USRE29948E - Crystalline silicates and catalytic conversion of organic compounds therewith - Google Patents

Crystalline silicates and catalytic conversion of organic compounds therewith Download PDF

Info

Publication number
USRE29948E
USRE29948E US05801944 US80194477A USRE29948E US RE29948 E USRE29948 E US RE29948E US 05801944 US05801944 US 05801944 US 80194477 A US80194477 A US 80194477A US RE29948 E USRE29948 E US RE29948E
Authority
US
Grant status
Grant
Patent type
Prior art keywords
sub
crystalline
composition
sodium
grams
Prior art date
Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
Expired - Lifetime
Application number
US05801944
Inventor
Francis G. Dwyer
Edwin E. Jenkins
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
ExxonMobil Oil Corp
Original Assignee
ExxonMobil Oil Corp
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Grant date

Links

Images

Classifications

    • BPERFORMING OPERATIONS; TRANSPORTING
    • B01PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01JCHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J31/00Catalysts comprising hydrides, coordination complexes or organic compounds
    • B01J31/02Catalysts comprising hydrides, coordination complexes or organic compounds containing organic compounds or metal hydrides
    • B01J31/0234Nitrogen-, phosphorus-, arsenic- or antimony-containing compounds
    • B01J31/0235Nitrogen containing compounds
    • B01J31/0254Nitrogen containing compounds on mineral substrates
    • BPERFORMING OPERATIONS; TRANSPORTING
    • B01PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01JCHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J29/00Catalysts comprising molecular sieves
    • B01J29/04Catalysts comprising molecular sieves having base-exchange properties, e.g. crystalline zeolites
    • B01J29/06Crystalline aluminosilicate zeolites; Isomorphous compounds thereof
    • B01J29/40Crystalline aluminosilicate zeolites; Isomorphous compounds thereof of the pentasil type, e.g. types ZSM-5, ZSM-8 or ZSM-11, as exemplified by patent documents US3702886, GB1334243 and US3709979, respectively
    • B01J29/405Crystalline aluminosilicate zeolites; Isomorphous compounds thereof of the pentasil type, e.g. types ZSM-5, ZSM-8 or ZSM-11, as exemplified by patent documents US3702886, GB1334243 and US3709979, respectively containing rare earth elements, titanium, zirconium, hafnium, zinc, cadmium, mercury, gallium, indium, thallium, tin or lead
    • BPERFORMING OPERATIONS; TRANSPORTING
    • B01PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01JCHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J29/00Catalysts comprising molecular sieves
    • B01J29/04Catalysts comprising molecular sieves having base-exchange properties, e.g. crystalline zeolites
    • B01J29/06Crystalline aluminosilicate zeolites; Isomorphous compounds thereof
    • B01J29/40Crystalline aluminosilicate zeolites; Isomorphous compounds thereof of the pentasil type, e.g. types ZSM-5, ZSM-8 or ZSM-11, as exemplified by patent documents US3702886, GB1334243 and US3709979, respectively
    • B01J29/42Crystalline aluminosilicate zeolites; Isomorphous compounds thereof of the pentasil type, e.g. types ZSM-5, ZSM-8 or ZSM-11, as exemplified by patent documents US3702886, GB1334243 and US3709979, respectively containing iron group metals, noble metals or copper
    • B01J29/46Iron group metals or copper
    • CCHEMISTRY; METALLURGY
    • C01INORGANIC CHEMISTRY
    • C01BNON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
    • C01B37/00Compounds having molecular sieve properties but not having base-exchange properties
    • C01B37/02Crystalline silica-polymorphs, e.g. silicalites dealuminated aluminosilicate zeolites
    • CCHEMISTRY; METALLURGY
    • C01INORGANIC CHEMISTRY
    • C01BNON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
    • C01B39/00Compounds having molecular sieve and base-exchange properties, e.g. crystalline zeolites; Their preparation; After-treatment, e.g. ion-exchange or dealumination
    • C01B39/02Crystalline aluminosilicate zeolites; Isomorphous compounds thereof; Direct preparation thereof; Preparation thereof starting from a reaction mixture containing a crystalline zeolite of another type, or from preformed reactants; After-treatment thereof
    • C01B39/06Preparation of isomorphous zeolites characterised by measures to replace the aluminium or silicon atoms in the lattice framework by atoms of other elements, i.e. by direct or secondary synthesis
    • C01B39/08Preparation of isomorphous zeolites characterised by measures to replace the aluminium or silicon atoms in the lattice framework by atoms of other elements, i.e. by direct or secondary synthesis the aluminium atoms being wholly replaced
    • CCHEMISTRY; METALLURGY
    • C01INORGANIC CHEMISTRY
    • C01BNON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
    • C01B39/00Compounds having molecular sieve and base-exchange properties, e.g. crystalline zeolites; Their preparation; After-treatment, e.g. ion-exchange or dealumination
    • C01B39/02Crystalline aluminosilicate zeolites; Isomorphous compounds thereof; Direct preparation thereof; Preparation thereof starting from a reaction mixture containing a crystalline zeolite of another type, or from preformed reactants; After-treatment thereof
    • C01B39/06Preparation of isomorphous zeolites characterised by measures to replace the aluminium or silicon atoms in the lattice framework by atoms of other elements, i.e. by direct or secondary synthesis
    • C01B39/08Preparation of isomorphous zeolites characterised by measures to replace the aluminium or silicon atoms in the lattice framework by atoms of other elements, i.e. by direct or secondary synthesis the aluminium atoms being wholly replaced
    • C01B39/085Group IVB- metallosilicates
    • CCHEMISTRY; METALLURGY
    • C07ORGANIC CHEMISTRY
    • C07CACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C7/00Purification; Separation; Use of additives
    • C07C7/12Purification; Separation; Use of additives by adsorption, i.e. purification or separation of hydrocarbons with the aid of solids, e.g. with ion-exchangers
    • C07C7/13Purification; Separation; Use of additives by adsorption, i.e. purification or separation of hydrocarbons with the aid of solids, e.g. with ion-exchangers by molecular-sieve technique
    • BPERFORMING OPERATIONS; TRANSPORTING
    • B01PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01JCHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J2229/00Aspects of molecular sieve catalysts not covered by B01J29/00
    • B01J2229/30After treatment, characterised by the means used
    • B01J2229/37Acid treatment
    • BPERFORMING OPERATIONS; TRANSPORTING
    • B01PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01JCHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J31/00Catalysts comprising hydrides, coordination complexes or organic compounds
    • B01J31/02Catalysts comprising hydrides, coordination complexes or organic compounds containing organic compounds or metal hydrides
    • B01J31/0234Nitrogen-, phosphorus-, arsenic- or antimony-containing compounds
    • B01J31/0235Nitrogen containing compounds
    • B01J31/0239Quaternary ammonium compounds
    • YGENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y10TECHNICAL SUBJECTS COVERED BY FORMER USPC
    • Y10STECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y10S423/00Chemistry of inorganic compounds
    • Y10S423/22MFI, e.g. ZSM-5. silicalite, LZ-241

Abstract

A crystalline metal organosilicate having the composition, in its anhydrous state, 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
:>1SiO2
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 a number greater than 0 but not exceeding 1, said organosilicate being characterized by a specified X-ray diffraction pattern. Said organosilicate is prepared by digesting a reaction mixture comprising (R4 N)2 O, sodium oxide, an oxide of a metal other than a metal of group IIIA, an oxide of silicon and water. The crystalline organosilicates are useful as adsorbents and in their catalytically active form as catalysts for organic compound conversion.

Description

BACKGROUND OF THE INVENTION

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.

SUMMARY OF THE INVENTION

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.

DESCRIPTION OF SPECIFIC EMBODIMENTS

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.

EXAMPLE 1

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______________________________________
EXAMPLE 2

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______________________________________
EXAMPLE 3

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______________________________________
EXAMPLE 4

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.)______________________________________
EXAMPLE 5

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.

EXAMPLE 6

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______________________________________
EXAMPLE 7

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______________________________________
EXAMPLE 8

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______________________________________
EXAMPLE 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______________________________________
EXAMPLE 10

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______________________________________

Claims (11)

We claim:
1. A crystal metal organosilicate having a composition, in its 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 sodium or sodium in combination with tin, calcium, nickel or zinc, R is a tetraalkylammonium and x is a number greater than 0 but not exceeding 1, said organosilicate having the X-ray diffraction lines set forth in Table I of the specification.
2. A crystalline silicate resulting from thermal treatment of the composition of claim 1 by heating to a temperature in the range of 200° to 600° C. for between 1 and 48 hours.
3. The composition of claim 1 which has been exchanged with ammonium ions.
4. The composition of claim 1 wherein R is tetrapropylammonium.
5. The composition of claim 1 wherein M comprises tin.
6. The composition of claim 1 wherein M comprises sodium.
7. The composition of claim 1 wherein M comprises calcium.
8. The composition of claim 1 wherein M comprises nickel.
9. The composition of claim 1 wherein M comprises zinc.
10. A method of preparing a crystalline metal organosilicate as defined in claim 1 which comprises preparing a mixture containing a tetraalkylammonium compound, sodium oxide, an oxide of tin, calcium, nickel, or zinc, an oxide of silicon and water and having a composition in terms of mole ratios of oxides falling within the following ranges:
______________________________________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______________________________________
wherein R is alkyl radical and M is total metal, maintaining the mixture at a temperature at about 100° C. to about 175° C. until crystals of said metal organosilicate are formed and separated and recovering said crystals.
11. A method of preparing a crystalline metal organosilicate as defined in claim 1 which comprises preparing a mixture containing a tetraalkylammonium compound, sodium oxide, an oxide of tin, calcium, nickel or zinc, an oxide of silicon and water and having a composition in terms of mole ratios of oxides falling within the following ranges:
______________________________________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______________________________________
wherein R is an alkyl radical and M is total metal, maintaining the mixture at a temperature at about 100° C. to about 175° C. until crystals of said metal organosilicate are formed and thereafter separating and recovering said crystals. .Iadd. 12. In a process for conducting in the presence of a solid porous catalyst a hydrocarbon conversion reaction, the improvement which comprises contacting charge hydrocarbons for said reaction at conversion conditions with a catalyst comprising the composition of claim 1. .Iaddend. .Iadd. 13. In a process for conducting in the presence of a solid porous catalyst an organic compound conversion reaction, the improvement which comprises contacting an organic compound charge for said reaction at conversion conditions with a catalyst comprising the composition of claim 2. .Iaddend..Iadd. 14. In a process for conducting in the presence of a solid porous catalyst a hydrocarbon conversion reaction, the improvement which comprises contacting charge hydrocarbons for said reaction at conversion conditions with a catalyst comprising the composition of claim 3. .Iaddend..Iadd. 15. The process of claim 12 wherein said catalyst comprises the composition of claim 4. .Iaddend..Iadd. 16. The process of claim 12 wherein said catalyst comprises the composition of claim 5. .Iaddend..Iadd. 17. The process of claim 12 wherein said catalyst comprises the composition of claim 6. .Iaddend..Iadd. 18. The process of claim 12 wherein said catalyst comprises the composition of claim 7. .Iaddend..Iadd. 19. The process of claim 12 wherein said catalyst comprises the composition of claim 8. .Iaddend..Iadd. 20. The process of claim 12 wherein said catalyst comprises the composition of claim 9. .Iaddend.
US05801944 1973-11-02 1977-05-31 Crystalline silicates and catalytic conversion of organic compounds therewith Expired - Lifetime USRE29948E (en)

