|Publication number||USRE29948 E|
|Application number||US 05/801,944|
|Publication date||Mar 27, 1979|
|Filing date||May 31, 1977|
|Priority date||Nov 2, 1973|
|Also published as||US3941871|
|Publication number||05801944, 801944, US RE29948 E, US RE29948E, US-E-RE29948, USRE29948 E, USRE29948E|
|Inventors||Francis G. Dwyer, Edwin E. Jenkins|
|Original Assignee||Mobil Oil Corporation|
|Export Citation||BiBTeX, EndNote, RefMan|
|Patent Citations (5), Non-Patent Citations (2), Referenced by (150), Classifications (38)|
|External Links: USPTO, USPTO Assignment, Espacenet|
0.9±0.2[xR.sub.2 O+(1-x)M.sub.2/n O]:<0.005 Al.sub.2 O.sub.3
0.9± 0.2[xR.sub.2 O+ (1-x)M.sub.2/n O]:<0.005 Al.sub.2 O.sub.3 :> 1 SiO.sub.2
______________________________________OH.sup.- /SiO.sub.2 .01-5R.sub.4 N.sup.- /(R.sub.4 N.sup.+ + Na.sup.+) .05-1.0H.sub.2 O/OH.sup.- 50-1000SiO.sub.2 /M.sub.2/n O >1______________________________________
______________________________________OH.sup.- /SiO.sub.2 .05-1.0R.sub.4 N.sup.+ /(R.sub.4 N.sup.+ + Na.sup.+) .1-.8H.sub.2 O/OH.sup.- 50-500SiO.sub.2 /M.sub.2/n O >3______________________________________
1. Field of the Invention
This invention relates to novel crystalline metal organosilicates and to methods for their preparation and to organic compound conversion, especially hydrocarbon conversion therewith.
2. Description of the Prior Art
Zeolitic materials, both natural and synthetic, have been known in the past to have catalytic capability for various types of hydrocarbon conversion reactions. Certain of these zeolitic materials comprising ordered porous crystalline aluminosilicates have a definite crystalline structure, as determined by X-ray diffraction, within which there are a number of small cavities which are interconnected by a number of still smaller channels. These cavities and channels are precisely uniform in size within a specific zeolitic material. Since the dimensions of these pores are such as to accept for adsorption purposes molecules of certain dimensions while rejecting those of larger dimensions, these materials have commonly been known to be "molecular sieves" and are utilized in a variety of ways to take advantage of the adsorptive properties of these compositions.
These molecular sieves include a wide variety of positive ion containing crystalline aluminosilicates, both natural and synthetic. These aluminosilicates can be described as a rigid three-dimensional network of SiO4 and AlO4 in which the tetrahedra are cross linked by the sharing of oxygen atoms whereby the ratio of the total aluminum and silicon atoms to oxygen is 1:2. The electrovalence of the tetrahedra containing aluminum is balanced by the inclusion in the crystal of a cation, for example an alkali metal or alkaline earth cation. Thus, a univalent positive sodium cation balances one negatively charged aluminosilicate tetrahedra where an alkaline earth metal cation is employed in the crystal structure of an aluminosilicate, it balances two negatively charged tetrahedra because of its doubly positive valence. One type of cation may be exchanged either entirely or partially by 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 size of the pores in a given aluminosilicate by suitable selection of the particular cation. The spaces between the tetrahedra are occupied by moles of water prior to dehydration.
One such group of crystalline aluminosilicates, designated as those of the ZSM-5 type, have been known and are particularly described in U.S. Pat. No. 3,702,886, the disclosure of which is incorporated herein by reference. The ZSM-5-type crystalline aluminosilicates have been prepared, for example, from a solution containing a tetraalkyl ammonium hydroxide, sodium oxide, an oxide of aluminum or gallium, an oxide of silicon or germanium and water and have been found to be characterized by a specific X-ray diffraction pattern.
The above crystalline aluminosilicates, as previously noted, have been characterized by the presence of aluminum and silicon, the total of such atoms to oxygen being 1:2. The amount of alumina present appears directly related to acidity characteristics of the resulting product. A low alumina content has been recognized as being advantageous in attaining a low degree of acidity which in many catalytic reactions is translated into low coke making properties and low aging rates.
In accordance with the present invention, there is provided a family of crystalline metal organosilicates which are essentially free of Group IIIA metals, i.e. aluminum and/or gallium. These organosilicates have surprisingly been found to be characterized by an X-ray diffraction pattern characteristic of the above-noted ZSM-5-type crystalline aluminosilicates. In addition to having such characteristic X-ray diffraction pattern, the crystalline organosilicates of the present invention can be identified in their anhydrous state in terms of mole ratios of oxides as follows:
0.9± 0.2 [xR.sub.2 O+ (1-x)M.sub. 2/n O]:< 0.005 Al.sub.2 O.sub.3 :> 1 SiO.sub.2
where M is a metal other than a metal of Group IIIA, n is the valence of said metal, R is an alkyl ammonium radical and x is greater than 0 but not exceeding 1. Preferably R is a tetraalkyl ammonium radical, the alkyl groups of which contain 2-5 carbon atoms.
In the above composition, R2 O and M2/n O may be removed by replacement with or conversion to other desired components which serve to enhance catalytic activity, stability and/or adsorption characteristics. It is particularly contemplated that R and/or M may be at least partially in the ammonium form as a result of ion exchange.
As above noted, the family of crystalline metal organosilicates disclosed and claimed herein have a definite X-ray diffraction pattern. Such X-ray diffraction pattern, similar to that for the ZSM-5 zeolites, shows the following significant lines:
TABLE I______________________________________Interplanar spacing d(A): Relative intensity______________________________________11.1 ±0.2 s10.0 ±0.2 s7.4 ±0.15 w7.1 ±0.15 w6.3 ±0.1 w6.04 ±0.1 w5.975.56 ±0.1 w5.01 ±0.1 w4.60 ±0.08 w4.25 ±0.08 w3.85 ±0.07 ys3.71 ±0.05 s3.04 ±0.03 w2.99 ±0.02 w2.94 ±0.02 w______________________________________
These values were determined by standard techniques. The radiation was the K-alpha doublet of copper and a Geiger Counter Spectrometer with a strip chart pen recorder was used. The peak heights, I, and the positions as a function of two times theta, where theta is the Bragg angle, were read from the spectrometer chart. From these, the relative intensities, 100 I/I0, where I0 is the intensity of the strongest line or peak and d(obs.), the interplanar spacing in A, corresponding to the recorded lines were calculated. In Table I the relative intensities are given in terms of the symbols s = strong, w = weak and vs = very strong.
The crystalline metal organosilicate of the present invention can be used either in the alkali metal form, e.g. the sodium form, other desired metal form, the ammonium form or the hydrogen form. Preferably, one or other of the last two forms is employed. They can also be used in intimate combination with a hydrogenation 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 suitably be impregnated on or physically intimately admixed with the crystalline organosilicate.
