpose is to develop meso-pores having pore size in the range of 20-100 A. Further, the attrition resistant catalyst produced by Absil et al. has improved activity for gasoline octane enhancement or light olefin production in the catalytic cracking of crude oil. However, the clay produced in the present invention shows improved lower bottom cracking. Thus, the objects and also the utility of the present invention and Absil et al. are totally different. It is essential to notice that the contact time between the phosphoric acid and the clay as described in Absil et al. should be less than 95 minutes, preferably less than 30 minutes and most preferably less than 15 minutes, which is not sufficient to develop meso-pores in the clay. By performing the process as described by Absil et al., the Applicants have found that the average pore diameter of the clay thus obtained is always greater than the average pore size of the base clay taken at the starting and always lies above 130 A. Thus, meso-pores are not developed in the clay by following the process of Absil et al. The Applicants have surprisingly found that if the contact time between the clay particles and the phosphoric acid is long, preferably not less than 3 hours and most preferably not less than 4 hours, meso-pores are developed in the clay. Thus, Absil et al does not teach or suggest the process of developing meso-pores in the clay and a person of ordinary skill in the art will not be able to envisage the novel step of developing meso-pores in the clay by reading Absil et al. OBJECTS OF THE PRESENT INVENTION: The main object of the present invention is to develop a process for preparing clay having meso-pores for use as a catalyst for cracking lower bottoms in hydrocarbon conversion reactions and also as an active base to support conventional catalysts. Another object of the present invention is to develop a process for preparing clay having an average pore diameter of 80-120A and capable of reducing undesirable bottoms during the process of cracking. Still another object of the present invention is to provide a novel catalyst system for hydrocarbon conversion reactions comprising an active clay support having meso pores (pore size in the range of 80-120 A) and a conventional zeolite catalyst. SUMMARY OF THE PRESENT INVENTION: The present invention provides a process for preparing clay having meso pores (pore size in the range of 80 to 120 A) while maintaining its surface area which comprises reacting phosphoric acid and clay and aging the reaction mixture for at least 4 hours. The clay thus obtained can act both as a catalyst for cracking lower bottoms in hydrocarbon conversion reactions and also as an active base to support conventional catalysts used in cracking, hydrocracking, reforming, isomensation and other refining processes. The availability of pore sizes in the range of 80 to 120A is responsible for bottom cracking of heavy residues. The present invention also provides a novel catalyst system for hydrocarbon conversion reactions comprising an active clay support having meso pores (pore size in the range of 80-120 A) and a conventional zeolite catalyst. STATEMENT OF THE INVENTION: Accordingly, the present invention provides a process for preparation of mesoporous clay comprising 20 to 40 weight percent phosphate and 60 to 80 weight percent clay and having meso-pores in the range of 80-120 A for use as a catalyst for cracking lower bottoms in hydrocarbon conversion reactions and also as an active base to support conventional catalysts, said process comprising the step of: (a) preparing clay slurry having from 50 to 70 weight percent freshly ground and optionally calcined clay; (b) decreasing the pH of the clay slurry of step (a) to a level such as herein described which is conducive to formation of a viscous mass complex; (c) contacting the clay slurry of step (b) with a phosphate ion source for at least 4 hours, and; (d) drying the slurry of step (c) to produce the mesoporous clay particles comprising 20 to 40 weight percent phosphate and 60 to 80 weight percent clay and having meso-pores in the range of 80 to 120 A. BRIEF DESCRIPTION OF THE ACCOMPANYING DRAWING: Figure 1 represents modified pore size distribution of clays incremental surface area Vs pore diameter. DETAILED DESCRIPTION OF THE PRESENT INVENTION: Accordingly, the present invention provides a method of preparing clay having meso-pores in the range of 80-120 A for use as a catalyst for cracking lower bottoms in hydrocarbon conversion reactions and also as an active base to support conventional catalysts, said process comprising the step of: (a) preparing clay