Priority Applications (1)

Application Number Priority Date Filing Date Title
US05412393 US3941871A (en) 1973-11-02 1973-11-02 Crystalline silicates and method of preparing the same

Related Parent Applications (1)

Application Number Title Priority Date Filing Date
US05412393 Reissue US3941871A (en) 1973-11-02 1973-11-02 Crystalline silicates and method of preparing the same

Publications (1)

Publication Number Publication Date
USRE29948E true USRE29948E (en) 1979-03-27

Family

ID=23632788

Family Applications (2)

Application Number Title Priority Date Filing Date
US05412393 Expired - Lifetime US3941871A (en) 1973-11-02 1973-11-02 Crystalline silicates and method of preparing the same
US05801944 Expired - Lifetime USRE29948E (en) 1973-11-02 1977-05-31 Crystalline silicates and catalytic conversion of organic compounds therewith

Family Applications Before (1)

Application Number Title Priority Date Filing Date
US05412393 Expired - Lifetime US3941871A (en) 1973-11-02 1973-11-02 Crystalline silicates and method of preparing the same

Country Status (1)

Country Link
US (2) US3941871A (en)

Cited By (127)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
FR2454328A1 (en) * 1979-04-20 1980-11-14 Du Pont crystalline silica and para-xylene process for preparing from toluene using it as catalyst
EP0050525A1 (en) * 1980-10-22 1982-04-28 The British Petroleum Company p.l.c. Synthetic modified crystalline silica
EP0061799A1 (en) * 1981-03-30 1982-10-06 Shell Internationale Research Maatschappij B.V. Crystalline silicates
EP0116203A1 (en) * 1982-12-09 1984-08-22 Mobil Oil Corporation Synthesis of zeolite ZSM-22 with a heterocyclic organic compound
EP0202797A2 (en) 1985-05-14 1986-11-26 Mobil Oil Corporation A method for the synthesis of zeolites
EP0216604A1 (en) 1985-09-23 1987-04-01 Mobil Oil Corporation Process for converting oxygenates into alkylated liquid hydrocarbons
EP0265018A2 (en) 1986-10-22 1988-04-27 ENIRICERCHE S.p.A. Bonded zeolites and process for preparing them
US4790927A (en) 1981-05-26 1988-12-13 Union Oil Company Of California Process for simultaneous hydrotreating and hydrodewaxing of hydrocarbons
US4877762A (en) 1981-05-26 1989-10-31 Union Oil Company Of California Catalyst for simultaneous hydrotreating and hydrodewaxing of hydrocarbons
US4970397A (en) * 1989-06-16 1990-11-13 Mobil Oil Corporation Method and apparatus for activating catalysts using electromagnetic radiation
US4990710A (en) * 1988-06-24 1991-02-05 Mobil Oil Corporation Tin-containing microporous crystalline materials and their use as dehydrogenation, dehydrocyclization and reforming catalysts
US5037529A (en) * 1989-12-29 1991-08-06 Mobil Oil Corp. Integrated low pressure aromatization process
US5103066A (en) * 1990-12-10 1992-04-07 Mobil Oil Corp. Dehydrogenation of alcohols over non-acidic metal-zeolite catalysts
US5110571A (en) * 1987-09-01 1992-05-05 Exxon Research And Engineering Company Stannosilicates and preparation thereof (C-2417)
US5110568A (en) * 1987-09-01 1992-05-05 Exxon Research And Engineering Company Stannosilicates and preparation thereof
US5122489A (en) * 1990-10-15 1992-06-16 Mobil Oil Corporation Non-acidic dehydrogenation catalyst of enhanced stability
US5124497A (en) * 1989-10-11 1992-06-23 Mobil Oil Corporation Production of mono-substituted alkylaromatics from C8 +N-paraffins
US5147837A (en) * 1990-10-22 1992-09-15 Mobil Oil Corporation Titania containing dehydrogenation catalysts
US5174978A (en) * 1991-10-04 1992-12-29 Mobil Oil Corp. Synthesis of crystalline ZSM-5-type material
US5174981A (en) * 1991-10-04 1992-12-29 Mobil Oil Corp. Synthesis of crystalline ZSM-5-type material
US5174977A (en) * 1991-10-04 1992-12-29 Mobil Oil Corp. Synthesis of crystalline ZSM-5-type material
US5192728A (en) * 1988-06-24 1993-03-09 Mobil Oil Corporation Tin-colating microporous crystalline materials and their use as dehydrogenation, dehydrocyclization reforming catalysts
US5209918A (en) * 1991-10-04 1993-05-11 Mobil Oil Corp. Synthesis of crystalline ZSM-5-type material
US5248841A (en) * 1982-04-30 1993-09-28 Mobil Oil Corporation Hydrocarbon conversion with ZSM-22 zeolite
US5310714A (en) * 1992-07-08 1994-05-10 Mobil Oil Corp. Synthesis of zeolite films bonded to substrates, structures and uses thereof
US5316661A (en) * 1992-07-08 1994-05-31 Mobil Oil Corporation Processes for converting feedstock organic compounds
US5344553A (en) * 1993-02-22 1994-09-06 Mobil Oil Corporation Upgrading of a hydrocarbon feedstock utilizing a graded, mesoporous catalyst system
US5349117A (en) * 1992-07-08 1994-09-20 Mobil Oil Corp. Process for sorption separation
US5350504A (en) * 1992-12-18 1994-09-27 Mobil Oil Corporation Shape selective hydrogenation of aromatics over modified non-acidic platinum/ZSM-5 catalysts
US5369071A (en) * 1992-12-11 1994-11-29 Mobil Oil Corporation Manufacture of improved catalyst
US5374411A (en) * 1987-08-28 1994-12-20 The Dow Chemical Company Crystalline aluminumphosphate compositions
US5430218A (en) * 1993-08-27 1995-07-04 Chevron U.S.A. Inc. Dehydrogenation using dehydrogenation catalyst and polymer-porous solid composite membrane
WO1996002612A1 (en) * 1992-12-18 1996-02-01 Mobil Oil Corporation Shape selective hydrogenation of aromatics
US5536857A (en) * 1994-07-05 1996-07-16 Ford Motor Company Single source volatile precursor for SiO2.TiO2 powders and films
WO1999003950A1 (en) * 1997-07-15 1999-01-28 Phillips Petroleum Company Aromatization process for converting cracked gasoline
US6392109B1 (en) 2000-02-29 2002-05-21 Chevron U.S.A. Inc. Synthesis of alkybenzenes and synlubes from Fischer-Tropsch products
US6441263B1 (en) 2000-07-07 2002-08-27 Chevrontexaco Corporation Ethylene manufacture by use of molecular redistribution on feedstock C3-5 components
US6455595B1 (en) 2000-07-24 2002-09-24 Chevron U.S.A. Inc. Methods for optimizing fischer-tropsch synthesis
US6472441B1 (en) 2000-07-24 2002-10-29 Chevron U.S.A. Inc. Methods for optimizing Fischer-Tropsch synthesis of hydrocarbons in the distillate fuel and/or lube base oil ranges
US6500233B1 (en) 2000-10-26 2002-12-31 Chevron U.S.A. Inc. Purification of p-xylene using composite mixed matrix membranes
US6541408B2 (en) 1997-12-19 2003-04-01 Exxonmobil Oil Corp. Zeolite catalysts having stabilized hydrogenation-dehydrogenation function
US6566569B1 (en) 2000-06-23 2003-05-20 Chevron U.S.A. Inc. Conversion of refinery C5 paraffins into C4 and C6 paraffins
US6670517B1 (en) 2000-08-24 2003-12-30 Exxon Mobil Chemical Patents Inc. Process for alkylating aromatics
US20040102532A1 (en) * 2002-11-25 2004-05-27 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
US6755900B2 (en) 2001-12-20 2004-06-29 Chevron U.S.A. Inc. Crosslinked and crosslinkable hollow fiber mixed matrix membrane and method of making same
US6806087B2 (en) 2000-08-14 2004-10-19 Chevron U.S.A. Inc. Use of microchannel reactors in combinatorial chemistry
US20040220438A1 (en) * 2001-02-07 2004-11-04 Shiou-Shan Chen Production of alkylaromatic compounds
US6864398B2 (en) 2000-04-03 2005-03-08 Chevron U.S.A. Inc. Conversion of syngas to distillate fuels
US6946493B2 (en) 2003-03-15 2005-09-20 Conocophillips Company Managing hydrogen in a gas to liquid plant
US6958363B2 (en) 2003-03-15 2005-10-25 Conocophillips Company Hydrogen use in a GTL plant
US6995295B2 (en) 2002-09-23 2006-02-07 Exxonmobil Chemical Patents Inc. Alkylaromatics production
WO2006107471A1 (en) 2005-03-31 2006-10-12 Exxonmobil Chemical Patents Inc. Alkylaromatics production using dilute alkene
WO2006107470A1 (en) 2005-03-31 2006-10-12 Exxonmobil Chemical Patents, Inc. Multiphase alkylaromatics production
US20070179329A1 (en) * 2006-01-31 2007-08-02 Clark Michael C Alkylaromatics production
US20070265481A1 (en) * 2006-05-10 2007-11-15 Clark Michael C Alkylaromatics production
EP1894909A2 (en) 2001-02-07 2008-03-05 ExxonMobil Chemical Patents Inc. Production of alkylaromatic compounds
US20080093263A1 (en) * 2004-11-05 2008-04-24 Wu Cheng Cheng Catalyst for Light Olefins and Lpg in Fludized Catalytic Units
WO2008088934A1 (en) 2007-01-19 2008-07-24 Exxonmobil Chemical Patents Inc. Liquid phase alkylation with multiple catalysts
WO2008100658A1 (en) 2007-02-12 2008-08-21 Exxonmobil Chemical Patents Inc. Production of high purity ethylbenzene from non-extracted feed and non-extracted reformate useful therein
US20090134065A1 (en) * 2005-06-29 2009-05-28 Wu-Cheng Cheng Pentasil Catalyst for Light Olefins in Fluidized Catalytic Units
US20090306446A1 (en) * 2006-05-24 2009-12-10 Exxonmobil Chemical Patents Inc. Monoalkylated Aromatic Compound Production
EP2258658A2 (en) 1997-10-03 2010-12-08 Polimeri Europa S.p.A. Process for preparing zeolites
US20110118521A1 (en) * 2008-07-22 2011-05-19 Duncan Carolyn B Preparation Of Molecular Sieve Catalysts And Their Use In The Production Of Alkylaromatic Hydrocarbons
US20110163002A1 (en) * 2008-09-15 2011-07-07 Patent Department Process for enhanced propylene yield from cracked hydrocarbon feedstocks and reduced benzene in resulting naphtha fractions
WO2011081785A1 (en) 2009-12-15 2011-07-07 Exxonmobil Research And Engineering Company Preparation of hydrogenation and dehydrogenation catalysts
US20110178342A1 (en) * 2008-10-06 2011-07-21 Badger Licensing Llc Process for producing cumene
WO2011096991A1 (en) 2010-02-05 2011-08-11 Exxonmobil Chemical Patents Inc. Dehydrogenation process
WO2011096995A1 (en) 2010-02-05 2011-08-11 Exxonmobil Chemical Patents Inc. Dehydrogenation process
US20110201858A1 (en) * 2008-10-06 2011-08-18 Badger Licensing Llc Process for producing cumene
US20110224468A1 (en) * 2008-10-10 2011-09-15 Vincent Matthew J Process for Producing Alkylaromatic Compounds
US20110224469A1 (en) * 2010-03-10 2011-09-15 Vincent Matthew J Alkylated Aromatics Production
EP2471895A1 (en) 2011-01-04 2012-07-04 ConocoPhillips Company Process to partially upgrade slurry oil
WO2012092440A1 (en) 2010-12-30 2012-07-05 Virent, Inc. Solvolysis of biomass using solvent from a bioreforming process
WO2012092436A1 (en) 2010-12-30 2012-07-05 Virent, Inc. Organo-catalytic biomass deconstruction
WO2012142490A1 (en) 2011-04-13 2012-10-18 Kior, Inc. Improved catalyst for thermocatalytic conversion of biomass to liquid fuels and chemicals
WO2012162403A1 (en) 2011-05-23 2012-11-29 Virent, Inc. Production of chemicals and fuels from biomass
WO2013059172A1 (en) 2011-10-17 2013-04-25 Exxonmobil Research And Engineering Company Process for producing phosphorus modified zeolite catalysts
WO2013077885A1 (en) 2011-11-23 2013-05-30 Virent, Inc. Dehydrogenation of alkanols to increase yield of aromatics
WO2013081994A1 (en) 2011-12-01 2013-06-06 Exxonmobil Research And Engineering Company Synthesis of high activity large crystal zsm-5
WO2013085681A1 (en) 2011-12-06 2013-06-13 Exxonmobil Chemical Patents Inc. Production process of para -xylene and apparatus thereof
WO2013119318A1 (en) 2012-02-08 2013-08-15 Exxonmobil Chemical Patents Inc. Production of monoalkyl aromatic compounds
WO2014003732A1 (en) 2012-06-27 2014-01-03 Badger Licensing Llc Process for producing cumene
WO2014008268A1 (en) 2012-07-05 2014-01-09 Badger Licensing Llc Process for producing cumene
WO2014011359A1 (en) 2012-07-13 2014-01-16 Badger Licensing Llc Process for producing phenol
WO2014018515A1 (en) 2012-07-26 2014-01-30 Badger Licensing Llc Process for producing cumene
WO2014028003A1 (en) 2012-08-14 2014-02-20 Stone & Webster Process Technology, Inc. Integrated process for producing cumene and purifying isopropanol
WO2014082862A1 (en) 2012-11-28 2014-06-05 Exxonmobil Chemical Patents Inc. Mfi with unusual morphology
WO2014084810A1 (en) 2012-11-27 2014-06-05 Badger Licensing Llc Production of styrene
WO2014099261A1 (en) 2012-12-21 2014-06-26 Exxonbobil Chemical Patents Inc. Synthesis of zsm-5
WO2014109766A1 (en) 2013-01-14 2014-07-17 Badger Licensing Llc Process for balancing gasoline and distillate production in a refinery
WO2014152370A2 (en) 2013-03-14 2014-09-25 Virent, Inc. Production of aromatics from di-and poly-oxygenates
WO2014182294A1 (en) 2013-05-08 2014-11-13 Badger Licensing Llc Aromatics alkylation process
WO2014190124A1 (en) 2013-05-22 2014-11-27 Virent, Inc. Hydrogenation of carboxylic acids to increase yield of aromatics
WO2014190161A1 (en) 2013-05-22 2014-11-27 Virent, Inc. Process for converting biomass to aromatic hydrocarbons
WO2015031363A1 (en) 2013-08-30 2015-03-05 Exxonmobil Chemical Patents Inc. Oxygen storage and production of c5+ hydrocarbons
WO2015084518A1 (en) 2013-12-06 2015-06-11 Exxonmobil Upstream Research Company Method and system for producing liquid hydrocarbons
WO2015084576A2 (en) 2013-12-06 2015-06-11 Exxonmobil Chemical Patents Inc. Hydrocarbon conversion
WO2015089256A1 (en) 2013-12-13 2015-06-18 Exxonmobil Research And Engineering Company Enhanced methane formation in reforming catalysts
WO2015094687A1 (en) 2013-12-20 2015-06-25 Exxonmobil Research And Engineering Company Bound catalyst for selective conversion of oxygenates to aromatics
WO2015094696A1 (en) 2013-12-20 2015-06-25 Exxonmobil Chemical Patents Inc. Process for converting oxygenates to aromatic hydrocarbons
WO2016025077A1 (en) 2014-08-15 2016-02-18 Exxonmobil Chemical Patents Inc. Aromatics production process
WO2016085908A1 (en) 2014-11-25 2016-06-02 Badger Licensing Llc Process for reducing the benzene content of gasoline
WO2016105888A1 (en) 2014-12-22 2016-06-30 Exxonmobil Research And Engineering Company Conversion of oxygenates to aromatics
EP3056470A1 (en) 2012-12-21 2016-08-17 ExxonMobil Chemical Patents Inc. Small crystal zsm-5 and its use
WO2016148755A1 (en) 2015-03-19 2016-09-22 Exxonmobil Chemical Patents Inc. Process and apparatus for the production of para-xylene
WO2016160081A1 (en) 2015-03-31 2016-10-06 Exxonmobil Chemical Patents Inc. Oxygenated hydrocarbon conversion zoned method
WO2016175898A1 (en) 2015-04-30 2016-11-03 Exxonmobil Chemical Patents Inc. Process and apparatus for the production of para-xylene
WO2016179133A1 (en) 2015-05-05 2016-11-10 Shell Oil Company Reduced emissions aromatics-containing jet fuels
WO2017048378A1 (en) 2015-09-17 2017-03-23 Exxonmobil Chemical Patents Inc. Process for recovering para-xylene using a metal organic framework adsorbent in a simulated moving-bed process
WO2017052856A1 (en) 2015-09-25 2017-03-30 Exxonmobil Chemical Patents Inc. Catalyst and its use in dehydrocyclization processes
WO2017065771A1 (en) 2015-10-15 2017-04-20 Badger Licensing Llc Production of alkylaromatic compounds
US9682899B2 (en) 2013-12-06 2017-06-20 Exxonmobil Chemical Patents Inc. Hydrocarbon conversion
WO2017112716A1 (en) 2015-12-21 2017-06-29 Shell Oil Company Methods of providing higher quality liquid kerosene based-propulsion fuels
US9714386B2 (en) 2014-07-24 2017-07-25 Exxonmobil Chemical Patents Inc. Production of xylenes from syngas
WO2017142526A1 (en) 2016-02-17 2017-08-24 Badger Licensing Llc Process for producing ethylbenzene
WO2017142666A1 (en) 2016-02-19 2017-08-24 Exxonmobil Research And Engineering Company Small crystal, high surface area emm-30 zeolites, their synthesis and use
WO2017146914A1 (en) 2016-02-26 2017-08-31 Exxonmobil Chemical Patents Inc. Process for recovering para-xylene
US9783463B2 (en) 2014-09-30 2017-10-10 Exxonmobil Chemical Patents Inc. Conversion of acetylene and methanol to aromatics
US9790145B2 (en) 2013-12-06 2017-10-17 Exxonmobil Chemical Patents Inc. Production of C2+ olefins
WO2017189137A1 (en) 2016-04-25 2017-11-02 Exxonmobil Chemical Patents Inc. Catalytic aromatization
WO2017188934A1 (en) 2016-04-26 2017-11-02 Badger Licensing Llc Process for reducing the benzene content of gasoline
US9809758B2 (en) 2014-07-24 2017-11-07 Exxonmobil Chemical Patents Inc. Production of xylenes from syngas
US9845272B2 (en) 2015-09-25 2017-12-19 Exxonmobil Chemical Patents Inc. Hydrocarbon conversion
US9938205B2 (en) 2014-10-10 2018-04-10 Exxonmobil Research And Engineering Company Apparatus and process for producing gasoline, olefins and aromatics from oxygenates
US9950971B2 (en) 2014-07-23 2018-04-24 Exxonmobil Chemical Patents Inc. Process and catalyst for methane conversion to aromatics
US9963406B2 (en) 2015-09-25 2018-05-08 Exxonmobil Chemical Patents Inc. Hydrocarbon conversion
US9964256B2 (en) 2014-12-22 2018-05-08 Exxonmobil Research And Engineering Company Conversion of organic oxygenates to hydrocarbons