The above organosilicates as synthesized or after impregnation can be beneficially converted to another form by thermal treatment. This can be done by heating to a temperature in the range of 200° to 600° C. in an atmosphere such as air, nitrogen, etc. and that atmospheric or subatmosphereic pressures for between 1 and 48 hours. Dehydration may also be performed at lower temperatures merely by placing the organosilicate in a vacuum, but a longer time is required to obtain a sufficient amount of dehydration.
The crystalline metal organosilicates of the invention can be suitably synthesized by preparing a solution containing (R4 N)2 O, sodium oxide, an oxide of a metal other than a metal of Group IIIA and water and having a composition in terms of mole ratios of oxides falling within the following ranges:
TABLE II______________________________________ Broad Preferred______________________________________OH.sup.- /SiO.sub.2 .01-5 .05-1.0R.sub.4 N.sup.+ /(R.sub.4 N.sup.+ + Na.sup.+) .05-1.0 .1-.8H.sub.2 O/OH.sup.- 50-1000 50-500SiO.sub.2 /M.sub.2/n O >1 >3______________________________________
wherein R is an alkyl radical, preferably between 2 and 5 carbon atoms and M is total metal. Thereafter, the mixture is maintained until crystals of the metal organosilicate are formed. Preferably, crystallization is performed under pressure in an autoclave or static bomb reactor. The temperature ranges from 100° C. to 200° C. generally, but at lower temperatures, e.g. about 100° C., crystallization time is longer. Thereafter, the crystals are separated from the liquid and recovered. Typical reaction conditions consist of heating the foregoing reaction mixture to a temperature from about 100° C. to 175° C. for a period of time of from about 6 hours to 60 days. The more preferred temperature range is from about 100° C. to 175° C. with the amount of time at a temperature in such range being from about 12 hours to 30 days.
The treatment of the amorphous mixture is carried out until crystals form. The resulting crystalline product is separated from the reaction medium, as by cooling to room temperature, filtering and water washing. The product so obtained is dried, e.g. at 230° F., for from about 8 to 24 hours. If desired, milder conditions may be employed, e.g. room temperature under vacuum.
The desired crystalline organosilicate can be prepared utilizing materials which supply the appropriate oxide. Such compositions include sodium silicate, colloidal silica, silica hydrosol, silica gel, silicic acid, sodium hydroxide, compounds of the desired metal, other than a metal of Group IIIA and tetraalkylammonium compounds, e.g. tetrapropylammonium bromide. In addition to tetrapropylammonium compounds, it is contemplated that tetramethyl, tetraethyl or tetrabutyl ammonium compounds may similarly be employed. It will be understood that each oxide component utilized in the reaction mixture for preparing the crystalline metal organosilicates of this invention can be supplied by one or more initial reactants and they can be mixed together in any order. For example, sodium oxide can be supplied by an aqueous solution of sodium hydroxide or by an aqueous solution of sodium silicate; tetrapropylammonium can be supplied in the form of its hydroxide as can the other tetraalkylammonium radicals noted hereinabove. The reaction mixture can be prepared either batchwise or continuously. Crystal size and crystallization time of the crystalline metal organosilicate composition will vary with the nature of the reaction mixture employed.
The crystalline organosilicates described herein are substantially free of alumina, but may contain very minor amounts of such oxide attributable primarily to the presence of aluminum impurities in the reactants and/or equipment employed. Thus, the molar ratio of alumina to silica will be in the range of 0 to less than 0.005 Al2 O3 to more than 1 mole of SiO2. Generally, the latter may range from >1 SiO2 up to 500 or more.
The crystalline metal organosilicates as synthesized can have the original components thereof replaced by a wide variety of others according to techniques well known in the art. Typical replacing components would include hydrogen, ammonium, alkyl ammonium and aryl ammonium and metals, other than metals of Group IIIA, including mixtures of the same. The hydrogen form may be prepared, for example, by substitution of original sodium with ammonium. The composition is then calcined at a temperature of, say, 1000° F. causing evolution of ammonia and retention of hydrogen in the composition. Of the replacing metals, preference is accorded to metals of Groups II, IV and VIII of the Periodic Table.
The crystalline silicates are then preferably washed with water and dried at a temperature ranging from 150° F. to about 600° F. and thereafter calcined in air or other inert gas at temperatures ranging from 500° F. to 1500° F. for periods of time ranging from 1 to 48 hours or more.
Regardless of the synthesized form of the organosilicate the spatial arrangement of atoms which form the basic crystal latices remain essentially unchanged by the described replacement of sodium or other alkali metal or by the presence in the initial reaction mixture of metals in addition to sodium, as determined by an X-ray powder diffraction pattern of the resulting organosilicate. The X-ray diffraction patterns of such products are essentially the same as those set forth in Table I above.
The crystalline silicates prepared in accordance with the instant invention are formed in a wide variety of particular sizes. Generally, the particles can be in the form of powder, a granule, or a molded product such as an extrudate having a particle size sufficient to pass through a 2 mesh (Tyler) screen and be maintained on a 400 mesh (Tyler) screen in cases where the catalyst is molded such as by extrusion. The aluminosilicate can be extruded before drying or dried or partially dried and then extruded.
In the case of many catalysts, it is desired to incorporate the new crystalline silicate with another material resistant to the temperatures and other conditions employed in organic processes. Such materials include active and inactive materials and synthetic and naturally occurring zeolites as well as inorganic materials such as clays, silica and/or metal oxides. 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 the material in conjunction with the new crystalline aluminosilicate, i.e. combined therewith which is active, tends to improve 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 economically and in an orderly manner without employing other means for controlling the rate of reaction. Normally, crystalline materials have been incorporated into naturally occurring clays, e.g. bentonite and kaolin to improve the crush strength of the catalyst under commercial operating conditions. These 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 a petroleum refinery the catalyst is often subjected to rough handling which tends to break the catalyst down into powder-like materials which cause problems in processing. These clay binders have been employed for the purpose of improving the crush strength of the catalyst.
Naturally occurring clays that can be composited with the crystalline metal organosilicate described herein include the montmorillonite and kaolin family, which families include the sub-bentonites and the kaolins known commonly as Dixie, McNamee, Georgia and Florida or others in which the main 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.
In addition to the foregoing materials, the crystalline metal organosilicate may be composited with a porous matrix material such as silica-alumina, silica-magnesia, silica-zirconia, silica-thoria, silica-berylia, silica-titania as well as ternary compositins such as silica-alumina-thoria, silica-alumina-zirconia, silica-alumina-magnesia and silica-magnesia-zirconia. The matrix can be in the form of a cogel. The relative proportions of finally divided crystalline metal organosilicate and inorganic oxide gel matrix can vary widely with the crystalline organosilicate content ranging from about 1 to 90 percent by weight and more usually in the range of about 2 to about 50 percent by weight of the composite.
