|Title of Invention||
"A SYNTHETIC PORUS CRYSTALLINE MATERIAL "
|Abstract||A synthetic porous crystalline material, of the kind such herein defined, having a 3-dimensional channel system comprising a first set of generally parallel channels each of which is defined by a 10-membered ring of tetrahedrally coordinated atoms, a second set of generally parallel channels which are also defined by 10-menbered rings of tetrahedrally coordinated atoms and which intersect with the channels of the first set, and a third set of generally parallel channels which intersect with the channels of said first and second sets and each of which is defined by a 9-membered ring of tetrahedrally coordinated atoms.|
|Full Text||The present invention relates to a synthetic porous crystalline material.
Field of the Invention
 This invention relates to a novel synthetic porous crystalline
material, ITQ-13, to a method for its preparation and to its use in catalytic conversion of organic compounds.
Description of the Prior Art
 Zeolitic materials, both natural and synthetic, have been demonstrated in the past to have catalytic properties for various types of hydrocarbon conversion. Certain zeolitic materials are ordered, porous crystalline metallosilicates having a definite crystalline structure as determined by X-ray diffraction, within which there are a large number of smaller cavities which may be interconnected by a number of still smaller channels or pores. These cavities and pores are uniform in size within a specific zeolitic material. Since the dimensions of these pores are such as to accept for adsorption molecules of certain dimensions while rejecting those of larger dimensions, these materials have come to be known as "molecular sieves" and are utilized in a variety of ways to take advantage of these properties.
 Such molecular sieves, both natural and synthetic, include a wide
variety of positive ion-containing crystalline silicates. These silicates can be described as a rigid three-dimensional framework of SiO4 and Periodic Table Group IIIA element oxide, e.g., AIO4, in which the tetrahedra are cross-linked by the sharing of oxygen atoms whereby the ratio of the total Group IIIA element and silicon atoms to oxygen atoms is 1:2. The electrovalence of the tetrahedra
containing the Group IIIA element is balanced by the inclusion in the crystal of a cation, for example an alkali metal or an alkaline earth metal cation. This can be expressed wherein the ratio of the Group IIIA element, e.g., aluminum, to the number of various cations, such as Ca/2, Sr/2, Na, K or Li, is equal to unity. One type of cation may be exchanged either entirely or partially with another type of cation utilizing ion exchange techniques in a conventional manner. By means of such cation exchange, it has been possible to vary the properties of a given silicate by suitable selection of the cation. The spaces between the tetrahedra are occupied by molecules of water prior to dehydration.
 Prior art techniques have resulted in the formation of a great variety of synthetic zeolites. Many of these zeolites have come to be designated by letter or other convenient symbols, as illustrated by zeolite A (U.S. Patent 2,882,243); zeolite X (U.S. Patent 2,882,244); zeolite Y (U.S. Patent 3,130,007); zeolite ZK-5 (U.S. Patent 3,247,195); zeolite ZK-4 (U.S. Patent 3,314,752); zeolite ZSM-5 (U.S. Patent 3,702,886); zeolite ZSM-11 (U.S. Patent 3,709,979); zeolite ZSM-12 (U.S. Patent 3,832,449), zeolite ZSM-20 (U.S. Patent 3,972,983); ZSM-35 (U.S. Patent 4,016,245); zeolite ZSM-23 (U.S. Patent 4,076,842); zeolite MCM-22 (U.S. Patent 4,954,325); and zeolite MCM-35 (U.S. Patent 4,981,663), merely to name a few.
 Although most frequently encountered in aluminosilicate form, many zeolites are known in silicate and borosilicate forms. For example, silicalite is a silicate form of ZSM-5 and is disclosed in U.S. Patent 4,061,724, whereas AMS-1B is a borosilicate form of ZSM-5 and is disclosed in U.S. Patent 4,269,813. In addition, GB-A-2,024,790 discloses borosilicate forms of zeolite beta (boralite B), ZSM-5 (boralite C) and ZSM-11 (boralite D).
 Many zeolites are synthesized in the presence of an organic directing agent, such as an organic nitrogen compound. For example, ZSM-5 may be synthesized in the presence of tetrapropylammonium cations and zeolite MCM-22 may be synthesized in the presence of hexamethyleneimine. It is also known from U.S. Patent No. 5,464,799 that zeolites EU-1 and NU-85 can be synthesized in the presence of hexamethonium bromide hexamethylenebis(trimethylammonium) bromide],
 It is also known to use fluoride-containing compounds, such as hydrogen fluoride, as mineralizing agents in zeolite synthesis. For example, EP-A-337,479 discloses the use of hydrogen fluoride in water at low pH to mineralize silica in glass for the synthesis of ZSM-5.