Families Citing this family (147)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US4088605A (en) * 1976-09-24 1978-05-09 Mobil Oil Corporation ZSM-5 containing aluminum-free shells on its surface
US4203869A (en) * 1976-09-24 1980-05-20 Mobil Oil Corporation ZSM-5 Containing aluminum-free shells on its surface
US4073865A (en) * 1976-09-27 1978-02-14 Union Carbide Corporation Silica polymorph and process for preparing same
US4238318A (en) * 1976-12-16 1980-12-09 Shell Oil Company Crystalline silicates and hydrocarbon-conversion processes employing same
NL175162C (en) * 1976-12-16 1984-10-01 Shell Int Research A process for the preparation of crystalline silicates, and applying the resultant silicates as catalyst or catalyst carrier.
US5182090A (en) * 1977-04-04 1993-01-26 Mobil Oil Corp. Synthesis of large crystal size zsm-5
US4104319A (en) * 1977-06-23 1978-08-01 Mobil Oil Corporation Ethylation of mono alkyl benzene
GB2002733B (en) * 1977-08-17 1982-02-24 Mobil Oil Corp Synthesis of large crystallite zeolites
US4375458A (en) * 1977-08-17 1983-03-01 Mobil Oil Corporation Synthesis of large crystallite zeolites
US4268420A (en) * 1978-04-18 1981-05-19 Standard Oil Company (Indiana) Hydrocarbon-conversion catalyst and its method of preparation
US4292458A (en) * 1978-04-18 1981-09-29 Standard Oil Company (Indiana) Production of hydrocarbons from alcohols
US4292457A (en) * 1978-04-18 1981-09-29 Standard Oil Company (Indiana) Alkylation of aromatic hydrocarbons
US4269813A (en) * 1977-09-26 1981-05-26 Standard Oil Company (Indiana) Crystalline borosilicate and process of preparation
DE2751443C3 (en) * 1977-11-17 1980-08-14 Union Carbide Corp., New York, N.Y. (V.St.A.)
US4327236A (en) * 1979-07-03 1982-04-27 Standard Oil Company (Indiana) Hydrocarbon-conversion catalyst and its method of preparation
DK155176C (en) * 1978-06-22 1989-07-17 Snam Progetti Process for the preparation of alumina-silica
DK149839C (en) * 1978-06-22 1987-03-16 Snam Progetti Synthetic material based on silicon dioxide and procedure for their production
DE2831334A1 (en) * 1978-07-17 1980-02-07 Basf Ag A process for the preparation of crystalline aluminosilicate
US4172843A (en) * 1978-07-21 1979-10-30 Mobil Oil Corporation Conversion of synthesis gas to high octane predominantly olefinic naphtha
US4363718A (en) * 1979-08-23 1982-12-14 Standard Oil Company (Indiana) Crystalline chromosilicates and process uses
US4299808A (en) * 1978-07-25 1981-11-10 Standard Oil Company (Indiana) Crystalline chromosilicates and process of preparation
DE2848849C2 (en) * 1978-11-10 1990-03-15 Mobil Oil Corp., New York, N.Y., Us
US4285919A (en) * 1978-12-26 1981-08-25 Standard Oil Company (Indiana) Method of preparing a metal-cation-deficient crystalline borosilicate
US4205053A (en) * 1979-02-01 1980-05-27 Mobil Oil Corporation Manufacture of nitrogenous zeolites
US4518703A (en) * 1979-02-16 1985-05-21 Union Oil Company Of California Crystalline silica catalysts
US4433187A (en) * 1979-02-16 1984-02-21 Union Oil Company Of California Process for selectively producing para-xylene
NL7902021A (en) * 1979-03-14 1980-09-16 Shell Int Research A process for the preparation of methane and / or ethane.
US4537758A (en) * 1979-03-21 1985-08-27 Mobil Oil Corporation Process for preparing highly siliceous porous ZSM-12 type crystalline material
US4452769A (en) * 1979-03-21 1984-06-05 Mobil Oil Corporation Method of preparing crystalline zeolite
US4289607A (en) * 1979-04-09 1981-09-15 Mobil Oil Corporation Catalytic conversion with crystalline zeolite product constituting ZSM-5/ZSM-11 intermediates
US4229424A (en) * 1979-04-09 1980-10-21 Mobil Oil Corporation Crystalline zeolite product constituting ZSM-5/ZSM-11 intermediates
DE3068017D1 (en) * 1979-07-12 1984-07-05 Mobil Oil Corp Method of preparing zeolite zsm-48, the zeolite so prepared and its use as catalyst for organic compound conversion
US4454365A (en) * 1981-07-09 1984-06-12 Standard Oil Company (Indiana) Hydrocarbon conversion with a crystalline chromosilicate catalyst
US4376757A (en) * 1979-11-07 1983-03-15 National Distillers & Chemical Corp. Synthetic crystalline silicate compositions and preparation thereof
US4462971A (en) * 1979-11-07 1984-07-31 National Distillers And Chemical Corporation Preparation of crystalline metal silicate and borosilicate compositions
US4423020A (en) * 1979-11-07 1983-12-27 National Distillers And Chemical Corporation Crystalline metal silicate compositions
US4331641A (en) * 1979-11-07 1982-05-25 National Distillers & Chemical Corp. Synthetic crystalline metal silicate compositions and preparation thereof
DK157361C (en) * 1979-12-21 1990-05-21 Snam Progetti A process for preparing titanium modified porous crystalline silica, and the use of this.
US4416766A (en) * 1980-04-28 1983-11-22 Chevron Research Company Hydrocarbon conversion with crystalline silicates
US4309275A (en) * 1980-04-28 1982-01-05 Chevron Research Company Hydrocarbon conversion with crystalline silicates to produce olefins
US4309276A (en) * 1980-04-28 1982-01-05 Chevron Research Company Hydrocarbon conversion with low-sodium silicalite
US4401555A (en) * 1980-04-28 1983-08-30 Chevron Research Company Hydrocarbon conversion with low-sodium crystalline silicates
US4354924A (en) * 1980-06-25 1982-10-19 Chevron Research Company Dual component chromia silicate cracking catalyst
US4310440A (en) * 1980-07-07 1982-01-12 Union Carbide Corporation Crystalline metallophosphate compositions
US4309280A (en) * 1980-07-18 1982-01-05 Mobil Oil Corporation Promotion of cracking catalyst octane yield performance
US4521298A (en) * 1980-07-18 1985-06-04 Mobil Oil Corporation Promotion of cracking catalyst octane yield performance
GB2084552A (en) * 1980-09-26 1982-04-15 Norton Co Silica polymorph
US4340465A (en) * 1980-09-29 1982-07-20 Chevron Research Company Dual component crystalline silicate cracking catalyst
JPS593932B2 (en) * 1980-12-03 1984-01-26 Mitsubishi Gas Chemical Co
DE3172377D1 (en) * 1980-12-12 1985-10-24 Exxon Research Engineering Co Composite zeolite
US4441991A (en) * 1981-04-21 1984-04-10 Mobil Oil Corporation Catalytic dewaxing of oils containing ammonia over highly siliceous porous crystalline materials of the zeolite ZSM-5 type
US4394362A (en) * 1981-04-28 1983-07-19 Chevron Research Company Crystalline silicate particle having an aluminum-containing outer shell
US4443329A (en) * 1981-07-09 1984-04-17 Exxon Research And Engineering Co. Crystalline silica zeolite-containing catalyst and hydrocarbon hydroprocesses utilizing the same
US4513090A (en) * 1981-07-09 1985-04-23 Exxon Research And Engineering Co. Crystalline silica zeolite-containing catalyst
EP0125355B1 (en) * 1981-11-12 1987-07-08 Mobil Oil Corporation Process for the preparation of zsm-5 or mordenite utilizing transition metal complexes during crystallization
US4388285A (en) * 1981-11-12 1983-06-14 Mobil Oil Corporation Process for the preparation of ZSM-5 utilizing transition metal complexes during crystallization
US4732747A (en) * 1983-04-11 1988-03-22 The Dow Chemical Company Magnesium silicate compositions and process for making
US4776946A (en) * 1981-12-30 1988-10-11 Union Oil Company Of California Hydrodewaxing process utilizing a catalyst containing a siliceous metal-containing crystalline composition
US4782166A (en) * 1981-12-30 1988-11-01 Union Oil Company Of California Process for producing maleic anhydride utilizing a catalyst containing a siliceous metal-containing crystalline composition
US4842720A (en) * 1981-12-30 1989-06-27 Union Oil Company Of California Fischer-Tropsch synthesis process utilizing a catalyst containing a siliceous metal-containing crystalline composition
US4828813A (en) * 1981-12-30 1989-05-09 Union Oil Company Of California Siliceous metal-containing crystalline compositions
US4520220A (en) * 1982-02-22 1985-05-28 Cosden Technology, Inc. Alkylation of aromatics employing silicalite catalysts
DE3360656D1 (en) 1982-04-29 1985-10-03 Mobil Oil Corp Method of preparing high silica zeolites with control of zeolite morphology
US4440871A (en) * 1982-07-26 1984-04-03 Union Carbide Corporation Crystalline silicoaluminophosphates
US4519998A (en) * 1982-08-26 1985-05-28 Centre De Recherche Industrielle Du Quebec Process for the preparation of a crystalline titanoborosilicate
US4576805A (en) * 1982-08-27 1986-03-18 Mobil Oil Corporation Increasing lattice metal content of porous inorganic crystalline compositions
CA1204718A (en) 1982-09-27 1986-05-20 Edward J. Rosinski Zeolite
EP0110650B1 (en) * 1982-11-22 1986-09-24 Mobil Oil Corporation Preparation of zeolites
JPS6335570B2 (en) * 1982-11-24 1988-07-15 Kogyo Gijutsuin
US4567029A (en) * 1983-07-15 1986-01-28 Union Carbide Corporation Crystalline metal aluminophosphates
US4801364A (en) * 1983-07-15 1989-01-31 Uop Separation and conversion processes using metal aluminophosphates
US4708857A (en) * 1983-07-26 1987-11-24 Centre De Recherche Industrielle Du Quebec Process for preparing a crystalline iron-borosilicate
US4781906A (en) * 1983-12-19 1988-11-01 Labofina, S.A. Crystalline silicas
US4772456A (en) * 1983-12-19 1988-09-20 Labofina, S.A. Process for preparing crystalline silicas
US4581214A (en) * 1984-01-17 1986-04-08 Union Oil Company Of California Shock calcined aluminosilicate zeolites
US4758328A (en) * 1984-01-17 1988-07-19 Union Oil Company Of California Shock calcined aluminosilicate zeolites
US4888167A (en) * 1984-04-13 1989-12-19 Uop Germanium-aluminum-phosphorus-oxide molecular sieve compositions