Employing the catalyst of this invention, containing a hydrogenation component, heavy petroleum residual stocks, cycle stocks, and other hydrocrackable charge stocks can be hydrocracked at temperatures between 400° F. and 825° F. using molar ratios of hydrogen to hydrocarbon charge in the range between 2 and 80. The pressure employed will vary between 10 and 2,500 psig and the liquid hourly spaced velocity between 0.1 and 10.
Employing the catalyst of this invention for catalytic cracking, hydrocarbon cracking stocks can be cracked at a liquid hourly space velocity between about 0.5 and 50, a temperature between about 550° F. and 1100° F., a pressure between about subatmospheric and several hundred atmospheres.
Employing a catalytically active form of a member of the family of zeolites of this invention containing a hydrogenation component, reforming stocks can be reformed employing a temperature between 700° F. and 1000° F. The pressure can be between 100 and 1000 psig, but is preferably between 200 and 700 psig. The liquid hourly space velocity is generally between 0.1 and 10, preferably between 0.5 and 4 and the hydrogen to hydrocarbon mole ratio is generally between 1 and 20, preferably between 4 and 12.
The catalyst can also be used for hydroisomerization of normal paraffins when provided with a hydrogenation component, e.g. platinum. Hydroisomerization is carried out at a temperature between 200° and 700° F., preferably 300° to 550° F., with a liquid hourly space velocity between 0.01 and 2, preferably between 0.25 and 0.50 employing hydrogen such that the hydrogen to hydrocarbon mole ratio is between 1:1 and 5:1. Additionally, the catalyst can be used for olefin isomerization employing temperatures between 30° F. and 500° F.
In order to more fully illustrate the nature of the invention and a manner of practicing the same, the following examples are presented.
In the examples which follow, whenever adsorption data are set forth, it was determined as follows:
A weighed sample of the material was contacted with the desired pure adsorbate vapor in an adsorption chamber at a pressure less than the vapor-liquid equilibrium pressure of the adsorbate at room temperature. This pressure was kept constant during the adsorption period which did not exceed about eight hours. Adsorption was complete when a constant pressure in the adsorption chamber was reached, i.e. 12 mm. of mercury for water and 20 mm. for n-hexane and cyclohexane. The increase in weight was calculated as the adsorption capacity of the sample.
A crystalline organosilicate containing tin and sodium was synthesized from tetrapropylammonium bromide, colloidal silica, stannous chloride and sodium hydroxide. A mixture of 19.1 grams of colloidal silica (30 weight percent SiO2), 15.6 grams of tetrapropylammonium bromide, 1.5 grams of NaOH, 1.0 gram of SnCl4.5 H2 O and 100 grams of water was prepared. This mixture was placed in an autoclave and maintained for 22 hours at 300° F. and autogenous pressure. The product was removed, filtered, water washed and dried at 230° F. X-ray diffraction analysis established the product as being crystalline and having the X-ray diffraction pattern set forth in Table I.
The reaction composition and product analysis are shown below:
______________________________________Reaction Composition Moles______________________________________SiO.sub.2 .095[(C.sub.3 H.sub.8).sub.4 N].sub.2 O .0294H.sub.2 O 6.3Na.sub.2 O .01875SnO.sub.2 .0029R.sub.4 N/R.sub.4 N + Na .610OH.sup.- /SiO.sub.2 .395H.sub.2 O/OH.sup.- 168.3SiO.sub.2 /M.sub.2/n O 4.38______________________________________
where R is propyl and M is total metal.
______________________________________Product Composition Wt. Percent______________________________________Al.sub.2 O.sub.3 0.06Na 3.1SiO.sub.3 91 (approx.)Sn 6.1______________________________________
A crystalline organosilicate containing sodium was produced from tetrapropylammonium bromide, colloidal silica and sodium hydroxide. A mixture of 19.1 grams of colloidal silica (30 weight percent SiO2), 15.6 grams tetrapropylammonium bromide, 1.0 gram NaOH and 100 grams of water was prepared. This mixture was placed in an autoclave and maintained for 24 hours at 300° F. and autogenous pressure. The product was removed, filtered, water washed and dried at 230° F. X-ray diffraction analysis established the product as being crystalline and having the X-ray diffraction pattern set forth in Table I.
The reaction composition and product analysis are shown below.
______________________________________Reaction Composition Moles______________________________________SiO.sub.2 .095[(C.sub.3 H.sub.8).sub.4 N]O .0294H.sub.2 O 6.3Na.sub.2 O .0125R.sub.4 N/R.sub.4 N + Na .701OH.sup.- /SiO.sub.2 .263H.sub.2 O/OH.sup.- 252.5SiO.sub.2 /Na.sub.2 O 7.6______________________________________Product Composition Wt. Percent______________________________________Al.sub.2 O.sub.3 0.13N 0.69Na 0.80SiO.sub.2 98.8Adsorption Wt. Percent______________________________________Cyclohexane 2.4Water 4.6______________________________________
A crystalline organosilicate containing sodium was synthesized from sodium silicate, sodium hydroxide, sulfuric acid and tetrapropylammonium bromide. A mixture of 40 grams of sodium silicate "Q" Brand (Na2 O/SiO2 = 0.299), 31.2 grams of tetrapropylammonium bromide, 0.5 gram NaOH, 4.6 grams H2 SO4 and 200 grams of water was prepared. This mixture was maintained for 6 days at 212° F. and atmospheric pressure. The product was removed, filtered, water washed and dried at about 250° F. X-ray diffraction analysis established the product as being crystalline and having the X-ray diffraction pattern set forth in Table I.
The reaction composition is shown below:
______________________________________Reaction Composition Moles______________________________________SiO.sub.2 .1896[(C.sub.3 H.sub.8).sub.4 N].sub.2 O .0587H.sub.2 O 12.5Na.sub.2 O .0943R.sub.4 N/R.sub.4 N + Na .384OH.sup.- /SiO.sub.2 .499H.sub.2 O /OH.sup.- 132.1SiO.sub.2 /Na.sub.2 O 2.01______________________________________
After calcination for 16 hours at 1000° F. in air, the product was used to effect selective separation of C8 aromatic isomers. As will be evident from the data shown below in Table III, ortho xylene and meta xylene are both very selectively excluded at 200° C., while para xylene and ethylbenzene are both sorbed.
TABLE III______________________________________A. Pure Components Retention Time. Sec.______________________________________ Mesitylene 10 o-Xylene 11 m-Xylene 11 p-Xylene 394 Ethylbenzene 319B. C.sub.8 -Aromatic Mixture Major Separation No Resolution Minor Separation OX, MX/PX, EB Number of Peaks 2 Resolution Excellent Capacity (μ l/g) III______________________________________
A crystalline organosilicate containing sodium was synthesized from sodium silicate, sulfuric acid, tetrapropylammonium bromide and water. A mixture of 80 grams of sodium silicate (Na2 O/SiO2 = 0.299), 8 grams of sulfuric acid, 60 grams of tetrapropylammonium bromide and 200 grams of water was prepared. This mixture was maintained at 212° F. for 66 hours and autogenous pressure. The product was removed, filtered, water washed and dried at about 250° F. X-ray diffraction analysis established the product as being crystalline and having the X-ray diffraction pattern set forth in Table I.
