GB2118063A - Catalysts and catalyst supporters - Google Patents

Catalysts and catalyst supporters Download PDF

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Publication number
GB2118063A
GB2118063A GB08309852A GB8309852A GB2118063A GB 2118063 A GB2118063 A GB 2118063A GB 08309852 A GB08309852 A GB 08309852A GB 8309852 A GB8309852 A GB 8309852A GB 2118063 A GB2118063 A GB 2118063A
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Prior art keywords
acid
alumina
weight
composition
percent
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GB8309852D0 (en
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Roger Jean Lussier
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WR Grace and Co
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WR Grace and Co
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    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J29/00—Catalysts comprising molecular sieves
    • B01J29/04—Catalysts comprising molecular sieves having base-exchange properties, e.g. crystalline zeolites
    • B01J29/06—Crystalline aluminosilicate zeolites; Isomorphous compounds thereof
    • B01J29/08—Crystalline aluminosilicate zeolites; Isomorphous compounds thereof of the faujasite type, e.g. type X or Y
    • B01J29/085—Crystalline aluminosilicate zeolites; Isomorphous compounds thereof of the faujasite type, e.g. type X or Y containing rare earth elements, titanium, zirconium, hafnium, zinc, cadmium, mercury, gallium, indium, thallium, tin or lead
    • B01J29/088—Y-type faujasite
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J29/00—Catalysts comprising molecular sieves
    • B01J29/04—Catalysts comprising molecular sieves having base-exchange properties, e.g. crystalline zeolites
    • B01J29/06—Crystalline aluminosilicate zeolites; Isomorphous compounds thereof
    • B01J29/08—Crystalline aluminosilicate zeolites; Isomorphous compounds thereof of the faujasite type, e.g. type X or Y
    • B01J29/084—Y-type faujasite
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J37/00—Processes, in general, for preparing catalysts; Processes, in general, for activation of catalysts
    • B01J37/0009—Use of binding agents; Moulding; Pressing; Powdering; Granulating; Addition of materials ameliorating the mechanical properties of the product catalyst
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J2229/00—Aspects of molecular sieve catalysts not covered by B01J29/00
    • B01J2229/30—After treatment, characterised by the means used
    • B01J2229/36—Steaming
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J2229/00—Aspects of molecular sieve catalysts not covered by B01J29/00
    • B01J2229/30—After treatment, characterised by the means used
    • B01J2229/37—Acid treatment
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J2229/00—Aspects of molecular sieve catalysts not covered by B01J29/00
    • B01J2229/30—After treatment, characterised by the means used
    • B01J2229/40—Special temperature treatment, i.e. other than just for template removal
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J2229/00—Aspects of molecular sieve catalysts not covered by B01J29/00
    • B01J2229/30—After treatment, characterised by the means used
    • B01J2229/42—Addition of matrix or binder particles
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J37/00—Processes, in general, for preparing catalysts; Processes, in general, for activation of catalysts
    • B01J37/0009—Use of binding agents; Moulding; Pressing; Powdering; Granulating; Addition of materials ameliorating the mechanical properties of the product catalyst
    • B01J37/0027—Powdering
    • B01J37/0045—Drying a slurry, e.g. spray drying

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  • Chemical & Material Sciences (AREA)
  • Engineering & Computer Science (AREA)
  • Materials Engineering (AREA)
  • Organic Chemistry (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Crystallography & Structural Chemistry (AREA)
  • Catalysts (AREA)
  • Production Of Liquid Hydrocarbon Mixture For Refining Petroleum (AREA)

Abstract

Catalysts and catalyst supports which comprise solid inorganic oxides, such as crystalline zeolites, clay and/or inorganic gels, are combined with an acid reacted metakaolin binder. The compositions may be spray dried and calcined to obtain dense, attrition resistant fluid cracking catalysts or used in the preparation of shaped catalyst supports.