US4882038A (en) * 1984-04-13 1989-11-21 Uop Process for the use of magnesium-aluminum-phosphorus-silicon-oxide molecular sieve compositions
US4992250A (en) * 1984-04-13 1991-02-12 Uop Germanium-aluminum-phosphorus-silicon-oxide molecular sieve compositions
US4758419A (en) 1984-04-13 1988-07-19 Union Carbide Corporation Magnesium-aluminum-phosphorus-silicon-oxide molecular sieve compositions
US4952384A (en) * 1984-04-13 1990-08-28 Uop Molecular sieve compositions
US4973785A (en) * 1984-04-13 1990-11-27 Uop Molecular sieve compositions
US4735806A (en) * 1984-04-13 1988-04-05 Union Carbide Corporation Gallium-aluminum-phosphorus-silicon-oxide molecular sieve compositions
US4789535A (en) * 1984-04-13 1988-12-06 Union Carbide Corporation Lithium-aluminum-phosphorus-oxide molecular sieve compositions
US4759919A (en) * 1984-04-13 1988-07-26 Union Carbide Corporation Chromium-aluminum-phosphorus-oxide molecular sieve compositions
US4737353A (en) * 1984-04-13 1988-04-12 Union Carbide Corporation Beryllium-aluminum-phosphorus-silicon-oxide molecular sieve compositions
US4935216A (en) * 1984-04-13 1990-06-19 Uop Zinc-aluminum-phosphorus-silicon-oxide molecular sieve compositions
US5032368A (en) * 1984-04-13 1991-07-16 Uop Gallium-aluminum-phosphorus-oxide molecular sieve compositions
US4940570A (en) * 1984-04-13 1990-07-10 Uop Beryllium-aluminum-phosphorus-oxide molecular sieve compositions
US4973460A (en) * 1984-04-13 1990-11-27 Uop Lithium-aluminum-phosphorus-silicon-oxide molecular sieve compositions
US4913888A (en) * 1984-04-13 1990-04-03 Uop Arsenic-aluminum-phosphorus-oxide molecular sieve compositions
US4824554A (en) * 1984-04-13 1989-04-25 Uop Processes for the use of cobalt-aluminum-phosphorus-silicon-oxide molecular sieve compositions
US4956165A (en) * 1984-04-13 1990-09-11 Uop Molecular sieve compositions
US4851106A (en) * 1984-04-13 1989-07-25 Uop Process for the use of chromium-aluminum-phosphorus-oxide molecular sieve compositions
US4894213A (en) * 1984-04-13 1990-01-16 Uop Arsenic-aluminum-phosphorus-silicon-oxide molecular sieve compositions
US4869805A (en) * 1984-04-26 1989-09-26 Uop Titanium-aluminum-silicon-oxide molecular sieve compositions
US4707345A (en) * 1984-04-26 1987-11-17 Union Carbide Corporation Titanium-aluminum-silicon-oxide molecular sieve compositions and process for preparing the same
US4892720A (en) * 1984-04-26 1990-01-09 Uop Substituted aluminosilicate compositions and process for preparing same
US5160717A (en) * 1984-04-26 1992-11-03 Uop Titanium-aluminum-silicon-oxide molecular sieve compositions
US4582694A (en) * 1984-06-21 1986-04-15 Union Oil Company Of California Shock calcined crystalline silica catalysts
US4758327A (en) * 1984-06-21 1988-07-19 Union Oil Company Of California Shock calcined crystalline silica catalysts
US4900529A (en) * 1984-09-04 1990-02-13 W. R. Grace & Co.-Conn. Process for making crystalline siliceous materials
US4557916A (en) * 1984-10-22 1985-12-10 J. M. Huber Corporation Synthetic calcium silicates and methods of preparation
US4705675A (en) * 1984-11-16 1987-11-10 The Standard Oil Company Synthesis of molecular sieving metallosilicates using silica-transition metal oxide sols
US4623530A (en) * 1985-02-20 1986-11-18 United States Steel Corporation Crystalline magnesia-silica composites and process for producing same
US5064865A (en) * 1985-07-01 1991-11-12 Quantum Chemical Corporation Crystalline aluminosilicate compositions, the preparation thereof and their use in the conversion of synthesis gas to low molecular weight hydrocarbons
US4980326A (en) * 1985-07-01 1990-12-25 Quantum Chemical Corporation Crystalline aluminosilicate compositions, the preparation thereof and their use in the conversion of synthesis gas to low molecular weight hydrocarbons
US5185136A (en) * 1985-08-08 1993-02-09 Exxon Research And Engineering Co. Trivalent transition-metal-aluminosilicate hydrocarbon conversion catalysts having mazzite-like structures, ECR-23-T (C-2491)
US5185138A (en) * 1985-08-08 1993-02-09 Exxon Research And Engineering Company Transistion-metal-aluminosilicate hydrocarbon conversion catalysts having an L type structure, ECR-22-D
US5185137A (en) * 1985-08-15 1993-02-09 Exxon Research And Engineering Company Divalent transition-metal-aluminosilicate hydrocarbon conversion catalysts having mazzite-like structures, ECR-23-D (C-2494)
US4908342A (en) * 1985-09-04 1990-03-13 Mobil Oil Corporation ZSM-5 zeolites having uniformly large crystals
LU86277A1 (en) * 1986-01-29 1987-09-03 Labofina Sa Process for catalytic treatment
US4889617A (en) * 1986-03-24 1989-12-26 Chevron Research Company Method of suppressing sodium poisoning of cracking catalysts during fluid catalytic cracking
US4961836A (en) * 1986-05-23 1990-10-09 Exxon Research And Engineering Company Synthesis of transition metal alumino-silicate IOZ-5 and use of it for hydrocarbon conversion
US4933161A (en) * 1987-02-04 1990-06-12 Exxon Research And Engineering Company Tin substitution into zeolite frameworks
US4952385A (en) * 1987-03-02 1990-08-28 Georgia Tech Research Corp. Ferrisilicate molecular sieve and use as a catalyst
GB8712880D0 (en) * 1987-06-02 1987-07-08 Shell Int Research Crystalline silicates
DE3719467A1 (en) * 1987-06-11 1988-12-29 Hoechst Ag Organic substituted ammonium silicates and processes for their preparation
US5052561A (en) * 1987-09-16 1991-10-01 Chevron Research & Technology Company Crystalline silicate catalyst and a reforming process using the catalyst
US5401488A (en) * 1987-12-15 1995-03-28 Uop Substitution of Sn in place of Al in the framework of molecular sieve via treatment with fluoride salts
US5186918A (en) * 1987-12-15 1993-02-16 Uop Substitution of Cr in place of Al in the framework of molecular sieve via treatment with fluoride salts
US4918256A (en) * 1988-01-04 1990-04-17 Mobil Oil Corporation Co-production of aromatics and olefins from paraffinic feedstocks
FR2629444B1 (en) * 1988-04-01 1990-12-07 Rhone Poulenc Chimie Zeolites based on silica and germanium oxide and synthesis method thereof
US4922051A (en) * 1989-03-20 1990-05-01 Mobil Oil Corp. Process for the conversion of C2 -C12 paraffinic hydrocarbons to petrochemical feedstocks
US5096692A (en) * 1989-06-29 1992-03-17 Ek Roger B Mineralogical conversion of asbestos waste
FR2663920B1 (en) * 1990-06-29 1993-07-02 Rhone Poulenc Chimie Zeolites based on silica and tin oxide and their process of synthesis.
EP0466545A1 (en) * 1990-06-29 1992-01-15 Rhone-Poulenc Chimie Zeolites based on silica and oxides of tetravalent elements, method for their synthesis and their use
FR2663919B1 (en) * 1990-06-29 1993-07-02 Rhone Poulenc Chimie Zeolites based on silica and zirconium oxide and their process of synthesis.
FR2666321B1 (en) * 1990-08-29 1992-12-11 Rhone Poulenc Chimie Process for the preparation of zeolites based on silica and oxides of tetravalent elements.
EP0473509A3 (en) * 1990-08-29 1992-03-18 Rhone-Poulenc Chimie Method for preparation of zeolites based on silica and, possibly, oxides of tetravalent elements
US5135643A (en) * 1990-09-28 1992-08-04 Union Oil Company Of California Process for producing aromatic compounds
US5167942A (en) * 1990-11-21 1992-12-01 Board Of Regents, The University Of Texas System Methods for the preparation of molecular sieves, including zeolites, using metal chelate complexes
US5256385A (en) * 1990-12-13 1993-10-26 Tosoh Corporation Adsorbent and cleaning method of waste gas containing ketonic organic solvents
FR2674517B1 (en) * 1991-03-27 1993-07-02 Rhone Poulenc Chimie Process for the preparation of zeolites based on silica and oxides of tetravalent elements.
CA2132902A1 (en) * 1993-09-27 1995-03-28 Kazuhide Terada Highly active zsm-5 zeolite and process for producing the same
US5583277A (en) * 1994-10-03 1996-12-10 Mobil Oil Corporation Removal of large molecules from a fluid
US5493061A (en) * 1994-12-09 1996-02-20 Council Of Scientific & Industrial Research Process for the conversion of phenol to hydroquinone and catechol
US5756789A (en) * 1995-06-08 1998-05-26 Texaco, Inc. Synthesis of metal--containing aluminophosphates with layered structure
DE69700720D1 (en) * 1996-05-14 1999-12-09 Showa Denko Kk Composite polyolefin-based material and its manufacturing method
US6177374B1 (en) * 1997-01-17 2001-01-23 Council Of Scientific & Industrial Research Catalyst comprising oxides of silicon, zinc and aluminium used for the preparation of LPG and high octane aromatics and a process for preparing the same
US5961818A (en) * 1997-02-20 1999-10-05 Council Of Scientific And Industrial Research Process for the production of LPG and high octane aromatic hydrocarbons from non-economically viable petroleum feed stock
JPH11140068A (en) * 1997-11-07 1999-05-25 Sumitomo Chem Co Ltd Production of propylene oxide
US6887457B2 (en) 2002-08-28 2005-05-03 Akzo Nobel N.V. Process for the preparation of catalysts comprising a pentasil-type zeolite
US20070060780A1 (en) * 2002-08-29 2007-03-15 Dennis Stamires Catalyst for the production of light olefins
US6923949B1 (en) 2004-03-05 2005-08-02 Exxonmobil Research And Engineering Company Synthesis of ZSM-48 crystals with heterostructural, non ZSM-48, seeding
US20160207846A1 (en) * 2015-01-15 2016-07-21 Exxonmobil Chemical Patents Inc. Process for Converting Syngas to Aromatics and Catalyst System Suitable Therefor
CN106629768A (en) * 2015-11-02 2017-05-10 中国石油化工股份有限公司 Synthetic method for uniform nanosized ZSM-5 molecular sieve