The reaction composition and product analysis are shown below:
______________________________________Reaction Composition Moles______________________________________SiO.sub.2 .379[(C.sub.3 H.sub.8).sub.4 N].sub.2 O .113H.sub.2 O 13.9Na.sub.2 O .176R.sub.4 N/R.sub.4 N + Na .391OH.sup.- /SiO.sub.2 .498H.sub.2 O/OH.sup.- 73.66SiO.sub.2 /Na.sub.2 O 2.15Product Composition Wt. Percent______________________________________Al.sub.2 O.sub. 3 0.18N 0.78Na 1.3SiO.sub.2 97 (approx.)______________________________________
A crystalline organosilicate containing sodium was synthesized from sodium silicate, sulfuric acid, sodium hydroxide, tetramethylammonium chloride, tetrapropylammonium bromide and water. A mixture of 40 grams of sodium silicate (Na2 O/SiO2 = 0.299), 1.5 grams of sodium hydroxides, 3 grams of sulfuric acid, 6 grams of tetramethylammonium chloride, 6 grams of tetrapropylammonium bromide and 231 grams of water was prepared. This mixture was maintained for 113 hours at 320° F. and autogenous pressure. The product was removed, filtered, water washed and dried at about 250° F. X-ray diffraction analysis showed the crystalline material to have the X-ray diffraction pattern set forth in Table I.
The reaction composition is shown below:
______________________________________ Reaction Composition Moles______________________________________SiO.sub.2 .1897[(C.sub.3 H.sub.8).sub.4 N].sub.2 O .0113[(CH.sub.3).sub.4 N].sub.2 O .0274H.sub.2 O 14.2Na.sub.2 O .0755R.sub.4 N/R.sub.4 N + Na .339OH.sup.- /SiO.sub.2 .473H.sub.2 O/OH.sup.- 158.1SiO.sub.2 /Na.sub.2 O 2.513______________________________________
where R is propyl + methyl.
A crystalline organosilicate containing sodium was synthesized from sodium silicate, sodium hydroxide, sulfuric acid, tetrapropylammonium bromide and water. A mixture of 160 grams of sodium silicate (Na2 O/SiO2 = 0.299), 2 grams of sodium hydroxide, 18.4 grams of sulfuric acid. 124.8 grams of tetrapropylammonium bromide and 800 grams of water was prepared. This mixture was maintained for 40 hours at 212° F. and autogenous pressure. The product was removed, filtered, water washed and dried at about 250° F. X-ray diffraction analysis showed the crystalline material to have the X-ray diffraction analysis set forth in Table I.
The reaction composition and product analysis are shown below:
______________________________________Reaction Composition Moles______________________________________SiO.sub.2 .759[(C.sub.3 H.sub.8).sub.4 N].sub.2 O .2347H.sub.2 O 50.02Na.sub.2 O .2521R.sub.4 N/R.sub.4 N + Na .482OH.sup.- /SiO.sub.2 .1696H.sub.2 O/OH.sup.- 388.7SiO.sub.2 /Na.sub.2 O 3.01______________________________________Product Composition Wt. Percent______________________________________Al.sub.2 O.sub.2 0.202Na 1.5SiO.sub.2 96.5______________________________________
A crystalline organosilicate containing zirconium and sodium was synthesized from colloidal silica, sodium hydroxide, zirconium oxide (25 percent solution), tetrapropylammonium bromide and water. A mixture of 50 grams of colloidal silica (30 weight percent SiO2), 1 gram of sodium hydroxide, 25 grams of zirconium oxide (25 percent solution), 20 grams of tetrapropylammonium bromide and 50 grams of water was prepared. This mixture was maintained for 25 days at 300° F. and autogeneous pressure. The product was removed, filtered, water washed and dried at about 250° F. X-ray diffraction analysis showed the crystalline material to have the X-ray diffraction pattern in Table I.
The reaction composition and product analysis are shown below:
______________________________________Reaction Composition Moles______________________________________SiO.sub.2 .2496[(C.sub.3 H.sub.8).sub.4 N].sub.2 O .0376H.sub.2 O 5.76Na.sub.2 O .0125ZrO.sub.2 .0507R.sub.4 N/R.sub.4 N + Na .750H.sub.2 O/OH.sup.- 230.4SiO.sub.2 /M.sub.2/n O 3.94Product Composition Wt. Percent______________________________________Al.sub.2 O.sub.3 <0.04N 0.52Na 0.24______________________________________
A crystalline organosilicate containing calcium and sodium was synthesized from colloidal silica, sodium hydroxide, calcium hydroxide, tetrapropylammonium bromide and water. A mixture of 50 grams of colloidal silica (30 weight percent of SiO2), 1 gram NaOH, 1 gram Ca(OH)2, 20 grams of tetrapropylammonium bromide and 100 grams of water was prepared. The mixture was maintained for 16 days at 212° F. and autogenous pressure. The product was removed, filtered, water washed and dried at about 250° F. X-ray analysis showed the crystalline material to have the X-ray diffraction pattern set forth in Table I.
Reaction composition and product analysis are shown below:
______________________________________Reaction Composition Moles______________________________________SiO.sub.2 .2496[(C.sub.3 H.sub.8).sub.4 N].sub.2 O .0376H.sub.2 O 7.50Na.sub.2 O .0125CaO .0135R.sub.4 N/R.sub.4 N + Na .750OH.sup.- /SiO.sub.2 .l00H.sub.2 O/OH.sup.- 300SiO.sub.2 /M.sub.2/n O 9.6______________________________________Product Composition Wt. Percent______________________________________Al.sub.2 O.sub.3 <0.04N 0.63Na 0.66SiO.sub.2 96 (approx.)Ca 2.9______________________________________
A crystalline organoslicate containing nickel and sodium was synthesized from colloidal silica, sodium hydroxide, nickel nitrate, tetrapropylammonium bromide and water. A mixture of 50 grams of colloidal silica (30 weight percent SiO2), 1.5 grams of NaOH, 4 grams of Ni(NO3)2.6 H2 O, 20 grams of tetrapropylammonium bromide and 60 grams of water was prepared. This mixture was maintained for 19 days at 212° F. and autogenous pressure. The product was removed, filtered, water washed and dried at about 250° F. X-ray diffraction analysis showed the crystalline material to have the X-ray diffraction pattern set forth in Table I. The reaction composition and product analysis are shown below:
______________________________________Reaction Composition Moles______________________________________SiO.sub.2 .2496[(C.sub.3 H.sub.8).sub.4 N].sub.2 O .0376H.sub.2 O 5.36Na.sub.2 O .0188NiO .01376R.sub.4 N/R.sub.4 N + Na .667OH.sup.- /SiO.sub.2 .150H.sub.2 O/OH.sup.- 142.9SiO.sub.2 /M.sub.2/n O 7.68______________________________________Product Composition Wt. Percent______________________________________Al.sub.2 O.sub.3 <0.04N 0.65Na 0.71SiO.sub.2 92 (approx.)Ni 7.0______________________________________
A crystalline organosilicate containing zinc and sodium was synthesized from colloidal silica, sodium hydroxide, zinc nitrate, tetrapropylammonium bromide and water. A mixture of 100 grams of colloidal silica, 4 grams NaOH, 4 grams of Zn(NO3)2.6 H2 O, 25 grams of tetrapropylammonium bromide and 100 grams of water was prepared. This mixture was maintained for 14 days at 212° F. and autogenous pressure. The product was removed, filtered, water washed, and dried at about 250° F. X-ray diffraction analysis showed the crystalline material to have the X-ray diffraction pattern set forth in Table I.