SUMMARY OF THE INVENTION
 The present invention is directed to a novel porous crystalline material, ITQ-13, having, in its calcined form, an X-ray diffraction pattern including values substantially as set forth in Table I below.
 The invention further resides in a method for preparing ITQ-13 and in the conversion of organic compounds contacted with an active form of ITQ-13.
DESCRIPTION OF DRAWINGS
 Figure 1 is a schematic illustration of a unit cell of ITQ-13, showing the positions of the tetrahedral atoms
 Figure 2 is a schematic illustration of the nine-ring channel system of ITQ-13, again showing the positions of the tetrahedral atoms.
 Figures 3 and 4 are illustrations similar to Figure 2 of the ten-ring channel systems of ITQ-13.
 Figures 5 and 6 shows the X-ray diffraction patterns of the as-synthesized and as-calcined products, respectively, of Example 2.
DESCRIPTION OF SPECIFIC EMBODIMENTS
 The synthetic porous crystalline material of this invention, ITQ-13, is a single crystalline phase which has a unique 3-dimensional channel system comprising three sets of channels. In particular, ITQ-13 comprises a first set of generally parallel channels each of which is defined by a 10-membered ring of tetrahedrally coordinated atoms, a second set of generally parallel channels which are also defined by 10-membered rings of tetrahedrally coordinated atoms and which are perpendicular to and intersect with the channels of the first set, and a third set of generally parallel channels which intersect with the channels of said first and second sets and each of which is defined by a 9-membered ring of tetrahedrally coordinated atoms. The first set of 10- ring channels each has cross-sectional dimensions of about 4.8 Angstrom by about 5.5 Angstrom, whereas the second set of 10-ring channels each has cross-sectional dimensions of about 5.0 Angstrom by about 5.7 Angstrom. The third set of 9-ring channels each has cross-sectional dimensions of about 4.0 Angstrom by about 4.9 Angstrom.
 The structure of ITQ-13 may be defined by its unit cell, which is the smallest structural unit containing all the structural elements of the material. Table 1 lists the positions of each tetrahedral atom in the unit cell in nanometers; each tetrahedral atom is bonded to an oxygen atom which is also bonded to an adjacent tetrahedral atom. Since the tetrahedral atoms may move about due to
other crystal forces (presence of inorganic or organic species, for example), a range of + 0.05 nm is implied for each coordinate position.
Table 1(Table Removed)
 ITQ-13 can be prepared in essentially pure form with little or no detectable impurity crystal phases and has an X-ray diffraction pattern which is distinguished from the patterns of other known as-synthesized or thermally treated crystalline materials by the lines listed in Table 2 below.
Table 2(Table Removed)
 These X-ray diffraction data were collected with a Scintag diffraction system, equipped with a germanium solid state detector, using copper K-alpha radiation. The diffraction data were recorded by step-scanning at 0.02 degrees of two-theta, where theta is the Bragg angle, and a counting time of 10 seconds for each step. The interplanar spacings, d's, were calculated in Angstrom units, and the relative intensities of the lines, I/I0 is one-hundredth of the intensity of the strongest line, above background, were derived with the use of a profile fitting routine (or second derivative algorithm). The intensities are uncorrected for Lorentz and polarization effects. The relative intensities are given in terms of the symbols vs = very strong (80-100), s = strong (60-80), m = medium (40-60), w = weak (20-40), and vw = very weak (0-20). It should be understood that diffraction data listed for this sample as single lines may consist of multiple overlapping lines which under certain conditions, such as differences in crystallographic changes, may appear as resolved or partially resolved lines. Typically, crystallographic changes can include minor changes in unit cell parameters and/or a change in crystal symmetry, without a change in the structure. These minor effects, including changes in relative intensities, can also occur as a result of differences in cation content, framework composition, nature and degree of pore filling, crystal size and shape, preferred orientation and thermal and/or hydrothermal history.