Description

SPECIFICATION Catalysts and catalyst supports The present invention relates to the preparation of catalysts and supports therefor and more particularly to the preparation of dense, hard, particulate hydrocarbon conversion catalysts which comprise catalytically active components such as crystalline zeolites dispersed in an inorganic oxide matrix.
Hydrocarbon conversion catalysts such as fluid catalytic cracking catalysts (FCC) are typically manufactured by spray drying aqueous slurries, catalytically active zeolites and matrix forming components such as inorganic oxide gels and/or clays. The resulting catalysts comprise small particles (microspheres) in which the zeolite crystals are dispersed throughout a matrix of relatively catalytically inactive gel or sol binder and clay. While the inorganic oxide matrix generally has little catalytic activity, the matrix provides the physical strength, size and porosity characteristics which are required to obtain a commercially acceptable catalyst composition. Furthermore, since FCC catalysts are produced and consumed in large quantities the matrix components should be relatively inexpensive.
It has been found that clay, particularly kaolin, due to its reasonable price and availability, constitutes a particularly suitable FCC catalyst component. The prior art describes preparation of clay based hydrocarbon conversion catalysts that have been both thermally and chemically treated to obtain the desired characteristics.
United States Patent No. 2,485,626 describes the preparation of clay based cracking catalyst wherein kaolin clay is heat treated, reacted with acid to remove part of the alumina component of the clay structure. Subsequently, the acid treated clay is washed free of soluble components, and finally formed into catalyst particles.
United States 3,406,124 describes a method for preparing catalysts which contain crystalline alumino-silicate zeolites dispersed in an inorganic oxide matrix. The matrix contains a clay component which is leached to remove a portion of the alumina of the clay structure as soluble aluminum salts.
Subsequently the aluminum salts are precipitated as aluminum hydroxide on the clay.
While the prior art describes the preparation of hydrocarbon conversion catalysts which may comprise or contain thermally/chemically treated clays, such as calcined/acid leached kaolin, the refining industry constantly requires low-cost catalysts which provide a high degree of activity and selectivity combined 'with substantial physical strength and attrition resistance.
The present invention provides improved catalysts, catalyst supports and inorganic binders therefor. More especially, the invention provides hydrocarbon conversion catalysts which are hard, dense-and relatively intexpensive to manufacture, and in particular, a zeolite containing FCC catalyst which contains substantial quantities of clay and/or clay derived matrix components.
Broadly, the present invention provides improved catalytic compositions (including catalysts, catalyst supports and inorganic binders) which contain an acid treated metakaolin that is obtained by heating (calcining) kaolin and reacting the resulting metakaolin with sufficient acid to react with up to about 25 mol percent of the alumina (Al203) present in the kaolin.
More specifically, dense, hard, attrition resistant catalytic compositions may be prepared in accordance with the present invention by combining particulate catalyst components or other inorganic solid with an acid treated metakaolin binder which is obtained by heating (calcining) kaolin to a temperature of about 700 to 9100C, and reacting the resulting metakaolin with sufficient acid to react with less than about 25 mol percent (and preferably for about 5 to 1 5 percent), of the structural alumina present in the metakaolin. The compositions are formed into particles which are then heat treated (calcined) at a temperature of about 300-8000C to obtain hard attrition resistant catalysts or catalyst supports.
While the process is particularly useful for the manufacture of zeolite containing FCC catalysts, the invention also provides catalyst supports. These catalysts and supports may comprise inorganic oxide gels and hydrogels such as clay, alumina, silica, and silica-alumina dispersed in, or combined with, a binder which comprises the acid treated metakaolin described above.
The acid treated metakaolin binder is obtained by first thermally treating kaolin at a temperature ol from about 700 to 91 OOC, and preferably 800 to 9000 C, for a period of from about one-quarter to 8 hours, and preferably one-quarter to 2 hours. The thermal treatment or calcination step, which may be conducted in the presence of air, converts the raw kaolin into a reactive form which is characterized as metakaolin.
The metakaolin is then reacted with a quantity of acid, such as hydrochloric or nitric acid or a;1 acid salt solution thereof such as aluminum chloride, aluminum nitrate, zirconyl chloride, etc.
The quantity of acid reacted with the metakaolin is sufficient to react with from about 2 to 25 and preferably from 5 to 1 5 percent of the alumina (Al203) present in the metakaolin. The reaction in the case of hydrochloric acid proceeds in accordance with the following overall reaction wherein metakaolin has the formula 2 SiO2.AI203.