The reaction composition and product analysis are shown below:
______________________________________Reaction Composition Moles______________________________________SiO.sub.2 .4992[(C.sub.3 H.sub.8).sub.4 N].sub.2 O .047H.sub.2 O 9.53Na.sub.2 O .05ZnO .0059R.sub.4 N/R.sub.4 N + Na .485OH.sup.- /SiO.sub.2 .200H.sub.2 O/OH.sup.- 95.3SiO.sub.2 /M.sub.2/n O 8.93______________________________________Product Composition Wt. Percent______________________________________Al.sub.2 O.sub.3 <0.04N 0.69Na 1.3SiO.sub.2 95 (approx.)ZnO 2.63______________________________________
|Cited Patent||Filing date||Publication date||Applicant||Title|
|US3506400 *||May 25, 1966||Apr 14, 1970||Exxon Research Engineering Co||High silica crystalline zeolites and process for their preparation|
|US3702886 *||Oct 10, 1969||Nov 14, 1972||Mobil Oil Corp||Crystalline zeolite zsm-5 and method of preparing the same|
|US3770845 *||Nov 17, 1970||Nov 6, 1973||Sun Oil Co||Paraffin hydroisomerization with a combined catalyst of a hydrogenation component and a polyvalent metal cation-exchanged zeolite|
|US3804741 *||Mar 9, 1972||Apr 16, 1974||Velsicol Chemical Corp||Hydrocarbon conversion and hydrocracking with layered complex metal silicate and chrysotile compositions|
|US4021331 *||May 25, 1976||May 3, 1977||Mobil Oil Corporation||Organic compound conversion by zeolite ZSM-20 catalysts|
|1||*||Barrer et al., "Journal of the Chemical Society", 1959, pp. 195-208.|
|2||*||Veda et al. "Molecular Sieve Zeolites-I", Copyright A.C.S., pp. 135-139.|
|Citing Patent||Filing date||Publication date||Applicant||Title|
|US4790927||Jan 9, 1984||Dec 13, 1988||Union Oil Company Of California||Process for simultaneous hydrotreating and hydrodewaxing of hydrocarbons|
|US4877762||Aug 22, 1988||Oct 31, 1989||Union Oil Company Of California||Catalyst for simultaneous hydrotreating and hydrodewaxing of hydrocarbons|
|US4970397 *||Jun 16, 1989||Nov 13, 1990||Mobil Oil Corporation||Method and apparatus for activating catalysts using electromagnetic radiation|
|US4990710 *||Jun 24, 1988||Feb 5, 1991||Mobil Oil Corporation||Tin-containing microporous crystalline materials and their use as dehydrogenation, dehydrocyclization and reforming catalysts|
|US5037529 *||Dec 29, 1989||Aug 6, 1991||Mobil Oil Corp.||Integrated low pressure aromatization process|
|US5103066 *||Dec 10, 1990||Apr 7, 1992||Mobil Oil Corp.||Dehydrogenation of alcohols over non-acidic metal-zeolite catalysts|
|US5110568 *||Sep 14, 1990||May 5, 1992||Exxon Research And Engineering Company||Stannosilicates and preparation thereof|
|US5110571 *||Feb 28, 1990||May 5, 1992||Exxon Research And Engineering Company||Stannosilicates and preparation thereof (C-2417)|
|US5122489 *||Oct 15, 1990||Jun 16, 1992||Mobil Oil Corporation||Non-acidic dehydrogenation catalyst of enhanced stability|
|US5124497 *||Oct 11, 1989||Jun 23, 1992||Mobil Oil Corporation||Production of mono-substituted alkylaromatics from C8 +N-paraffins|
|US5147837 *||Oct 22, 1990||Sep 15, 1992||Mobil Oil Corporation||Titania containing dehydrogenation catalysts|
|US5174977 *||Oct 4, 1991||Dec 29, 1992||Mobil Oil Corp.||Synthesis of crystalline ZSM-5-type material|
|US5174978 *||Oct 4, 1991||Dec 29, 1992||Mobil Oil Corp.||Synthesis of crystalline ZSM-5-type material|
|US5174981 *||Oct 4, 1991||Dec 29, 1992||Mobil Oil Corp.||Synthesis of crystalline ZSM-5-type material|
|US5192728 *||Oct 6, 1989||Mar 9, 1993||Mobil Oil Corporation||Tin-colating microporous crystalline materials and their use as dehydrogenation, dehydrocyclization reforming catalysts|
|US5209918 *||Oct 4, 1991||May 11, 1993||Mobil Oil Corp.||Synthesis of crystalline ZSM-5-type material|
|US5248841 *||Apr 30, 1982||Sep 28, 1993||Mobil Oil Corporation||Hydrocarbon conversion with ZSM-22 zeolite|
|US5283385 *||May 4, 1992||Feb 1, 1994||Mobil Oil Corporation||Upgrading of normal pentane to cyclopentane|
|US5284986 *||Oct 26, 1992||Feb 8, 1994||Mobil Oil Corporation||Upgrading of normal pentane to cyclopentene|
|US5304694 *||May 15, 1992||Apr 19, 1994||Mobil Oil Corporation||Isobutene and isoamylene production|
|US5310714 *||Jul 8, 1992||May 10, 1994||Mobil Oil Corp.||Synthesis of zeolite films bonded to substrates, structures and uses thereof|
|US5316661 *||Apr 16, 1993||May 31, 1994||Mobil Oil Corporation||Processes for converting feedstock organic compounds|
|US5344553 *||Feb 22, 1993||Sep 6, 1994||Mobil Oil Corporation||Upgrading of a hydrocarbon feedstock utilizing a graded, mesoporous catalyst system|
|US5349117 *||Nov 8, 1993||Sep 20, 1994||Mobil Oil Corp.||Process for sorption separation|
|US5350504 *||Dec 18, 1992||Sep 27, 1994||Mobil Oil Corporation||Shape selective hydrogenation of aromatics over modified non-acidic platinum/ZSM-5 catalysts|
|US5369071 *||Dec 11, 1992||Nov 29, 1994||Mobil Oil Corporation||Manufacture of improved catalyst|
|US5374411 *||Jun 15, 1988||Dec 20, 1994||The Dow Chemical Company||Crystalline aluminumphosphate compositions|
|US5430218 *||Aug 27, 1993||Jul 4, 1995||Chevron U.S.A. Inc.||Dehydrogenation using dehydrogenation catalyst and polymer-porous solid composite membrane|