Citations (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US3506400A (en) * 1966-05-25 1970-04-14 Exxon Research Engineering Co High silica crystalline zeolites and process for their preparation
US3702886A (en) * 1969-10-10 1972-11-14 Mobil Oil Corp Crystalline zeolite zsm-5 and method of preparing the same
US3770845A (en) * 1970-11-17 1973-11-06 Sun Oil Co Paraffin hydroisomerization with a combined catalyst of a hydrogenation component and a polyvalent metal cation-exchanged zeolite
US3804741A (en) * 1970-08-31 1974-04-16 Velsicol Chemical Corp Hydrocarbon conversion and hydrocracking with layered complex metal silicate and chrysotile compositions
US4021331A (en) * 1974-11-25 1977-05-03 Mobil Oil Corporation Organic compound conversion by zeolite ZSM-20 catalysts

Patent Citations (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US3506400A (en) * 1966-05-25 1970-04-14 Exxon Research Engineering Co High silica crystalline zeolites and process for their preparation
US3702886A (en) * 1969-10-10 1972-11-14 Mobil Oil Corp Crystalline zeolite zsm-5 and method of preparing the same
US3804741A (en) * 1970-08-31 1974-04-16 Velsicol Chemical Corp Hydrocarbon conversion and hydrocracking with layered complex metal silicate and chrysotile compositions
US3770845A (en) * 1970-11-17 1973-11-06 Sun Oil Co Paraffin hydroisomerization with a combined catalyst of a hydrogenation component and a polyvalent metal cation-exchanged zeolite
US4021331A (en) * 1974-11-25 1977-05-03 Mobil Oil Corporation Organic compound conversion by zeolite ZSM-20 catalysts

Non-Patent Citations (2)

* Cited by examiner, † Cited by third party
Title
Barrer et al., "Journal of the Chemical Society", 1959, pp. 195-208. *
Veda et al. "Molecular Sieve Zeolites-I", Copyright A.C.S., pp. 135-139. *