slurry having from 50 to 70 weight percent freshly ground and optionally calcined clay; (b) decreasing the pH of the clay slurry of step (a) to a level which is conducive to formation of a viscous mass complex; (c) contacting the clay slurry of step (b) with a phosphate ion source for at least 4 hours, and (d) drying the slurry of step (c) to produce dry clay particles such that the clay particles obtained have meso-pores in the range of 80 to 120 A and will comprise of about 20 to about 40 weight percent phosphate and from about 60 to about 80 weight percent clay. In an embodiment of-the present invention, the phosphate ion source is phosphoric acid. In another embodiment of the present invention, the starting clay is optionally calcined at a temperature ranging between 500°C and 900 °C. In yet another embodiment of the present invention, the starting clay is calcined for 60 minutes to 240 minutes. In still another embodiment of the present invention, wherein prior to the step of drying, additional amount of water is added to the concentrated clay slurry to bring the concentration of clay in the slurry to about 40 weight percent. In a further embodiment of the present invention, prior to the step of drying, a dispersing agent selected from the group consisting of sodium pyrophosphate or sodium meta acrylate is optionally added to the clay slurry. In one more embodiment of the present invention, the drying of the clay/phosphate slurry in step (d) is accomplished by spray drying. In one another embodiment of the present invention, the dried clay particles are optionally calcined at temperatures ranging between 500°C and 900 °C. In an embodiment of the present invention, the dried clay particles are calcined for 60 minutes to 240 minutes. In another embodiment of the present invention, the clay is naturally occurring clay and preferably kaolin. In still another embodiment of the present invention, the pore modified clay is obtained without affecting the surface area of the clay. In a further embodiment of the present invention, the pore modified clay is obtained without affecting the thermal stability of the clay. In one more embodiment of the present invention, the pore modified clay provides access to bulk sized hydrocarbon molecules that constitute major portion of the bottom of the barrel. In another embodiment of the present invention, the pore modified clay thus obtained shows 3 to 10% increase in bottom reduction when used in FCC catalyst composition. In yet another embodiment of the present invention, the pore modified clay acts both as a catalyst and support for conventional catalysts used in cracking, hydrocracking, reforming, isomensation and other refining processes. The catalytically active clay composite is taken in the range of 1-5 wt % and mixed with FCC catalyst for obtaining enhanced yields of liquefied petroleum gas. The present invention is further explained in the form of the following preferred embodiments which are given to make the present invention more clear to a person skilled in the art and hence, should not be construed to limit the scope of the invention in any manner. In a preferred method, for preparing the pore modified active clay support, 1) clay slurry having from 50 to 70 weight percent freshly ground clay, optionally calcined is prepared (2) its pH is reduced to a level which is conducive to formation of an viscous mass complex, (3) the clay slurry is then provided with phosphate ions by introducing therein phosphate component such that the clay particles ultimately made from the slurry comprises of about 20 to about 40 weight percent phosphate and from about 60 to about 80 weight percent clay; (4) the slurry is then dried to produce solid clay particles, (5) the dried solid clay particles thus obtained are calcined to produce pore modified clay particles. As per the preferred method of this invention it has been shown that the starting clay could be in any form, either fresh or calcined. The calcinations can be conducted at temperature range between 500 to 900°C. The textural studies were conducted in Accelerated Surface Area and Porosimetry(ASAP)-2010 unit from M/S Micromentics®, USA. Nitrogen adsorption isotherm data were generated for all the samples and BJH approximation was used to determine pore size distribution data. The data generated for the base clay and pore modified clay are given in the Table 1. This table provides a comparison of pore size distribution of base and modified clay on incremental pore area and volume basis in the range of pores between 15 and 250 A. This is the range where the tailoring is attained due to modification. The data in the table indicate that in the whole zone there is observed an increase in pore area or volume after modification. Table 1: Comparison of Pore Size Distribution of base and modified clay on incremental pore area and volume basis. Average Pore Diameter A Incremental Pore Area (m2/g) Incremental Pore Volume (g/cc) Base Clay Modified C/ay Base Clay Modified Clay 250 2.722 3.002 0.018263 0.017386 190 0.61 0.735 0.002443 0.003436 170 0.676 0.8 0.002802 0.003274 150 0.745 0.89 0.0035378 0.003267 130 0.83 1.015 0.0018372 0.003221 110 0.953 1.203 0.002579 0.003253 90 1.153 1.485 0.002516 0.003305 70 1.453 2.047 0.002494 0.0035 50 2.525 . 