|US5536857 *||Jul 5, 1994||Jul 16, 1996||Ford Motor Company||Single source volatile precursor for SiO2.TiO2 powders and films|
|US5873994 *||Jul 15, 1997||Feb 23, 1999||Phillips Petroleum Company||Process for aromatization of a cracked gasoline feedstock using a catalyst containing an acid leached zeolite and tin|
|US6392109||Feb 29, 2000||May 21, 2002||Chevron U.S.A. Inc.||Synthesis of alkybenzenes and synlubes from Fischer-Tropsch products|
|US6441263||Jul 7, 2000||Aug 27, 2002||Chevrontexaco Corporation||Ethylene manufacture by use of molecular redistribution on feedstock C3-5 components|
|US6455595||Jul 24, 2000||Sep 24, 2002||Chevron U.S.A. Inc.||Methods for optimizing fischer-tropsch synthesis|
|US6472441||Jul 24, 2000||Oct 29, 2002||Chevron U.S.A. Inc.||Methods for optimizing Fischer-Tropsch synthesis of hydrocarbons in the distillate fuel and/or lube base oil ranges|
|US6500233||Oct 26, 2000||Dec 31, 2002||Chevron U.S.A. Inc.||Purification of p-xylene using composite mixed matrix membranes|
|US6541408||Oct 29, 2001||Apr 1, 2003||Exxonmobil Oil Corp.||Zeolite catalysts having stabilized hydrogenation-dehydrogenation function|
|US6566569||Jun 23, 2000||May 20, 2003||Chevron U.S.A. Inc.||Conversion of refinery C5 paraffins into C4 and C6 paraffins|
|US6649662||Jun 20, 2002||Nov 18, 2003||Chevron U.S.A. Inc.||Methods for optimizing fischer-tropsch synthesis of hydrocarbons in the distillate fuel and/or lube base oil ranges|
|US6670517||Aug 24, 2000||Dec 30, 2003||Exxon Mobil Chemical Patents Inc.||Process for alkylating aromatics|
|US6755900||Dec 18, 2002||Jun 29, 2004||Chevron U.S.A. Inc.||Crosslinked and crosslinkable hollow fiber mixed matrix membrane and method of making same|
|US6806087||May 28, 2002||Oct 19, 2004||Chevron U.S.A. Inc.||Use of microchannel reactors in combinatorial chemistry|
|US6864398||Dec 28, 2001||Mar 8, 2005||Chevron U.S.A. Inc.||Conversion of syngas to distillate fuels|
|US6872753||Mar 15, 2003||Mar 29, 2005||Conocophillips Company||Managing hydrogen and carbon monoxide in a gas to liquid plant to control the H2/CO ratio in the Fischer-Tropsch reactor feed|
|US6946493||Mar 15, 2003||Sep 20, 2005||Conocophillips Company||Managing hydrogen in a gas to liquid plant|
|US6958363||Mar 15, 2003||Oct 25, 2005||Conocophillips Company||Hydrogen use in a GTL plant|
|US6995295||Sep 23, 2002||Feb 7, 2006||Exxonmobil Chemical Patents Inc.||Alkylaromatics production|
|US7411101||Feb 6, 2002||Aug 12, 2008||Exxonmobil Chemical Patents Inc.||Production of alkylaromatic compounds|
|US7425659||Jan 31, 2006||Sep 16, 2008||Exxonmobil Chemical Patents Inc.||Alkylaromatics production|
|US7501547||May 10, 2006||Mar 10, 2009||Exxonmobil Chemical Patents Inc.||Alkylaromatics production|
|US7772448||Jan 28, 2009||Aug 10, 2010||Badger Licensing Llc||Alkylaromatics production|
|US7868218||Jun 9, 2010||Jan 11, 2011||Exxonmobil Chemical Patents Inc.||Alkylaromatics production|
|US7923590||Jun 27, 2008||Apr 12, 2011||Exxonmobil Chemical Patents Inc||Production of alkylaromatic compounds|
|US8247629||Apr 17, 2007||Aug 21, 2012||Exxonmobil Chemical Patents Inc.||Monoalkylated aromatic compound production|
|US8357830||Jun 29, 2012||Jan 22, 2013||Exxonmobil Chemical Patents Inc.||Monoalkylated aromatic compound production|
|US8445738||Sep 23, 2009||May 21, 2013||Badger Licensing Llc||Process for producing cumene|
|US8524967||Nov 14, 2012||Sep 3, 2013||Exxonmobil Chemical Patents Inc.||Monoalkylated aromatic compound production|
|US8586496||Jun 19, 2009||Nov 19, 2013||Exxonmobil Chemical Patents Inc.||Preparation of molecular sieve catalysts and their use in the production of alkylaromatic hydrocarbons|
|US8629311||Mar 10, 2010||Jan 14, 2014||Stone & Webster, Inc.||Alkylated aromatics production|
|US8633342||Sep 24, 2009||Jan 21, 2014||Badger Licensing Llc||Process for producing alkylaromatic compounds|
|US8877996||Nov 8, 2013||Nov 4, 2014||Exxonmobil Chemical Patents Inc.||Alkylated aromatics production|
|US8884088||Dec 17, 2010||Nov 11, 2014||Exxonmobil Chemical Patents Inc.||Dehydrogenation process|
|US9365779||Nov 3, 2005||Jun 14, 2016||W. R. Grace & Co.-Conn.||Catalyst for light olefins and LPG in fludized catalytic units|
|US9403736||Mar 14, 2014||Aug 2, 2016||Virent, Inc.||Production of aromatics from di- and polyoxygenates|
|US9440892||Mar 14, 2014||Sep 13, 2016||Virent, Inc.||Production of aromatics from di- and polyoxygenates|
|US9617490||Dec 11, 2014||Apr 11, 2017||Exxonmobil Research And Engineering Company||Vehicle powertrain with onboard catalytic reformer|
|US9682899||Nov 17, 2014||Jun 20, 2017||Exxonmobil Chemical Patents Inc.||Hydrocarbon conversion|
|US9682900||Nov 17, 2014||Jun 20, 2017||Exxonmobil Chemical Patents Inc.||Hydrocarbon conversion|
|US9714386||Jun 29, 2015||Jul 25, 2017||Exxonmobil Chemical Patents Inc.||Production of xylenes from syngas|
|US9725327||Nov 14, 2013||Aug 8, 2017||Exxonmobil Chemical Patents Inc.||MFI with unusual morphology|
|US20040102532 *||Mar 15, 2003||May 27, 2004||Conocophillips Company||Managing hydrogen and carbon monoxide in a gas to liquid plant to control the H2/CO ratio in the Fischer-Tropsch reactor feed|