 The crystalline material of this invention has a composition involving the molar relationship:
wherein X is a trivalent element, such as aluminum, boron, iron, indium, and/or gallium, preferably boron; Y is a tetravalent element such as silicon, tin, titanium and/or germanium, preferably silicon; and n is at least about 5, such as about 5 to oo, and usually from about 40 to about oo. It will be appreciated from the permitted values for n that ITQ-13 can be synthesized in totally siliceous form in which the trivalent element X is absent or essentially absent.
 Processes for synthesizing ITQ-13 employ fluorides, in particular HF, as a mineralizing agent and hence, in its as-synthesized form, ITQ-13 has a formula, on an anhydrous basis and in terms of moles of oxides per n moles of YO2, as follows:
wherein R is an organic moiety. The R and F components, which are associated with the material as a result of their presence during crystallization, are easily removed by post-crystallization methods hereinafter more particularly described.
 The crystalline material of the invention is thermally stable and in the calcined form exhibits a high surface area and significant hydrocarbon sorption capacity.
 To the extent desired and depending on the X2O3/YO2 molar ratio of the material, any cations in the as-synthesized ITQ-13 can be replaced in accordance with techniques well known in the art, at least in part, by ion exchange with other cations. Preferred replacing cations include metal ions, hydrogen ions,
hydrogen precursor, e.g., ammonium ions and mixtures thereof. Particularly preferred cations are those which tailor the catalytic activity for certain hydrocarbon conversion reactions. These include hydrogen, rare earth metals and metals of Groups IIA, IIIA, IVA, VA, IB, IIB, IIIB, IVB, VB, VIB, VIIB and VIII of the Periodic Table of the Elements.
 The crystalline material of the invention may be subjected to treatment to remove part or all of any organic constituent. This is conveniently effected by thermal treatment in which the as-synthesized material is heated at a temperature of at least about 370°C for at least 1 minute and generally not longer than 20 hours. While subatmospheric pressure can be employed for the thermal treatment, atmospheric pressure is desired for reasons of convenience. The thermal treatment can be performed at a temperature up to about 925°C. The thermally treated product, especially in its metal, hydrogen and ammonium forms, is particularly useful in the catalysis of certain organic, e.g., hydrocarbon, conversion reactions.
 The crystalline material of the invention can be intimately combined with a hydrogenating component such as tungsten, vanadium, molybdenum, rhenium, nickel, cobalt, chromium, manganese, or a noble metal such as platinum or palladium where a hydrogenation-dehydrogenation function is to be performed. Such component can be in the composition by way of cocrystallization, exchanged into the composition to the extent a Group IIIA element, e.g., aluminum, is in the structure, impregnated therein or intimately physically admixed therewith. Such component can be impregnated in or on to it such as, for example, in the case of platinum, by treating the silicate with a solution containing a platinum metal-containing ion. Thus, suitable platinum compounds for this purpose include chloroplatinic acid, platinous chloride and various compounds containing the platinum amine complex.
 The crystalline material of this invention, when employed either as an adsorbent or as a catalyst in an organic compound conversion process should be dehydrated, at least partially. This can be done by heating to a temperature in the range of 200°C to about 370°C in an atmosphere such as air, nitrogen, etc., and at atmospheric, subatmospheric or superatmospheric pressures for between 30 minutes and 48 hours. Dehydration can also be performed at room temperature merely by placing the ITQ-13 in a vacuum, but a longer time is required to obtain a sufficient amount of dehydration.
 The silicate and borosilicate forms of the crystalline material of the invention can be prepared from a reaction mixture containing sources of water, optionally an oxide of boron, an oxide of tetravalent element Y, e.g., silicon, a directing agent (R) as described below and fluoride ions, said reaction mixture having a composition, in terms of mole ratios of oxides, within the following ranges: (Table Removed)
 The organic directing agent R used herein is the hexamethonium [hexamethylenebis(trimethylammonium) dication and preferably is hexamethonium dihydroxide. Hexamethonium dihydroxide can readily be prepared by anion exchange of commercially available hexamethonium bromide.
 Crystallization of ITQ-13 can be carried out at either static or stirred conditions in a suitable reactor vessel, such as for example, polypropylene jars or Teflon®-lined or stainless steel autoclaves, at a temperature of about 120°C to about 160°C for a time sufficient for crystallization to occur at the temperature used, e.g., from about 12 hours to about 30 days. Thereafter, the crystals are separated from the liquid and recovered.
 It should be realized that the reaction mixture components can be supplied by more than one source. The reaction mixture can be prepared either batch-wise or continuously. Crystal size and crystallization time of the new crystalline material will vary with the nature of the reaction mixture employed and the crystallization conditions.