3.725 . 0.003054 0.004466 30 5.125 7.029 0.003829 ' 0.005288 15 0.378 0.407 0.000176 0.000193 A graphical representation of this pore size distribution is shown in Figure 1 in the form of bar chart. The data is shown for the base clay or the starting clay and two clay samples A and C modified as per the process of the present invention and in accordance with examples 1 and 3. Figure 1 shows significant increase in number of pores having diameter in the lower regions i.e. between 15 and 150 A for samples A and C. It is to be noted that, irrespective of prior calcination of clay samples, the final modified clay contain such tailored porosity. This effect is more when the final clay is washed to remove the leached alumina atoms. Thus modified clay in final dried form could be used as catalyst or catalyst support. Also, modified clay in the slurry form could be used as support in any aqueous precursor slurry for catalyst. The pore-modified clay prepared as per the process of this invention has many useful properties which could be put to use in catalysis in general and refining catalysis in particular. As specific examples of use, the following can be sited, however they are not limiting. 1. As Catalyst support 2. As Bottom Cracking Component We shall now discuss in brief the above examples. Catalyst Support: Cracking catalyst using pore modified clay of the present invention is made as per the following preferred embodiment. Pore modified clay slurry prepared by the process of present invention is added to finely dispersed alumina and the resulting mixture is combined with a solution of zeolite powder under high shear mixing conditions to obtain a spray drier feed slurry that contains 20 to 45 wt% solids which preferably comprises (on a dry basis) 1 to 10 wt% alumina, 4-8 wt% phosphate, 0.3-10 wt% zeolite and 70 to 90 wt% kaolin. The catalyst slurry is held in a spray dryer feed storage tank under mixing conditions and is spray dried at a temperature of 200°C to 400°C and calcined for 1 hour at a temperature of 450-600 °C. In the present invention, part of the clay can be substituted with other finely divided inorganic components such as other types of clays, silica, alumina, silica-alumina gels and sols may be included. The paniculate spray dried catalyst has a particle size range of 20 to 150 microns, preferably 20-120 microns and is held in catalyst storage container prior to use. The catalyst may be used as in a conventional FCC unit wherein the it is reacted with a hydrocarbon feedstock at 400 to 700°C, preferably at 400-600°C and regenerated at 500 to 850T, preferably at 500-750X, to remove coke. Typically the catalyst possesses an attrition index of 3-15, and preferably 5-10, as determined by the IOC Attrition Index Test described as follows The catalyst samples were calcined at 538 °C for 3 hours prior to measurement for attrition resistance (index). In the method catalyst attrition at high, constant air jet velocity was measured The fines were removed continuously from the attrition zone by elutriation into a flask-thimble assembly, and weighed at periodic intervals. It is assumed that the test conditions are similar to those encountered in hydrocarbon conversion operations. The attrited or overhead catalyst so measured is expressed as the weight percent overhead. Percent attrition is calculated as follows: Grams overhead in 5-20 hours period * 100 50 gnu (initial) charge — gms overhead in 0-5 hrs. peri Percent attrition is also referred to as attrition index. Lower the index, better is the attrition index property of catalyst. Spray drying of gas inlet/outlet temperature of 300 to 350°C/100-200°C is used in the preparation of FCC catalysts. This catalyst could be used to crack feedstock such as gas-oil, residual oil and mixtures thereof Bottom Cracking Component: The pore-modified clay prepared as per the process of this invention can be used as a bottom cracking component also. The presence of higher amount of meso pores in the range of 20-90A is