Cited By (172)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
FR2454328A1 (en) * 1979-04-20 1980-11-14 Du Pont crystalline silica and para-xylene process for preparing from toluene using it as catalyst
EP0050525A1 (en) * 1980-10-22 1982-04-28 The British Petroleum Company p.l.c. Synthetic modified crystalline silica
EP0061799A1 (en) * 1981-03-30 1982-10-06 Shell Internationale Research Maatschappij B.V. Crystalline silicates
US4790927A (en) 1981-05-26 1988-12-13 Union Oil Company Of California Process for simultaneous hydrotreating and hydrodewaxing of hydrocarbons
US4877762A (en) 1981-05-26 1989-10-31 Union Oil Company Of California Catalyst for simultaneous hydrotreating and hydrodewaxing of hydrocarbons
US5248841A (en) * 1982-04-30 1993-09-28 Mobil Oil Corporation Hydrocarbon conversion with ZSM-22 zeolite
EP0116203A1 (en) * 1982-12-09 1984-08-22 Mobil Oil Corporation Synthesis of zeolite ZSM-22 with a heterocyclic organic compound
EP0202797A2 (en) 1985-05-14 1986-11-26 Mobil Oil Corporation A method for the synthesis of zeolites
EP0216604A1 (en) 1985-09-23 1987-04-01 Mobil Oil Corporation Process for converting oxygenates into alkylated liquid hydrocarbons
EP0265018A2 (en) 1986-10-22 1988-04-27 ENIRICERCHE S.p.A. Bonded zeolites and process for preparing them
US5374411A (en) * 1987-08-28 1994-12-20 The Dow Chemical Company Crystalline aluminumphosphate compositions
US5110571A (en) * 1987-09-01 1992-05-05 Exxon Research And Engineering Company Stannosilicates and preparation thereof (C-2417)
US5110568A (en) * 1987-09-01 1992-05-05 Exxon Research And Engineering Company Stannosilicates and preparation thereof
US5284986A (en) * 1988-06-24 1994-02-08 Mobil Oil Corporation Upgrading of normal pentane to cyclopentene
US5283385A (en) * 1988-06-24 1994-02-01 Mobil Oil Corporation Upgrading of normal pentane to cyclopentane
US5192728A (en) * 1988-06-24 1993-03-09 Mobil Oil Corporation Tin-colating microporous crystalline materials and their use as dehydrogenation, dehydrocyclization reforming catalysts
US5304694A (en) * 1988-06-24 1994-04-19 Mobil Oil Corporation Isobutene and isoamylene production
US4990710A (en) * 1988-06-24 1991-02-05 Mobil Oil Corporation Tin-containing microporous crystalline materials and their use as dehydrogenation, dehydrocyclization and reforming catalysts
US4970397A (en) * 1989-06-16 1990-11-13 Mobil Oil Corporation Method and apparatus for activating catalysts using electromagnetic radiation
US5124497A (en) * 1989-10-11 1992-06-23 Mobil Oil Corporation Production of mono-substituted alkylaromatics from C8 +N-paraffins
US5037529A (en) * 1989-12-29 1991-08-06 Mobil Oil Corp. Integrated low pressure aromatization process
US5122489A (en) * 1990-10-15 1992-06-16 Mobil Oil Corporation Non-acidic dehydrogenation catalyst of enhanced stability
US5147837A (en) * 1990-10-22 1992-09-15 Mobil Oil Corporation Titania containing dehydrogenation catalysts
US5103066A (en) * 1990-12-10 1992-04-07 Mobil Oil Corp. Dehydrogenation of alcohols over non-acidic metal-zeolite catalysts
US5174981A (en) * 1991-10-04 1992-12-29 Mobil Oil Corp. Synthesis of crystalline ZSM-5-type material
US5174978A (en) * 1991-10-04 1992-12-29 Mobil Oil Corp. Synthesis of crystalline ZSM-5-type material
US5209918A (en) * 1991-10-04 1993-05-11 Mobil Oil Corp. Synthesis of crystalline ZSM-5-type material
US5174977A (en) * 1991-10-04 1992-12-29 Mobil Oil Corp. Synthesis of crystalline ZSM-5-type material
US5310714A (en) * 1992-07-08 1994-05-10 Mobil Oil Corp. Synthesis of zeolite films bonded to substrates, structures and uses thereof
US5316661A (en) * 1992-07-08 1994-05-31 Mobil Oil Corporation Processes for converting feedstock organic compounds
US5349117A (en) * 1992-07-08 1994-09-20 Mobil Oil Corp. Process for sorption separation
US5369071A (en) * 1992-12-11 1994-11-29 Mobil Oil Corporation Manufacture of improved catalyst
US5350504A (en) * 1992-12-18 1994-09-27 Mobil Oil Corporation Shape selective hydrogenation of aromatics over modified non-acidic platinum/ZSM-5 catalysts
WO1996002612A1 (en) * 1992-12-18 1996-02-01 Mobil Oil Corporation Shape selective hydrogenation of aromatics
US5344553A (en) * 1993-02-22 1994-09-06 Mobil Oil Corporation Upgrading of a hydrocarbon feedstock utilizing a graded, mesoporous catalyst system
US5430218A (en) * 1993-08-27 1995-07-04 Chevron U.S.A. Inc. Dehydrogenation using dehydrogenation catalyst and polymer-porous solid composite membrane
US5536857A (en) * 1994-07-05 1996-07-16 Ford Motor Company Single source volatile precursor for SiO2.TiO2 powders and films
WO1999003950A1 (en) * 1997-07-15 1999-01-28 Phillips Petroleum Company Aromatization process for converting cracked gasoline
US5873994A (en) * 1997-07-15 1999-02-23 Phillips Petroleum Company Process for aromatization of a cracked gasoline feedstock using a catalyst containing an acid leached zeolite and tin
EP2258658A2 (en) 1997-10-03 2010-12-08 Polimeri Europa S.p.A. Process for preparing zeolites
US6541408B2 (en) 1997-12-19 2003-04-01 Exxonmobil Oil Corp. Zeolite catalysts having stabilized hydrogenation-dehydrogenation function
US6392109B1 (en) 2000-02-29 2002-05-21 Chevron U.S.A. Inc. Synthesis of alkybenzenes and synlubes from Fischer-Tropsch products
US6864398B2 (en) 2000-04-03 2005-03-08 Chevron U.S.A. Inc. Conversion of syngas to distillate fuels
US6566569B1 (en) 2000-06-23 2003-05-20 Chevron U.S.A. Inc. Conversion of refinery C5 paraffins into C4 and C6 paraffins
US6441263B1 (en) 2000-07-07 2002-08-27 Chevrontexaco Corporation Ethylene manufacture by use of molecular redistribution on feedstock C3-5 components
US6472441B1 (en) 2000-07-24 2002-10-29 Chevron U.S.A. Inc. Methods for optimizing Fischer-Tropsch synthesis of hydrocarbons in the distillate fuel and/or lube base oil ranges
US6649662B2 (en) 2000-07-24 2003-11-18 Chevron U.S.A. Inc. Methods for optimizing fischer-tropsch synthesis of hydrocarbons in the distillate fuel and/or lube base oil ranges
US6455595B1 (en) 2000-07-24 2002-09-24 Chevron U.S.A. Inc. Methods for optimizing fischer-tropsch synthesis
US6806087B2 (en) 2000-08-14 2004-10-19 Chevron U.S.A. Inc. Use of microchannel reactors in combinatorial chemistry
US6670517B1 (en) 2000-08-24 2003-12-30 Exxon Mobil Chemical Patents Inc. Process for alkylating aromatics
US6500233B1 (en) 2000-10-26 2002-12-31 Chevron U.S.A. Inc. Purification of p-xylene using composite mixed matrix membranes
US20080262279A1 (en) * 2001-02-07 2008-10-23 Shiou-Shan Chen Production of Alkylaromatic Compounds
US20040220438A1 (en) * 2001-02-07 2004-11-04 Shiou-Shan Chen Production of alkylaromatic compounds
US7411101B2 (en) 2001-02-07 2008-08-12 Exxonmobil Chemical Patents Inc. Production of alkylaromatic compounds
EP1894909A2 (en) 2001-02-07 2008-03-05 ExxonMobil Chemical Patents Inc. Production of alkylaromatic compounds
US7923590B2 (en) 2001-02-07 2011-04-12 Exxonmobil Chemical Patents Inc Production of alkylaromatic compounds
US6755900B2 (en) 2001-12-20 2004-06-29 Chevron U.S.A. Inc. Crosslinked and crosslinkable hollow fiber mixed matrix membrane and method of making same
US6995295B2 (en) 2002-09-23 2006-02-07 Exxonmobil Chemical Patents Inc. Alkylaromatics production
US6872753B2 (en) 2002-11-25 2005-03-29 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
US20040102532A1 (en) * 2002-11-25 2004-05-27 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
US6946493B2 (en) 2003-03-15 2005-09-20 Conocophillips Company Managing hydrogen in a gas to liquid plant
US6958363B2 (en) 2003-03-15 2005-10-25 Conocophillips Company Hydrogen use in a GTL plant
US20080093263A1 (en) * 2004-11-05 2008-04-24 Wu Cheng Cheng Catalyst for Light Olefins and Lpg in Fludized Catalytic Units
US9365779B2 (en) 2004-11-05 2016-06-14 W. R. Grace & Co.-Conn. Catalyst for light olefins and LPG in fludized catalytic units
WO2006107470A1 (en) 2005-03-31 2006-10-12 Exxonmobil Chemical Patents, Inc. Multiphase alkylaromatics production
WO2006107471A1 (en) 2005-03-31 2006-10-12 Exxonmobil Chemical Patents Inc. Alkylaromatics production using dilute alkene
US20090134065A1 (en) * 2005-06-29 2009-05-28 Wu-Cheng Cheng Pentasil Catalyst for Light Olefins in Fluidized Catalytic Units
US20070179329A1 (en) * 2006-01-31 2007-08-02 Clark Michael C Alkylaromatics production
US7425659B2 (en) 2006-01-31 2008-09-16 Exxonmobil Chemical Patents Inc. Alkylaromatics production
WO2007089381A2 (en) 2006-01-31 2007-08-09 Exxonmobil Chemical Patents Inc. Alkylaromatics production
US7501547B2 (en) 2006-05-10 2009-03-10 Exxonmobil Chemical Patents Inc. Alkylaromatics production
US20090137855A1 (en) * 2006-05-10 2009-05-28 Clark Michael C Alkylaromatics Production
US20070265481A1 (en) * 2006-05-10 2007-11-15 Clark Michael C Alkylaromatics production
US7868218B2 (en) 2006-05-10 2011-01-11 Exxonmobil Chemical Patents Inc. Alkylaromatics production
US7772448B2 (en) 2006-05-10 2010-08-10 Badger Licensing Llc Alkylaromatics production
US20100249472A1 (en) * 2006-05-10 2010-09-30 Clark Michael C Alkylaromatics Production
WO2007133353A1 (en) 2006-05-10 2007-11-22 Exxonmobil Chemical Patents Inc. Mixed phase, multistage alkylaromatics production
US8357830B2 (en) 2006-05-24 2013-01-22 Exxonmobil Chemical Patents Inc. Monoalkylated aromatic compound production
US8524967B2 (en) 2006-05-24 2013-09-03 Exxonmobil Chemical Patents Inc. Monoalkylated aromatic compound production
US8247629B2 (en) 2006-05-24 2012-08-21 Exxonmobil Chemical Patents Inc. Monoalkylated aromatic compound production
US20090306446A1 (en) * 2006-05-24 2009-12-10 Exxonmobil Chemical Patents Inc. Monoalkylated Aromatic Compound Production
WO2008088934A1 (en) 2007-01-19 2008-07-24 Exxonmobil Chemical Patents Inc. Liquid phase alkylation with multiple catalysts
WO2008100658A1 (en) 2007-02-12 2008-08-21 Exxonmobil Chemical Patents Inc. Production of high purity ethylbenzene from non-extracted feed and non-extracted reformate useful therein
US20110118521A1 (en) * 2008-07-22 2011-05-19 Duncan Carolyn B Preparation Of Molecular Sieve Catalysts And Their Use In The Production Of Alkylaromatic Hydrocarbons
US8586496B2 (en) 2008-07-22 2013-11-19 Exxonmobil Chemical Patents Inc. Preparation of molecular sieve catalysts and their use in the production of alkylaromatic hydrocarbons