2 SiO2.AI203 + 1 HCI M [2 SiO2.(A1203)0.9] + 0.3 H2O + 0.2 AI Cl3 + 0.4 HCI To achieve the desired level of acid treatment, the quantity of acid used is equal to or less than about 1.5 mols of acid per mol of alumina present in the clay. As little as 0.25 mol of acid per mol of alumina is sufficient to provide the desired acid reacted metakaolin product in less than about 24 hours.
The most preferred level of acid is about 0.50 to 1.0 mol of acid per mol alumina in the metakaolin. The desired quantity of acid is combined with sufficient water to provide from about 2.0 to 20 parts by weight acid solution per part by weight metakaolin. The reaction with acid is conducted at a temperature of from about 60 to 1 000C for a period of from about 1 to 24 hours. The resulting acid/metakaolin reaction product contains from about 5 to 50 percent by weight clay solids admixed with a liquid phase which comprises an aqueous solution of a complex acid/aluminum reaction product which has a pH from about 2.0 to 4.0. This acidic aluminum reaction product solution together with the acid leached metakaolin solids comprises the binder or intermediate which is used in the preparation of the catalysts and catalyst supports of the present invention.The ratio of the acid leached clay solid to complex acidic aluminum solution is from about 8/1 to 9.8/1, preferably 9/1 to 9.5/1 parts by weight.
To obtain a cracking catalyst which contains the acid-metakaolin reaction product described above, the acid-metakaolin reaction mixture is admixed with the desired quantity of catalytic components and/or gelled with a base and formed into catalyst particles. The added components typically comprise crystalline zeolites such as type X, type Y (synthetic faujasite), ZSM zeolite and/or other desired catalyst components such as clay, alumina and silica-alumina hydrogels. Subsequent to mixing the acid reacted metakaolin binder slurry with the catalyst components, the soluble aluminum components of the binder may be precipitated as alumina by the addition of a base such as ammonium hydroxide. or sodium hydroxide. It is also contemplated that the acid reacted metakaolin reaction product may be gelled without added catalyst ingredients.In the alumina precipitating step, sufficient base is added to raise the pH of the reaction mixture to a level of about 5.0 to 9.0.
Zeolite components may be initially mixed with the acid-metakaolin binder slurry in the sodium form. or the zeolites may be pre-exchanged with hydrogen and/or stabilizing ions such as rare earth ions. Typical exchanged/thermally treated zeolites comprise the calcined rare earth exchanged type X and Y zeolites (CREX and CREY) described in United States Reissue Patent No. 28,629. In addition, the zeolite component may comprise an ultrastable type zeolite such as described in U.S. Patent Nos.
3.293,192 and 3,449,070. It is also contemplated that other catalytically active zeolites such as ZSM 5, 11 and mordenite may be utilized alone or as blends with the previously mentioned zeolites.
The fluid cracking catalysts (FCC) prepared herein generally comprise from about 5.0 to 20 parts by weight acid metakaolin binder (dry basis) and from about 95 to 80 parts by weight solid components such as zeolite, alumina and clays, (including the base-gelled acid-leached metakaolin described herein). The binder is thoroughly admixed with the solid components to obtain a spray dryer feed slurry which contains from about 20 to 60 percent by weight solids. The slurry is then spray dried using conventional techniques to obtain microspheroidalFCC catalyst particles which are then calcined at a temperature of from about 300 to 8000 C. These calcined particles may then be ion exchanged and/or washed to remove undesirable soluble salts.Typically, the spray dried product is contacted with solutions of ammonium sulfate and/or rare earth chloride ions.
In the event the acid treated metakaolin binders contemplated herein are utilized to prepare supports, such as used in the preparation of hydroprocessing catalysts, the acid metakaolin reaction mixture described above is gelled and/or admixed with the desired solid components which typically comprise zeolites, clay and inorganic oxide gels such as alumina, silica and silica alumina (including the base gelled acid reacted metakaolin described herein). The mixtures which comprise from Lsout 5 to 40 parts acid treated kaolin binder and 95 to 60 parts inorganic solids may be optionally reacted with a base to precipitate alumina. The mixtures are then formed into catalyst particles having the desired shape and size. Typical forming techniques such as pilling, extruding and granulating may be utilized.The resultant formed particles are then subjected to calcination and a temperature of from about 300 to 8000C to obtain hard attrition resistant particles. The resulting calcined particles may then be combined with catalytically active metals such as selected from group VI and group VIII of the Periodic Table to obtain catalysts useful for hydrocracking and hydrosulfurization, demetallization and so forth. In particular, it is found that from about 1 to 20 weight percent non-noble metals, such as cobalt, molybdenum, chromium and nickel may be impregnated or placed upon the catalysts supports contemplated herein using conventional techniques. In addition it is found that from about 0.1 to 2 weight percent noble metals such as platinum, palladium and rhodium may be combined with the supports to obtain useful, catalytically active products.