|US20040220438 *||Feb 6, 2002||Nov 4, 2004||Shiou-Shan Chen||Production of alkylaromatic compounds|
|US20070179329 *||Jan 31, 2006||Aug 2, 2007||Clark Michael C||Alkylaromatics production|
|US20070265481 *||May 10, 2006||Nov 15, 2007||Clark Michael C||Alkylaromatics production|
|US20080093263 *||Nov 3, 2005||Apr 24, 2008||Wu Cheng Cheng||Catalyst for Light Olefins and Lpg in Fludized Catalytic Units|
|US20080262279 *||Jun 27, 2008||Oct 23, 2008||Shiou-Shan Chen||Production of Alkylaromatic Compounds|
|US20090134065 *||Mar 23, 2006||May 28, 2009||Wu-Cheng Cheng||Pentasil Catalyst for Light Olefins in Fluidized Catalytic Units|
|US20090137855 *||Jan 28, 2009||May 28, 2009||Clark Michael C||Alkylaromatics Production|
|US20090306446 *||Apr 17, 2007||Dec 10, 2009||Exxonmobil Chemical Patents Inc.||Monoalkylated Aromatic Compound Production|
|US20100249472 *||Jun 9, 2010||Sep 30, 2010||Clark Michael C||Alkylaromatics Production|
|US20110118521 *||Jun 19, 2009||May 19, 2011||Duncan Carolyn B||Preparation Of Molecular Sieve Catalysts And Their Use In The Production Of Alkylaromatic Hydrocarbons|
|US20110163002 *||Sep 11, 2009||Jul 7, 2011||Patent Department||Process for enhanced propylene yield from cracked hydrocarbon feedstocks and reduced benzene in resulting naphtha fractions|
|US20110178342 *||Sep 23, 2009||Jul 21, 2011||Badger Licensing Llc||Process for producing cumene|
|US20110201858 *||Sep 23, 2009||Aug 18, 2011||Badger Licensing Llc||Process for producing cumene|
|US20110224468 *||Sep 24, 2009||Sep 15, 2011||Vincent Matthew J||Process for Producing Alkylaromatic Compounds|
|US20110224469 *||Mar 10, 2010||Sep 15, 2011||Vincent Matthew J||Alkylated Aromatics Production|
|EP0050525A1 *||Oct 21, 1981||Apr 28, 1982||The British Petroleum Company p.l.c.||Synthetic modified crystalline silica|
|EP0061799A1 *||Mar 9, 1982||Oct 6, 1982||Shell Internationale Research Maatschappij B.V.||Crystalline silicates|
|EP0116203A1 *||Nov 21, 1983||Aug 22, 1984||Mobil Oil Corporation||Synthesis of zeolite ZSM-22 with a heterocyclic organic compound|
|EP0202797A2||Apr 29, 1986||Nov 26, 1986||Mobil Oil Corporation||A method for the synthesis of zeolites|
|EP0216604A1||Sep 18, 1986||Apr 1, 1987||Mobil Oil Corporation||Process for converting oxygenates into alkylated liquid hydrocarbons|
|EP0265018A2||Oct 19, 1987||Apr 27, 1988||ENIRICERCHE S.p.A.||Bonded zeolites and process for preparing them|
|EP1894909A2||Feb 6, 2002||Mar 5, 2008||ExxonMobil Chemical Patents Inc.||Production of alkylaromatic compounds|
|EP2258658A2||Sep 18, 1998||Dec 8, 2010||Polimeri Europa S.p.A.||Process for preparing zeolites|
|EP2471895A1||Dec 15, 2011||Jul 4, 2012||ConocoPhillips Company||Process to partially upgrade slurry oil|
|EP3056470A1||Nov 22, 2013||Aug 17, 2016||ExxonMobil Chemical Patents Inc.||Small crystal zsm-5 and its use|
|WO1996002612A1 *||Jul 19, 1994||Feb 1, 1996||Mobil Oil Corporation||Shape selective hydrogenation of aromatics|
|WO1999003950A1 *||Mar 23, 1998||Jan 28, 1999||Phillips Petroleum Company||Aromatization process for converting cracked gasoline|
|WO2006107470A1||Mar 1, 2006||Oct 12, 2006||Exxonmobil Chemical Patents, Inc.||Multiphase alkylaromatics production|
|WO2006107471A1||Mar 1, 2006||Oct 12, 2006||Exxonmobil Chemical Patents Inc.||Alkylaromatics production using dilute alkene|
|WO2007089381A2||Jan 3, 2007||Aug 9, 2007||Exxonmobil Chemical Patents Inc.||Alkylaromatics production|
|WO2007133353A1||Apr 9, 2007||Nov 22, 2007||Exxonmobil Chemical Patents Inc.||Mixed phase, multistage alkylaromatics production|
|WO2008088934A1||Jan 3, 2008||Jul 24, 2008||Exxonmobil Chemical Patents Inc.||Liquid phase alkylation with multiple catalysts|
|WO2008100658A1||Jan 10, 2008||Aug 21, 2008||Exxonmobil Chemical Patents Inc.||Production of high purity ethylbenzene from non-extracted feed and non-extracted reformate useful therein|
|WO2011081785A1||Dec 6, 2010||Jul 7, 2011||Exxonmobil Research And Engineering Company||Preparation of hydrogenation and dehydrogenation catalysts|
|WO2011096991A1||Dec 17, 2010||Aug 11, 2011||Exxonmobil Chemical Patents Inc.||Dehydrogenation process|
|WO2011096995A1||Dec 17, 2010||Aug 11, 2011||Exxonmobil Chemical Patents Inc.||Dehydrogenation process|
|WO2012092436A1||Dec 29, 2011||Jul 5, 2012||Virent, Inc.||Organo-catalytic biomass deconstruction|
|WO2012092440A1||Dec 29, 2011||Jul 5, 2012||Virent, Inc.||Solvolysis of biomass using solvent from a bioreforming process|
|WO2012162403A1||May 23, 2012||Nov 29, 2012||Virent, Inc.||Production of chemicals and fuels from biomass|
|WO2013059161A1||Oct 16, 2012||Apr 25, 2013||Exxonmobil Research And Engineering Company||Phosphorus modified zeolite catalysts|
|WO2013059169A1||Oct 16, 2012||Apr 25, 2013||Exxonmobil Research And Engineering Company||Phosphorus modified zeolite catalysts|
|WO2013059172A1||Oct 16, 2012||Apr 25, 2013||Exxonmobil Research And Engineering Company||Process for producing phosphorus modified zeolite catalysts|
|WO2013077885A1||Nov 29, 2011||May 30, 2013||Virent, Inc.||Dehydrogenation of alkanols to increase yield of aromatics|