 Synthesis of the new crystals may be facilitated by the presence of at least 0.01 percent, preferably 0.10 percent and still more preferably 1 percent, seed crystals (based on total weight) of crystalline product.
 Aluminosilicate ITQ-13 can readily be produced from the silicate and borosilicate forms by post-synthesis methods well-known in the art, for example by ion exchange of the borosilicate material with a source of aluminum ions.
 The crystals prepared by the instant invention can be shaped into a wide variety of particle sizes. Generally speaking, the particles can be in the form of a powder, a granule, or a molded product, such as an extrudate having particle size sufficient to pass through a 2 mesh (Tyler) screen and be retained on a 400 mesh (Tyler) screen. In cases where the catalyst is molded, such as by extrusion, the crystals can be extruded before drying or partially dried and then extruded.
 The crystalline material of this invention can be used as an adsorbent or, particularly in its aluminosilicate form, as a catalyst to catalyze a wide variety of chemical conversion processes including many of present commercial/industrial importance. Examples of chemical conversion processes which are effectively catalyzed by the crystalline material of this invention, by itself or in combination with one or more other catalytically active substances including other crystalline catalysts, include those requiring a catalyst with acid activity.
 As in the case of many catalysts, it may be desirable to incorporate the new crystal with another material resistant to the temperatures and other conditions employed in organic conversion processes. Such materials include active and inactive materials and synthetic or naturally occurring zeolites as well as inorganic materials such as clays, silica and/or metal oxides such as alumina. The latter may be either naturally occurring or in the form of gelatinous precipitates or gels including mixtures of silica and metal oxides. Use of a material in conjunction with the new crystal, i.e., combined therewith or present during synthesis of the new crystal, which is active, tends to change the conversion and/or selectivity of the catalyst in certain organic conversion processes. Inactive materials suitably serve as diluents to control the amount of conversion in a given process so that products can be obtained in an economic and orderly manner without employing other means for controlling the rate of reaction. These materials may be incorporated into naturally occurring clays, e.g., bentonite and kaolin, to improve the crush strength of the catalyst under commercial operating conditions. Said materials, i.e., clays, oxides, etc., function as binders for the catalyst. It is desirable to provide a catalyst having good crush strength because in commercial use it is desirable to prevent the catalyst from breaking down into powder-like materials. These clay and/or oxide binders have been employed normally only for the purpose of improving the crush strength of the catalyst.
 Naturally occurring clays which can be composited with the new crystal include the montmorillonite and kaolin family, which families include the subbentonites, and the kaolins commonly known as Dixie, McNamee, Georgia and Florida clays or others in which the main mineral constituent is halloysite, kaolinite, dickite, nacrite, or anauxite. Such clays can be used in the raw state as originally mined or initially subjected to calcination, acid treatment or chemical modification. Binders useful for compositing with the present crystal also include inorganic oxides, such as silica, zirconia, titania, magnesia, beryllia, alumina, and mixtures thereof.
 In addition to the foregoing materials, the new crystal can be composited with a porous matrix material such as silica-alumina, silica-magnesia, silica-zirconia, silica-thoria, silica-beryllia and silica-titania as well as ternary compositions such as silica-alumina-thoria, silica-alumina-zirconia, silica-alumina-magnesia and silica-magnesia-zirconia.
 The relative proportions of finely divided crystalline material and inorganic oxide matrix vary widely, with the crystal content ranging from about 1 to about 90 percent by weight and more usually, particularly when the composite is prepared in the form of beads, in the range of about 2 to about 80 weight percent of the composite.
 In order to more fully illustrate the nature of the invention and the manner of practicing same, the following examples are presented.
Example 1 - Preparation of Hexamethonium Dihvdroxide.
 Hexamethonium dihydroxide was prepared by direct anionic exchange using a resin, Amberlite IRN-78, as hydroxide source, the resin having been
washed with distilled water prior to use until the water was at a pH of 7. The procedure involved dissolving 36.22 g of hexamethonium dibromide in 120 g of distilled water and contacting the resulting solution with 200 g of Amberlite IRN-78 resin for 12 hours under mechanical stirring. After stirring, the mixture was filtered and the resin washed with water to yield a solution of hexamethonium dihydroxide, which was then rotary-evaporated at 50°C for 1 hour. Titration with 0.1N hydrochloric acid showed the hexamethonium dihydroxide concentration of the final solution to be about 6.25X10"4 mol/g of solution.