The following Examples illustrate the present invention EXAMPLE 1 A sample of kaolin clay having a particle size less than 2.0 microns which possessed the initial chemical composition 51.8 weight percent Six,, 42.2 percent Al203 was calcined for one half hour at 9000C. A 300 g sample of the calcined clay was then added to 3 liters of a solution which contained 102 ml of 37 percent HCI. The resulting slurry was refluxed at a temperature of 1000C for 4 hours. The reaction mixture was then combined with 500 g of calcined, rare earth exchanged type Y zeolite (CREY) which contained 0.79 percent Na2O, and 2323 g (dry basis) raw kaolin. The slurry was homogenized and subsequently spray dried. The physical properties of the resulting catalyst product are summarized in the Table.
EXAMPLE 2 A 9000 g sample of metakaolin, which was obtained by calcining raw kaolin for one half-hour at 9000 C, was admixed with 60 1 of an acid solution which contained 3042 ml of 37% HCI. This mixture was then boiled under reflux for seven and one-half hours. The slurry pH was adjusted to about 6.0 by the addition of 30 percent ammonium hydroxide. The gelled reaction mixture was then filtered, washed twice with 10 gal of hot deionized water, and reslurried in approximately 25 gal of hot deionized water and recovered by filtration. 450 g D.B. (2074 g as is) of this filter cake was dispersed in a blender along with a slurry which comprised 500 g of the CREY described in Example 1 and 2175 g (dry basis), 2529 g as is of raw kaolin, and approximately 8,000 g of water.The mixture was homogenized by recirculation through a centrifugal pump and subsequently spray dried. The physical properties of the catalyst obtained in this example are set forth in the Table.
EXAMPLE 3 A 1400 g sample of the metakaolin described in Example 2 was combined with 4.2 1 of a solution which contained 472.6 ml of 37% HCI dissolved in water. This mixture was boiled under reflux for 2 hours. The reaction mixture was then combined in the blender with 559.4 g CREY and 2120 g (dry basis) kaolin. The slurry was then thoroughly mixed and spray dried to obtain microspheroidal particles.
The catalyst particles were then calcined 2 hours at 5400 C. This sample had the physical properties described in the Table.
EXAMPLE 4 A 6750 g sample of the metakaolin described in Example 2 was added to 80 1 of the solution which contained 2286 ml of 37% HCI. This mixture was then boiled under reflux for 7 hours. 6 1 of the resulting slurry was combined with a 2175 g (dry basis) sample of raw kaolin and 434 g (dry basis) CREY. The slurry was then mixed thoroughly, spray dried and calcined 2 hours at 5400 C. The physical properties of the catalyst obtained in this example are summarized in the Table.
EXAMPLE 5 This example shows that a portion of the acid leached clay slurry can be used to bind an ammonium hydroxide gelled acid leached clay of the type described in Example 2. 600 g of kaolin was calcined one-half hour at 9000 C, was added to 6.0 1 solution containing 204 ml 37.0% HCI and boiled under reflux for approximately 4 hours. A blended slurry of 180 g as is CREY (0.79% Na2O) and 2,215 g dry basis (1 0, & 9 g as is) washed ammonium hydroxide gelled acid leached clay obtained by the procedure set forth in Example 2 was added. The slurry was thoroughly mixed and spray dried. The properties of this catalyst sample are set forth in the Table.
EXAMPLE 6 A 5,200 g dry basis sample of the washed ammonium hydroxide gelled acid leached metakaolin of Example 2 was slurried in a total of about 30,000 g of water and spray dried. The properties are set forth in the Table.
EXAMPLE 7 450 g of the calcined clay described in Example 1 was added to 4.5 1 solution containing 1 53.0 ml conc. HCI and boiled 4 hours under reflux. To this slurry 500 g of CREY and 2,529 g (raw) kaolin clay were added, the slurry briefly homogenized and spray dried. This sample, of composition 1 5 percent acid treated clay, 12.5 percent CREY, 72.5 percent kaolin clay, had the properties indicated in the Table.
TABLE Density Attrition Resistance Example # *ABD/**CD Davision Index/Jersey Index'') Microactivityl2} 1 0.72/0.81 4/0.6 2 0.59/0.81 13/0.3 73.4 3 0.68A83 13/2.0 4 0.70/0.81 14/2.1 5 0.65/0.86 12/0.3 58 6 0.62/0.71 19/1.6 44.
7 0.67/83 14/2.2 70.0 (11 Attrition Resistance measured after calcination for 2 hours at 10000F (5380C) as determined by the method set forth in U.S. Patent No. 4,247,420.
12) Microactivity volume % conversion as determined by use of the test as described by Henderson et al at 9000F (4820C), 16 WHSV, 3 c/o after an 8 hour, 13500F (7320C), 100 steam deactivation.
* ABD -- Apparent Bulk Density (g/cc) ** CD -- Compacted Density (g/cc) The above Examples clearly indicate that valuable catalyst compositions may be obtained using the teachings of the invention.