US20110163002A1 (en) * 2008-09-15 2011-07-07 Patent Department Process for enhanced propylene yield from cracked hydrocarbon feedstocks and reduced benzene in resulting naphtha fractions
US20110201858A1 (en) * 2008-10-06 2011-08-18 Badger Licensing Llc Process for producing cumene
US20110178342A1 (en) * 2008-10-06 2011-07-21 Badger Licensing Llc Process for producing cumene
US8445738B2 (en) 2008-10-06 2013-05-21 Badger Licensing Llc Process for producing cumene
US8633342B2 (en) 2008-10-10 2014-01-21 Badger Licensing Llc Process for producing alkylaromatic compounds
US20110224468A1 (en) * 2008-10-10 2011-09-15 Vincent Matthew J Process for Producing Alkylaromatic Compounds
WO2011081785A1 (en) 2009-12-15 2011-07-07 Exxonmobil Research And Engineering Company Preparation of hydrogenation and dehydrogenation catalysts
US8884088B2 (en) 2010-02-05 2014-11-11 Exxonmobil Chemical Patents Inc. Dehydrogenation process
WO2011096995A1 (en) 2010-02-05 2011-08-11 Exxonmobil Chemical Patents Inc. Dehydrogenation process
WO2011096991A1 (en) 2010-02-05 2011-08-11 Exxonmobil Chemical Patents Inc. Dehydrogenation process
US20110224469A1 (en) * 2010-03-10 2011-09-15 Vincent Matthew J Alkylated Aromatics Production
US8877996B2 (en) 2010-03-10 2014-11-04 Exxonmobil Chemical Patents Inc. Alkylated aromatics production
US8629311B2 (en) 2010-03-10 2014-01-14 Stone & Webster, Inc. Alkylated aromatics production
WO2012092440A1 (en) 2010-12-30 2012-07-05 Virent, Inc. Solvolysis of biomass using solvent from a bioreforming process
WO2012092436A1 (en) 2010-12-30 2012-07-05 Virent, Inc. Organo-catalytic biomass deconstruction
EP2471895A1 (en) 2011-01-04 2012-07-04 ConocoPhillips Company Process to partially upgrade slurry oil
WO2012142490A1 (en) 2011-04-13 2012-10-18 Kior, Inc. Improved catalyst for thermocatalytic conversion of biomass to liquid fuels and chemicals
WO2012162403A1 (en) 2011-05-23 2012-11-29 Virent, Inc. Production of chemicals and fuels from biomass
WO2013059172A1 (en) 2011-10-17 2013-04-25 Exxonmobil Research And Engineering Company Process for producing phosphorus modified zeolite catalysts
US9821299B2 (en) 2011-10-17 2017-11-21 Exxonmobil Research And Engineering Company Process for producing phosphorus modified zeolite catalysts
WO2013059161A1 (en) 2011-10-17 2013-04-25 Exxonmobil Research And Engineering Company Phosphorus modified zeolite catalysts
WO2013059169A1 (en) 2011-10-17 2013-04-25 Exxonmobil Research And Engineering Company Phosphorus modified zeolite catalysts
WO2013077885A1 (en) 2011-11-23 2013-05-30 Virent, Inc. Dehydrogenation of alkanols to increase yield of aromatics
WO2013081994A1 (en) 2011-12-01 2013-06-06 Exxonmobil Research And Engineering Company Synthesis of high activity large crystal zsm-5
WO2013085681A1 (en) 2011-12-06 2013-06-13 Exxonmobil Chemical Patents Inc. Production process of para -xylene and apparatus thereof
WO2013119318A1 (en) 2012-02-08 2013-08-15 Exxonmobil Chemical Patents Inc. Production of monoalkyl aromatic compounds
WO2014003732A1 (en) 2012-06-27 2014-01-03 Badger Licensing Llc Process for producing cumene
WO2014008268A1 (en) 2012-07-05 2014-01-09 Badger Licensing Llc Process for producing cumene
WO2014011359A1 (en) 2012-07-13 2014-01-16 Badger Licensing Llc Process for producing phenol
WO2014018515A1 (en) 2012-07-26 2014-01-30 Badger Licensing Llc Process for producing cumene
WO2014028003A1 (en) 2012-08-14 2014-02-20 Stone & Webster Process Technology, Inc. Integrated process for producing cumene and purifying isopropanol
WO2014084810A1 (en) 2012-11-27 2014-06-05 Badger Licensing Llc Production of styrene
WO2014082862A1 (en) 2012-11-28 2014-06-05 Exxonmobil Chemical Patents Inc. Mfi with unusual morphology
US9725327B2 (en) 2012-11-28 2017-08-08 Exxonmobil Chemical Patents Inc. MFI with unusual morphology
EP3056470A1 (en) 2012-12-21 2016-08-17 ExxonMobil Chemical Patents Inc. Small crystal zsm-5 and its use
WO2014099261A1 (en) 2012-12-21 2014-06-26 Exxonbobil Chemical Patents Inc. Synthesis of zsm-5
US9757716B2 (en) 2012-12-21 2017-09-12 Exxonmobil Chemical Patents Inc. Synthesis of ZSM-5
WO2014109766A1 (en) 2013-01-14 2014-07-17 Badger Licensing Llc Process for balancing gasoline and distillate production in a refinery
US9440892B2 (en) 2013-03-14 2016-09-13 Virent, Inc. Production of aromatics from di- and polyoxygenates
WO2014152370A2 (en) 2013-03-14 2014-09-25 Virent, Inc. Production of aromatics from di-and poly-oxygenates
US9403736B2 (en) 2013-03-14 2016-08-02 Virent, Inc. Production of aromatics from di- and polyoxygenates
WO2014182294A1 (en) 2013-05-08 2014-11-13 Badger Licensing Llc Aromatics alkylation process
WO2014190124A1 (en) 2013-05-22 2014-11-27 Virent, Inc. Hydrogenation of carboxylic acids to increase yield of aromatics
WO2014190161A1 (en) 2013-05-22 2014-11-27 Virent, Inc. Process for converting biomass to aromatic hydrocarbons
WO2015031363A1 (en) 2013-08-30 2015-03-05 Exxonmobil Chemical Patents Inc. Oxygen storage and production of c5+ hydrocarbons
WO2015084518A1 (en) 2013-12-06 2015-06-11 Exxonmobil Upstream Research Company Method and system for producing liquid hydrocarbons
US9957206B2 (en) 2013-12-06 2018-05-01 Exxonmobil Chemical Patents Inc. Hydrocarbon conversion
US9790145B2 (en) 2013-12-06 2017-10-17 Exxonmobil Chemical Patents Inc. Production of C2+ olefins
US9828308B2 (en) 2013-12-06 2017-11-28 Exxonmobil Chemical Patents Inc. Hydrocarbon conversion
US9682899B2 (en) 2013-12-06 2017-06-20 Exxonmobil Chemical Patents Inc. Hydrocarbon conversion
WO2015084576A2 (en) 2013-12-06 2015-06-11 Exxonmobil Chemical Patents Inc. Hydrocarbon conversion
US9682900B2 (en) 2013-12-06 2017-06-20 Exxonmobil Chemical Patents Inc. Hydrocarbon conversion
WO2015089256A1 (en) 2013-12-13 2015-06-18 Exxonmobil Research And Engineering Company Enhanced methane formation in reforming catalysts
WO2015089257A1 (en) 2013-12-13 2015-06-18 Exxonmobil Research And Engineering Company Natural gas vehicle powertrain with onboard catalytic reformer
WO2015089254A1 (en) 2013-12-13 2015-06-18 Exxonmobil Research And Engineering Company Vehicle powertrain with onboard catalytic reformer
US9617490B2 (en) 2013-12-13 2017-04-11 Exxonmobil Research And Engineering Company Vehicle powertrain with onboard catalytic reformer
US9895682B2 (en) 2013-12-20 2018-02-20 Exxonmobil Research And Engineering Company Catalyst for selective conversion of oxygenates to aromatics
WO2015094679A1 (en) 2013-12-20 2015-06-25 Exxonmobil Research And Engineering Company Catalyst for selective conversion of oxygenates to aromatics
US9783460B2 (en) 2013-12-20 2017-10-10 Exxonmobil Chemical Patents Inc. Process for converting oxygenates to aromatic hydrocarbons
WO2015094687A1 (en) 2013-12-20 2015-06-25 Exxonmobil Research And Engineering Company Bound catalyst for selective conversion of oxygenates to aromatics
WO2015094685A1 (en) 2013-12-20 2015-06-25 Exxonmobil Research And Engineering Company Alumina bound catalyst for selective conversion of oxygenates to aromatics
US9790139B2 (en) 2013-12-20 2017-10-17 Exxonmobil Chemical Patents Inc. Process for converting oxygenates to aromatic hydrocarbons
WO2015094696A1 (en) 2013-12-20 2015-06-25 Exxonmobil Chemical Patents Inc. Process for converting oxygenates to aromatic hydrocarbons
US9950971B2 (en) 2014-07-23 2018-04-24 Exxonmobil Chemical Patents Inc. Process and catalyst for methane conversion to aromatics
US9714386B2 (en) 2014-07-24 2017-07-25 Exxonmobil Chemical Patents Inc. Production of xylenes from syngas
US9809758B2 (en) 2014-07-24 2017-11-07 Exxonmobil Chemical Patents Inc. Production of xylenes from syngas
WO2016025077A1 (en) 2014-08-15 2016-02-18 Exxonmobil Chemical Patents Inc. Aromatics production process
US9783463B2 (en) 2014-09-30 2017-10-10 Exxonmobil Chemical Patents Inc. Conversion of acetylene and methanol to aromatics
US9938205B2 (en) 2014-10-10 2018-04-10 Exxonmobil Research And Engineering Company Apparatus and process for producing gasoline, olefins and aromatics from oxygenates
WO2016085908A1 (en) 2014-11-25 2016-06-02 Badger Licensing Llc Process for reducing the benzene content of gasoline
WO2016105888A1 (en) 2014-12-22 2016-06-30 Exxonmobil Research And Engineering Company Conversion of oxygenates to aromatics
US9964256B2 (en) 2014-12-22 2018-05-08 Exxonmobil Research And Engineering Company Conversion of organic oxygenates to hydrocarbons
WO2016148755A1 (en) 2015-03-19 2016-09-22 Exxonmobil Chemical Patents Inc. Process and apparatus for the production of para-xylene
WO2016160081A1 (en) 2015-03-31 2016-10-06 Exxonmobil Chemical Patents Inc. Oxygenated hydrocarbon conversion zoned method
WO2016175898A1 (en) 2015-04-30 2016-11-03 Exxonmobil Chemical Patents Inc. Process and apparatus for the production of para-xylene
WO2016179133A1 (en) 2015-05-05 2016-11-10 Shell Oil Company Reduced emissions aromatics-containing jet fuels
WO2017048378A1 (en) 2015-09-17 2017-03-23 Exxonmobil Chemical Patents Inc. Process for recovering para-xylene using a metal organic framework adsorbent in a simulated moving-bed process
WO2017052856A1 (en) 2015-09-25 2017-03-30 Exxonmobil Chemical Patents Inc. Catalyst and its use in dehydrocyclization processes
US9963406B2 (en) 2015-09-25 2018-05-08 Exxonmobil Chemical Patents Inc. Hydrocarbon conversion
US9845272B2 (en) 2015-09-25 2017-12-19 Exxonmobil Chemical Patents Inc. Hydrocarbon conversion
WO2017065771A1 (en) 2015-10-15 2017-04-20 Badger Licensing Llc Production of alkylaromatic compounds
WO2017112716A1 (en) 2015-12-21 2017-06-29 Shell Oil Company Methods of providing higher quality liquid kerosene based-propulsion fuels
WO2017142526A1 (en) 2016-02-17 2017-08-24 Badger Licensing Llc Process for producing ethylbenzene
WO2017142666A1 (en) 2016-02-19 2017-08-24 Exxonmobil Research And Engineering Company Small crystal, high surface area emm-30 zeolites, their synthesis and use
WO2017146914A1 (en) 2016-02-26 2017-08-31 Exxonmobil Chemical Patents Inc. Process for recovering para-xylene
WO2017189137A1 (en) 2016-04-25 2017-11-02 Exxonmobil Chemical Patents Inc. Catalytic aromatization
WO2017188934A1 (en) 2016-04-26 2017-11-02 Badger Licensing Llc Process for reducing the benzene content of gasoline