conducive in accommodating bulkier hydrocarbon molecules which form the major part of high boiling fractions named as bottom. Presence of meso pores and secondary acid centers due to uprooted alumina molecules makes cracking of bottoms easier. Catalyst made as per process above when evaluated for bottom cracking confirm this and is shown in the Table 5 elsewhere in this application. Having described the basic aspect of our invention the following specific examples are given to illustrate specific preferred embodiments, Example-1: Uncalcined clay 1064 gm of kaolin clay was freshly ground and clay slurry having from 50 to 70 weight percent clay was prepared by adding 821 gm of demmeralised water (DM) to the clay. The pH of the slurry was reduced by addition of phosphoric acid to a level which is conducive to formation of a viscous mass complex. The clay slurry is then provided with phosphate ions by introducing therein 122g of phosphoric acid (85 wt %, LR grade, SD Fine Chem, Mumbai, India) solution such that the clay particles ultimately made from the slurry comprises of about 20 to about 40 weight percent phosphate and from about 60 to about 80 weight percent clay. The slurry was aged for 4 hours and then dried at 110 °C for 16 hours to produce solid clay particles. The solid clay particles thus obtained are calcined at 500°C for 1 hour to produce pore modified clay particles. The product is identified as A. Example-2: Clay calcined at 500°C 1064 gm of kaolin clay calcined at 500°C for 1 hour was freshly ground and clay slurry having from 50 to 70 weight percent clay was prepared by adding 821 gm of demineralised water to the clay. The pH of the slurry was reduced by addition of phosphoric acid to a level which is conducive to formation of an viscous mass complex. The clay slurry is then provided with phosphate ions by introducing therein 122g of phosphoric acid (85 wt %, LR grade, SD Fine Chem, Mumbai, India) solution such that the clay particles ultimately made from the slurry comprises of about 20 to about 40 weight percent phosphate and from about 60 to about 80 weight percent clay. The slurry was aged for 4 hours and then dried at 110°C for 16 hours to produce solid clay particles. The solid clay particles are calcined at 500°C for 1 hour to produce pore modified clay particles. The product is identified as B. Example-3: Clay calcined at 900°C 1064 gm of kaolin clay calcined at 900°C for 1 hour was freshly ground and clay slurry having from 50 to 70 weight percent clay was prepared by adding 821 gm of demineralised water to the clay. The pH of the slurry was reduced by addition of phosphoric acid to a level which is conducive to formation of an viscous mass complex. The clay slurry is men provided with phosphate ions by introducing therein 122g of phosphoric acid (85 wt %, LR grade, SD Fine Chem, Mumbai, India) solution such that the clay particles ultimately made from the slurry comprises of about 20 to about 40 weight percent phosphate and from about 60 to about 80 weight percent clay. The slurry was aged for 4 hours and then dried at 110 °C for 16 hours to produce solid particles and calcined at 500°C for 1 hour to produce pore modified clay particles. The product is identified as C. The average pose size values of these clays are given in table 2. These data were generated by nitrogen adsorption studies on modified clay samples. Table 2: Comparison of the average pore size of the base clay with the catalysts obtained in Examples 1, 2 and 3. Property Base clay Clay A ClayB ClayC Average Pore Diameter (A) 122 89 85 82.3 Example-4: Formulation of cracking catalyst using pore modified active clay support 2008 gm pore modified active clay support slurry prepared as per example 1, having pH of 1.2 was taken in a.10 liter container and kept under stirring. To this slurry, 625 gm of alumina with a solid content of 20wt% and pH of 8.5 was added under stirring. The mixture was homogenized by vigorous stirring for 10 minutes and the pH of the mixture was recorded as 2.5. 