Claims (14)

1. A method of preparing a catalytic composition which comprises: (a) calcining kaolin at 700 to 9100C for one quarter to 2 hours; (b) reacting the the-calcined kaolin with acid under conditions such that up to 25 mol percent of the alumina present reacts with the said acid: (c) mixing the acid-treated calcined kaolin reaction product with an inorganic solid; (d) forming the mixture obtained into particles; and (e) calcining the said particles at 300 to 8000 C.
2. A method according to claim 1 wherein 5 to 15 mol percent of the alumina reacts with the acid.
3. A method according to claim 1 or 2 wherein the acid used is hydrochloric acid, nitric acid, an acid-reacting salt of such an acid, or a mixture thereof.
4. A method according to any of claims 1 to 3 wherein the said inorganic solid is produced in situ by reacting the product of the acid treatment with a base to precipitate soluble alumina components.
5. A method according to any of claims 1 to 4 wherein the said inorganic solid is a crystalline zeolite, silica, alumina, silica-alumina hydrogel, clay or a mixture of two or more of these.
6. A method according to claim 5 wherein the said inorganic solid is a fluid cracking catalyst composition containing up to 50 percent by weight of a crystalline zeolite.
7. A method according to claim 6 wherein the said zeolite is a rare earth-exchanged type Y zeolite.
8. A method according to claim 6 or 7 wherein the said catalyst composition contains up to 80 percent by weight of raw clay.
9. A method according to any one of claims 1 to 8 wherein up to about 20 parts by weight of the inorganic solid is mixed with each part by weight of the acid treated calcined kaolin produced in step (b).
10. A method according to any of claims 1 to 9 wherein the mixture is formed by spray drying, extruding, pilling or granulating.
11. A method according to claim 1 substantially as described in any one of the foregoing Examples.
12. A particulate catalytic composition comprising: (a) a solid, inorganic oxide, and (b) an acid reacted metakaolin binder in which up to 25 mol percent of the alumina thereof has been reacted with an inorganic acid.
13. A composition according to claim 12 wherein the solid inorganic oxide component is selected from crystalline zeolites silica, alumina, silica-alumina hydrogels, clays and mixtures thereof.
14. A composition according to claim 1 3 wherein said composition comprises a fluid cracking catalyst composition that contains up to 50 percent by weight of a crystalline zeolite.
1 5. A composition according to claim 14 wherein the said zeolite is rare earth exchanged type Y zeolite.
1 6. A composition according to claim 14 or 1 5 wherein the said composition includes up to 80 percent by weight raw kaolin.
1 7. A composition according to any of claims 12 to 1 6 which contains 2 to 20 parts by weight water per part by weight metakaolin.
1 8. A particulate catalytic composition as claimed in any of claims 12 to 17 when produced by the process as claimed in any one of claims 1 to 11.
GB08309852A 1982-04-12 1983-04-12 Catalysts and catalyst supporters Withdrawn GB2118063A (en)

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AU (1) AU566582B2 (en)
CA (1) CA1211425A (en)
DE (1) DE3312639A1 (en)
FR (1) FR2524817A1 (en)
GB (1) GB2118063A (en)
IT (1) IT1164166B (en)
NL (1) NL8301268A (en)

Cited By (9)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
EP0358261A1 (en) * 1988-09-06 1990-03-14 Petroleo Brasileiro S.A. - Petrobras Kaolin containing fluid cracking catalyst
FR2670687A1 (en) * 1990-12-21 1992-06-26 Shell Int Research PROCESS FOR THE EXTRUSION OF CRYSTALLINE ALUMINOSILICATES.
EP0568170A1 (en) * 1992-04-27 1993-11-03 W.R. Grace & Co.-Conn. Catalytic cracking catalysts and additives
US6787501B2 (en) 2001-07-02 2004-09-07 Exxonmobil Chemical Patents Inc. Molecular sieve catalyst composition, its making and use in conversion processes
US6872680B2 (en) 2002-03-20 2005-03-29 Exxonmobil Chemical Patents Inc. Molecular sieve catalyst composition, its making and use in conversion processes
US7271123B2 (en) 2002-03-20 2007-09-18 Exxonmobil Chemical Patents Inc. Molecular sieve catalyst composition, its making and use in conversion process
WO2008016969A2 (en) * 2006-08-03 2008-02-07 Shell Oil Company A highly stable heavy hydrocarbon hydrodesulfurization catalyst and methods of making and use thereof
US7824541B2 (en) 2006-08-03 2010-11-02 Shell Oil Company Catalyst and process for the manufacture of ultra-low sulfur distillate product
US11498060B2 (en) 2013-10-17 2022-11-15 Shell Usa, Inc. Ultra-stable heavy hydrocarbon hydroprocessing catalyst and methods of making and use thereof