Example 2 - Synthesis of Purely Siliceous ITQ-13
 The synthesis gel used for this synthesis had the following molar composition:
1 SiO2: 0.28 R(OH)2: 0.56 HF: 7 H2O where R(OH)2 is hexamethonium dihydroxide.
 The synthesis gel was produced by hydrolyzing 17.33 g of tetraethylorthosilicate (TEOS) with 74.6 g of the hexamethonium dihydroxide solution of Example 1 under continuous mechanical stirring at 200 rpm until the ethanol and the appropriate amount of water were evaporated to yield the above gel reaction mixture. Then, a solution of 1.94 g of HF (48 wt% in water) and 1 g of water was slowly added to the resultant hexamethonium silicate solution. The reaction mixture was mechanically and finally manually stirred until a homogeneous gel was formed. The resulting gel was very thick as consequence of the small amount of water present. The gel was autoclaved at 135°C for 28 days under continuous stirring at 60 rpm. The pH of the final gel (prior to filtration) was 7.3- 7.8. The solid product, the novel crystalline material ITQ-13, was recovered by filtration, washed with distilled water and dried at 100°C overnight.
The occluded hexamethonium and fluoride ions were removed from the product by heating the product from room temperature to 540°C at l°C/min under N2 flow (60 ml/mm). The temperature was kept at 540°C under N2 for 3 hours and then, the flow was switched to air and the temperature kept at 540°C for a further 3 hours in order to bum off the remaining organic. X-ray diffraction analysis of the as-synthesized and calcined samples gave the results listed in Tables 3 and 4, respectively and shown in Figures 5 and 6, respectively.
Table 3(Table Removed)
Table 4(Table Removed)
Example 3 - Synthesis of Purely Siliceous ITQ-13
[00411 The process of Example 2 was repeated with the varying water/silica molar ratios and crystallization times listed in Table 5 below but with all other parameters remaining unchanged. In each case the synthesis yielded the novel crystalline material ITQ-13.
Table 5(Table Removed)
xample 4 - Synthesis of Borosilicate ITQ-13
 The synthesis gel used for this synthesis had the following molar composition:
1 SiO2: 0.01 B2O3: 0.29 R(OH)2: 0.64 HF : 7 H2O
where R(OH)2is hexamethonium dihydroxide and 4 wt% of the SiO2 was added as ITQ-13 as seeds to accelerate the crystallization.
 The gel was prepared by hydrolyzing 13.87 g of TEOS in 62.18 g of the hexamethonium dihydroxide solution of Example 1 containing 0.083 g of boric acid. The hydrolysis was effected under continuous mechanical stirring at 200 rpm, until the ethanol and an appropriate amount of water were evaporated to yield the above gel reaction mixture. After the hydrolysis step, a suspension of 0.16 g of as-synthesized ITQ-13 in 3.2 g of water was added as seeds and then a solution of 1.78 g of HF (48 wt% in water) and 1 g of water were slowly added to produce the required reaction mixture. The reaction mixture was mechanically and finally manually stirred until a homogeneous gel was formed. The resulting gel was very
thick as a consequence of the small amount of water present. The gel was autoclaved at 135°C for 21 days under continuous stirring at 60 rpm. The pH of the final gel (prior of filtration) was 6.5-7.5. The solid was recovered by filtration, washed with distilled water and dried at 100°C, overnight. The occluded hexamethonium and fluoride ions were removed by the thermal treatment described in Example 2. X-ray analysis showed the calcined and as-synthesized to be pure ITQ-13, whereas boron analysis indicated the Si/B atomic ratio of the final solid to be about 60.
Example 5 - Synthesis of Borosilicate ITQ-13
 The process of Example 4 was repeated with the varying crystallization times listed in Table 5 below but with all other parameters remaining unchanged. In each case the synthesis yielded the novel crystalline material ITQ-13 with the Si/B atomic ratio given in Table 6.
Table 6(Table Removed)
* This borosilicate ITQ-13 sample was used in Example 7 below.
Example 6 - Synthesis of Borosilicate ITO-13
 The process of Example 4 was repeated but with the synthesis gel having the following molar composition:
1 SiO2: 0.005 B203: 0.285 R(OH)2: 0.60 HF: 7 H2O
where R(OH)2is hexamethonium dihydroxide and 4 wt% of the SiO2 was added as ITQ-13 seeds. Crystallization was conducted at 135°C for various times between 7 and 21 days and gave ITQ-13 products with Si/B atomic ratios as shown in Table 7.