|WO2013081994A1||Nov 27, 2012||Jun 6, 2013||Exxonmobil Research And Engineering Company||Synthesis of high activity large crystal zsm-5|
|WO2013085681A1||Nov 14, 2012||Jun 13, 2013||Exxonmobil Chemical Patents Inc.||Production process of para -xylene and apparatus thereof|
|WO2013119318A1||Dec 13, 2012||Aug 15, 2013||Exxonmobil Chemical Patents Inc.||Production of monoalkyl aromatic compounds|
|WO2014003732A1||Jun 27, 2012||Jan 3, 2014||Badger Licensing Llc||Process for producing cumene|
|WO2014008268A1||Jul 2, 2013||Jan 9, 2014||Badger Licensing Llc||Process for producing cumene|
|WO2014011359A1||Jun 17, 2013||Jan 16, 2014||Badger Licensing Llc||Process for producing phenol|
|WO2014018515A1||Jul 23, 2013||Jan 30, 2014||Badger Licensing Llc||Process for producing cumene|
|WO2014028003A1||Aug 14, 2012||Feb 20, 2014||Stone & Webster Process Technology, Inc.||Integrated process for producing cumene and purifying isopropanol|
|WO2014082862A1||Nov 14, 2013||Jun 5, 2014||Exxonmobil Chemical Patents Inc.||Mfi with unusual morphology|
|WO2014084810A1||Nov 27, 2012||Jun 5, 2014||Badger Licensing Llc||Production of styrene|
|WO2014099261A1||Nov 22, 2013||Jun 26, 2014||Exxonbobil Chemical Patents Inc.||Synthesis of zsm-5|
|WO2014109766A1||Jan 14, 2013||Jul 17, 2014||Badger Licensing Llc||Process for balancing gasoline and distillate production in a refinery|
|WO2014152370A2||Mar 14, 2014||Sep 25, 2014||Virent, Inc.||Production of aromatics from di-and poly-oxygenates|
|WO2014182294A1||May 8, 2013||Nov 13, 2014||Badger Licensing Llc||Aromatics alkylation process|
|WO2014190124A1||May 22, 2014||Nov 27, 2014||Virent, Inc.||Hydrogenation of carboxylic acids to increase yield of aromatics|
|WO2014190161A1||May 22, 2014||Nov 27, 2014||Virent, Inc.||Process for converting biomass to aromatic hydrocarbons|
|WO2015031363A1||Aug 26, 2014||Mar 5, 2015||Exxonmobil Chemical Patents Inc.||Oxygen storage and production of c5+ hydrocarbons|
|WO2015084518A1||Nov 3, 2014||Jun 11, 2015||Exxonmobil Upstream Research Company||Method and system for producing liquid hydrocarbons|
|WO2015084576A2||Nov 17, 2014||Jun 11, 2015||Exxonmobil Chemical Patents Inc.||Hydrocarbon conversion|
|WO2015089254A1||Dec 11, 2014||Jun 18, 2015||Exxonmobil Research And Engineering Company||Vehicle powertrain with onboard catalytic reformer|
|WO2015089256A1||Dec 11, 2014||Jun 18, 2015||Exxonmobil Research And Engineering Company||Enhanced methane formation in reforming catalysts|
|WO2015089257A1||Dec 11, 2014||Jun 18, 2015||Exxonmobil Research And Engineering Company||Natural gas vehicle powertrain with onboard catalytic reformer|
|WO2015094679A1||Dec 4, 2014||Jun 25, 2015||Exxonmobil Research And Engineering Company||Catalyst for selective conversion of oxygenates to aromatics|
|WO2015094685A1||Dec 4, 2014||Jun 25, 2015||Exxonmobil Research And Engineering Company||Alumina bound catalyst for selective conversion of oxygenates to aromatics|
|WO2015094687A1||Dec 4, 2014||Jun 25, 2015||Exxonmobil Research And Engineering Company||Bound catalyst for selective conversion of oxygenates to aromatics|
|WO2015094696A1||Dec 4, 2014||Jun 25, 2015||Exxonmobil Chemical Patents Inc.||Process for converting oxygenates to aromatic hydrocarbons|
|WO2016025077A1||Jun 18, 2015||Feb 18, 2016||Exxonmobil Chemical Patents Inc.||Aromatics production process|
|WO2016085908A1||Nov 24, 2015||Jun 2, 2016||Badger Licensing Llc||Process for reducing the benzene content of gasoline|
|WO2016105888A1||Dec 2, 2015||Jun 30, 2016||Exxonmobil Research And Engineering Company||Conversion of oxygenates to aromatics|
|WO2016148755A1||Dec 15, 2015||Sep 22, 2016||Exxonmobil Chemical Patents Inc.||Process and apparatus for the production of para-xylene|
|WO2016160081A1||Dec 7, 2015||Oct 6, 2016||Exxonmobil Chemical Patents Inc.||Oxygenated hydrocarbon conversion zoned method|
|WO2016175898A1||Dec 15, 2015||Nov 3, 2016||Exxonmobil Chemical Patents Inc.||Process and apparatus for the production of para-xylene|
|WO2016179133A1||May 3, 2016||Nov 10, 2016||Shell Oil Company||Reduced emissions aromatics-containing jet fuels|
|WO2017048378A1||Jul 29, 2016||Mar 23, 2017||Exxonmobil Chemical Patents Inc.||Process for recovering para-xylene using a metal organic framework adsorbent in a simulated moving-bed process|
|WO2017052856A1||Aug 18, 2016||Mar 30, 2017||Exxonmobil Chemical Patents Inc.||Catalyst and its use in dehydrocyclization processes|
|WO2017065771A1||Oct 15, 2015||Apr 20, 2017||Badger Licensing Llc||Production of alkylaromatic compounds|
|WO2017112716A1||Dec 21, 2016||Jun 29, 2017||Shell Oil Company||Methods of providing higher quality liquid kerosene based-propulsion fuels|
|U.S. Classification||208/110, 423/DIG.22, 423/713, 556/10, 556/173, 423/326, 534/11, 556/9, 208/134, 423/335, 556/400, 423/332, 502/62, 423/705, 208/119|
|International Classification||C01B39/08, B01J29/46, C07C7/13, C01B37/02, B01J29/40, B01J31/02|
|Cooperative Classification||Y10S423/22, B01J29/46, B01J2229/37, C01B37/02, B01J31/0254, B01J29/405, C07C7/13, C01B39/085, C01B39/08, B01J31/0239|
|European Classification||B01J31/02E2S, C07C7/13, C01B37/02, C01B39/08D, C01B39/08, B01J29/40Z, B01J29/46|