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WO2006005275A1 (en) 2004-07-09 2006-01-19 Fuesting, Bernd Shaped bodies made of powders or granulated metal, method for the production thereof and their use

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GB1599598A (en) * 1977-04-07 1981-10-07 Hoechst Ag Process for the preparation of ethylene glycol

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Publication number Priority date Publication date Assignee Title
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GB1599598A (en) * 1977-04-07 1981-10-07 Hoechst Ag Process for the preparation of ethylene glycol

Cited By (21)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
EP0358261A1 (en) * 1988-09-06 1990-03-14 Petroleo Brasileiro S.A. - Petrobras Kaolin containing fluid cracking catalyst
US5082815A (en) * 1988-09-06 1992-01-21 Petroleo Brasileiro, S.A.-Petrobras Kaolin containing fluid cracking catalyst
AU628076B2 (en) * 1988-09-06 1992-09-10 Petroleo Brasileiro S.A. - Petrobras Kaolin-containing fluid cracking catalyst
FR2670687A1 (en) * 1990-12-21 1992-06-26 Shell Int Research PROCESS FOR THE EXTRUSION OF CRYSTALLINE ALUMINOSILICATES.
EP0494470A1 (en) * 1990-12-21 1992-07-15 Shell Internationale Researchmaatschappij B.V. Process for extruding crystalline aluminosilicates
EP0568170A1 (en) * 1992-04-27 1993-11-03 W.R. Grace & Co.-Conn. Catalytic cracking catalysts and additives
US7301065B2 (en) 2001-07-02 2007-11-27 Exxonmobil Chemical Patents Inc. Molecular-sieve catalyst composition, its making and use in conversion processes
US7160831B2 (en) 2001-07-02 2007-01-09 Exxonmobil Chemical Patents Inc. Molecular sieve catalyst composition, its making and use in conversion processes
US6787501B2 (en) 2001-07-02 2004-09-07 Exxonmobil Chemical Patents Inc. Molecular sieve catalyst composition, its making and use in conversion processes
US6872680B2 (en) 2002-03-20 2005-03-29 Exxonmobil Chemical Patents Inc. Molecular sieve catalyst composition, its making and use in conversion processes
US7271123B2 (en) 2002-03-20 2007-09-18 Exxonmobil Chemical Patents Inc. Molecular sieve catalyst composition, its making and use in conversion process
US7820036B2 (en) 2006-08-03 2010-10-26 Shell Oil Company Highly stable heavy hydrocarbon hydrodesulfurization catalyst and methods of making and use thereof
WO2008016969A3 (en) * 2006-08-03 2008-03-27 Shell Oil Co A highly stable heavy hydrocarbon hydrodesulfurization catalyst and methods of making and use thereof
WO2008016969A2 (en) * 2006-08-03 2008-02-07 Shell Oil Company A highly stable heavy hydrocarbon hydrodesulfurization catalyst and methods of making and use thereof
US7824541B2 (en) 2006-08-03 2010-11-02 Shell Oil Company Catalyst and process for the manufacture of ultra-low sulfur distillate product
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CN101511470B (en) * 2006-08-03 2013-07-10 国际壳牌研究有限公司 A highly stable heavy hydrocarbon hydrodesulfurization catalyst and methods of making and use thereof
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CA1211425A (en) 1986-09-16
AU566582B2 (en) 1987-10-22
AU1327283A (en) 1983-10-20
NL8301268A (en) 1983-11-01
IT1164166B (en) 1987-04-08
IT8320537A0 (en) 1983-04-11
JPS58193732A (en) 1983-11-11
GB8309852D0 (en) 1983-05-18
DE3312639A1 (en) 1983-10-13
FR2524817A1 (en) 1983-10-14

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