Table 7(Table Removed)
Example 7 - Synthesis of Aluminosilicate ITQ-13
[00461 The synthesis of aluminum-containing ITQ-13 was carried out by Al exchange of borosilicate ITQ-13 zeolite using the procedure described below.
 14.08 g of AI(NO3)3.9H2O were dissolved in 85.92 g of water to yield a solution containing 8wt% AI(NO3)3. 0.74 g of calcined B-ITQ-13 from Example 5 were suspended in 10.5 g of the above A1(NO3)3 solution under stirring and the suspension was transferred to autoclaves and heated at 135°C for 3 days under continuous stirring at 60 rpm. The resulting solid was filtered,
washed with distilled water until the water was at neutral pH and dried at 100°C, overnight.
 X-ray analysis of the resultant product showed it to be pure ITQ-13. Chemical analysis indicated the product to have a Si/AI atomic ratio of 80 and a Si/B atomic ratio greater than 500.
1. A synthetic porous crystalline material, of the kind such herein defined, having a 3-dimensional channel system comprising a first set of generally parallel channels each of which is defined by a 10-membered ring of tetrahedrally coordinated atoms, a second set of generally parallel channels which are also defined by 10-menbered rings of tetrahedrally coordinated atoms and which intersect with the channels of the first set, and a third set of generally parallel channels which intersect with the channels of said first and second sets and each of which is defined by a 9-membered ring of tetrahedrally coordinated atoms.
2. The synthetic porous crystalline material as claimed in claim 1 further comprising a framework of tetrahedral atoms bridged by oxygen atoms, the tetrahedral atom framework being defined by a unit cell with atomic coordinates in nanometers, as defined herein, wherein each coordinate position may vary within + 0.05 nanometer.
3. The synthetic porous crystalline material as claimed in claim 1 wherein an X-ray diffraction pattern including values substantially as defined herein.
4. The synthetic porous crystalline material as claimed in claim 3 having a composition comprising the molar relationship:
wherein n is at least 5, X is a trivalent element of the kind such herein defined, and Y is a tetravalent element, of the kind such herein defined.
5. The synthetic porous crystalline material as claimed in claim 4 having a composition, on
an anhydrous basis and in terms of moles of oxides per moles of YO2, expressed by the
wherein R is an organic moiety.
6. The synthetic porous crystalline material as claimed in claim 5 wherein said R comprises
a hexamethonium dication.
7. The synthetic porous crystalline material as claimed in claim 4 wherein X is a trivalent element selected from the group consisting of boron, iron, indium, gallium, aluminum, and a combination thereof; and Y is a tetravalent element selected from the group consisting of silicon, tin, titanium, germanium, and a combination thereof.
8. The synthetic porous crystalline material as claimed in claim 4 wherein X comprises boron or aluminum and Y comprises silicon.
9. A siliceous form of the synthetic porous crystalline material as claimed in claim 4.
10. A method for synthesizing a synthetic porous crystalline material as claimed in claim 3 which comprises (i) preparing a mixture capable of forming said material, said mixture comprising sources of water, optionally an oxide of boron, an oxide of tetravalent element Y, a directing agent (R) and fluoride ions, wherein R is a hexamethonium dication, said reaction mixture having a composition, in terms of mole ratios of oxides, within the following ranges:
YO2/B2O3 at least 5
(ii) maintaining said mixture under sufficient conditions including a temperature of from 120°C to 160°C until crystals of said material are formed ; and (iii) recovering said crystalline material from step (ii).
11. The method as claimed in claim 10 wherein the mixture has a composition, in terms of
mole ratios, within the following ranges:
YO2/B2O3 at least 40
|Indian Patent Application Number||1774/DELNP/2003|
|PG Journal Number||17/2011|
|Date of Filing||29-Oct-2003|
|Name of Patentee||EXXONMOBIL RESEARCH AND ENGINEERING COMPANY|
|Applicant Address||1545 ROUTE 22 EAST, P.O. BOX 900, ANNANDALE, NEW JERSEY 08801-0900, U.S.A.|
|PCT International Classification Number||C01B 37/02|
|PCT International Application Number||PCT/US02/14411|
|PCT International Filing date||2002-05-07|