130.21 gm of ZSM-5 zeolite (procured from M/s Zeolysl, USA) with moisture content of 4 wt%, was ground to a fine paste with equal amount of de-mineralized water and 0.35 wt% of hexa sodium metaphosphate (based on volatile free zeolite) and added to support-alumina slurry mixture under stirring. Stirring was continued for another 10 minutes, pH was recorded as 2.9. Final slurry with solid concentration of 30-wt %, was spray dried with a feed rate of 80 g/min. Spray dried micro spheres were then calcined at 500 °C for 1 hour. Calcined catalyst micro spheres were sieved and fraction between, 100 and 325 mesh were considered. This fraction was selected for further characterization. The catalyst was analyzed for surface area, which was found to be 49 m2/g. Physical properties of the catalyst prepared as per the present invention are provided below in table 3. Table 3: Properties of the Catalyst Property Value Surface Area (m2/g) 49 Average Bulk Density 0.79 Attrition Index (wt%) 3.5 The calcined catalyst was steam deactivated at 750°C for 3 hrs and was evaluated for performance at Simulated MAT conditions with standard feed. The readings of the same are given in Table 4. Table 4: Standard Feedstock Distillation Data Wt% °C IBP 315 5 327 10 334 20 346 30 356 40 365 50 375 60 386 70 399 80 415 90 440 95 463 FBP 528 Pour Point 36 Density 15 °C (g/cc) 0.87 CCR (wt%) 0.008 RCR (wt%) 0.04 Table 5 below provides performance data of catalyst prepared using pore modified clay support as per the process of the present invention and compares it with that of a commercial catalyst. The data in column 2 is for a case when typical commercial catalyst was taken for performance studies. This table shows that catalyst prepared as per the process reduces undesirable bottom (370 + wt%) compared to others. The catalytic activity is also enhanced. Table 5: Performance of the Catalyst Sample No. Base Clay With Pore Modified Active Clay Support Conversion (Wt%) 58.12 63.29 Catalyst to Oil Ratio 0.90 0.90 370+ (wt%) 14.82 11.30 We Claim; 1. A process for preparation of mesoporous clay comprising 20 to 40 weight percent phosphate and 60 to 80 weight percent clay and having meso-pores in the range of 80-120 A for use as a catalyst for cracking lower bottoms in hydrocarbon conversion reactions and also as an active base to support conventional catalysts , said process comprising the step of: (a) preparing clay slurry having from 50 to 70 weight percent freshly ground and optionally calcined clay; (b) decreasing the pH of the clay slurry of step (a) to a level such as herein described which is conducive to formation of a viscous mass complex; (c) contacting the clay slurry of step (b) with a phosphate ion source for at least 4 hours, and; (d) drying the slurry of step (c) to produce the mesoporous clay particles comprising 20 to 40 weight percent phosphate and 60 to 80 weight percent clay and having meso-pores in the range of 80 to 120 A. 2. A process as claimed in claim 1, wherein the phosphate ion source is phosphoric acid. 3. A process as claimed in claim 1, wherein the starting clay is optionally calcined at a temperature ranging between 500°C and 900 °C. 4. A process as claimed in claim 3, wherein the starting clay is calcined for 60 minutes to 240 minutes. 5. A process as claimed in claim 1, wherein prior to the step of drying, additional amount of water is added to the concentrated clay slurry to bring the concentration of clay in the slurry to about 40 weight percent. ,6. A process as claimed in claim 1, wherein prior to the step of drying, a dispersing agent selected from the group consisting of sodium pyrophosphate or sodium meta acrylate is optionally added to the clay slurry. 7. A process as claimed in claim 1, wherein the drying of the clay/phosphate slurry in step (d) is accomplished by spray drying. 8. A process as claimed in claim 1, wherein the dry clay particles are optionally calcined at temperatures ranging between about 500°C and about 900 °C. 9. A process as claimed in claim 8, wherein the dry clay particles are calcined for 60 minutes to 240 minutes. A process as claimed in claim I, wherein the clay is naturally occurring clay and preferably, kaolin. 11. A process for preparing clay having meso-pores in the range of 80-120 A substantially as herein described with reference to the accompanying drawing and the foregoing examples. Dated this 16th day of March, 2004. G. DEEPAK SRINIWAS Of K& S Partners Agent for the Applicants

Documents:

328-mum-2004 cancelled pages(11-2-2005).pdf

328-mum-2004 claims(11-2-2005).pdf

328-mum-2004 correspondence(22-2-2007).pdf

328-mum-2004 correspondence(ipo)(19-6-2007).pdf

328-mum-2004 drawing(11-2-2005).pdf

328-mum-2004 form 1(17-3-2004).pdf

328-mum-2004 form 1(19-5-2004).pdf

328-mum-2004 form 19(19-5-2004).pdf

328-mum-2004 form 2(granted)(11-2-2005).pdf

328-mum-2004 form 26(3-5-2004).pdf

328-mum-2004 form 3(17-3-2004).pdf

328-mum-2004 form 5(19-5-2004).pdf

328-mum-2004 petition under rule 137(14-2-2000).pdf

328-mum-2004 power of attorney(11-2-2005).pdf

328-mum-2004-claims(granted)-(11-2-2005).doc

328-MUM-2004-CORRESPONDENCE(30-1-2012).pdf

328-MUM-2004-FORM 15 (30-1-2012).pdf

328-mum-2004-form 2(granted)-(11-2-2005).doc

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