Also Published As

Publication number Publication date Type
US3941871A (en) 1976-03-02 grant

Similar Documents

Publication Publication Date Title
US3699139A (en) Synthetic crystalline aluminosilicate
US3692470A (en) Crystalline zeolite zsm-10
US4826667A (en) Zeolite SSZ-25
US5252527A (en) Zeolite SSZ-32
US3702886A (en) Crystalline zeolite zsm-5 and method of preparing the same
US5106801A (en) Zeolite SSZ-31
US5202014A (en) Zeolite SSZ-25
Ravishankar et al. Characterization and catalytic properties of zeolite MCM-22
US4962250A (en) Process for the conversion of paraffins to olefins and/or aromatics and non-acidic zeolite catalyst therefor
US4544538A (en) Zeolite SSZ-13 and its method of preparation
US4962256A (en) Process for preparing long chain alkyl aromatic compounds
US5001295A (en) Process for preparing dialkylnaphthalene
US4331643A (en) Use of diazobicyclooctane (DABCO) as a template in zeolite synthesis
US5200377A (en) Zeolite SSZ-28
US3992466A (en) Hydrocarbon conversion
US4556477A (en) Highly siliceous porous crystalline material ZSM-22 and its use in catalytic dewaxing of petroleum stocks
US4203869A (en) ZSM-5 Containing aluminum-free shells on its surface
US5166111A (en) Low-aluminum boron beta zeolite
US4968402A (en) Process for upgrading hydrocarbons
US4568654A (en) Zeolite ZSM-51 composition
US4091007A (en) Preparation of zeolites
US4523047A (en) Process for syngas conversions to liquid hydrocarbon products utilizing ZSM-45 zeolite
US4963337A (en) Zeolite SSZ-33
US3950496A (en) Synthetic zeolite ZSM-18
US4088605A (en) ZSM-5 containing aluminum-free shells on its surface