WO1988008329A1 - Procede permettant de preparer un catalyseur a zeolithe lie avec un oxyde refractaire de faible acidite - Google Patents

Procede permettant de preparer un catalyseur a zeolithe lie avec un oxyde refractaire de faible acidite Download PDF

Info

Publication number
WO1988008329A1
WO1988008329A1 PCT/US1988/001446 US8801446W WO8808329A1 WO 1988008329 A1 WO1988008329 A1 WO 1988008329A1 US 8801446 W US8801446 W US 8801446W WO 8808329 A1 WO8808329 A1 WO 8808329A1
Authority
WO
WIPO (PCT)
Prior art keywords
silica
zeolite
low acidity
refractory oxide
binder
Prior art date
Application number
PCT/US1988/001446
Other languages
English (en)
Inventor
Robert Peter Absil
Philip Jay Angevine
Joseph Anthony Herbst
John Paul Mcwilliams
Original Assignee
Mobil Oil Corporation
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
Application filed by Mobil Oil Corporation filed Critical Mobil Oil Corporation
Publication of WO1988008329A1 publication Critical patent/WO1988008329A1/fr
Priority to DK731588A priority Critical patent/DK731588A/da

Links

Classifications

    • 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
    • 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
    • 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
    • B01J29/70—Crystalline aluminosilicate zeolites; Isomorphous compounds thereof of types characterised by their specific structure not provided for in groups B01J29/08 - B01J29/65
    • B01J29/7007—Zeolite Beta

Definitions

  • This invention relates to a method for preparing a mechanically stable zeolite catalyst composition possessing a refractory oxide binder of low acidity, e.g., a silica binder.
  • zeolite designates the class of porous crystalline silicates, which contain silicon and oxygen atoms as the major components.
  • Other framework components can be present in minor amount, usually less than about 14 mole ., and preferably less than 4.. These components include aluminum,, gallium, iron, boron, etc., and combinations thereof.
  • the crystalline aluminosilicates constitute an especially well known type of zeolite.
  • aluminosilicate zeolites have long been used as catalysts for a wide variety of organic conversion processes.
  • aluminosilicate zeolites are incorporated with a matrix, or binder, material in order to impart mechanical stability thereto.
  • matrix materials have included alumina and/or clays since these materials are fairly easy to extrude and provide extrudates of good physical strength.
  • the method comprises mixing silica-rich solids, preferably a mixture of silica with a zeolite such as ZSM-4 (Omega), ZSM-5, ZSM-11, ZSM-12, ZSM-23, ZSM-35, ZSM-38, ZSM-48, Beta, X, Y, L, ferrierite, mordenite, dachiardite, clinoptilolite, offretite, erionite, gmelinite or chabazite with water and an alkali metal base such as sodium hydroxide or a basic salt such as an alkali-metal carbonate, borate, phosphate or silicate as an extrusion aid followed by mulling, extruding and subsequently drying the extrudate.
  • a zeolite such as ZSM-4 (Omega), ZSM-5, ZSM-11, ZSM-12, ZSM-23, ZSM-35, ZSM-38, ZSM-48, Beta, X, Y, L, ferrierite
  • Silica-bound zeolite catalysts prepared in accordance with the method described in U.S. Patent No. 4,582,815 are indicated to be useful in hydrocarbon conversions such as hydrocracking, isomerization, hydrogenation, dehydrogenation, polymerization, reforming, catalytic cracking and catalytic hydrocracking.
  • a low acidity refractory oxide-bound zeolite possessing excellent mechanical stability and low binder acidity, making it especially useful as a catalyst for certain kinds of hydrocarbon conversions can be prepared by a method which comprises: a) providing a substantially homogeneous mixture of zeolite, water and a low acidity refractory oxide binder containing at least an extrusion-facilitating amount of said binder in a colloidal state to provide an extrudable mass, said mixture being substantially free of added alkali metal base and/or basic salt; b) extruding the extrudable mass resulting from step
  • step (a) drying the extrudate resulting from step (b); and d) calcining the dried extrudate resulting from step
  • the calcined extrudate can be subjected to other operations such as base exchange, dealumination, steaming and impregnating with catalytically active metal(s), the details of which are well known in the art.
  • low acidity refractory oxide binders such as silica do not interact with zeolites to any appreciable extent. Consequently, zeolites can be bound with low acidity refractory oxides in accordance with the method of this invention without increasing the zeolite's intrinsic activity as might occur with an alumina binder.
  • the use of low-acidity refractory oxide-bound zeolites having lower levels of inherent activity than their alumina-bound counterparts can result in lower coke production and significant increases in cycle length.
  • the zeolite's intrinsic catalytic activity may actually be decreased by binding the zeolite with low acidity refractory oxides, such as silica.. More particularly, zeolite activity may be reduced by binding zeolites such as ZSM-5, Y, Beta, etc. with low acidity refractory oxides such as Si_ 2 and Ti0 2 .
  • this reduction in activity is a result of a chemical reaction of the binder with the zeolite, whereby high acidity oxides such as alumina in the zeolite framework become replaced by low acidity refractory oxides from the binder.
  • zeolites with a silica to alumina molar ratio of 70 or less may become enriched with framework silicon content by binding the zeolite with silica and treating the mixture at elevated temperatures.
  • Zeolites treated in this manner may exhibit lower exchange capacities, hexane cracking (e.g., as measured by alpha value) and toluene disproportionation activities, and shifts in x-ray diffraction patterns.
  • a silica-bound, low sodium, framework dealuminated zeolite Y e.g., ultrastable Y (USY) zeolite
  • USY ultrastable Y
  • the low acidity refractory oxide-bound zeolite catalysts of the present invention are capable of maintaining their structural integrity in low pH solutions, the zeolite dispersed in such, a binder can be treated with an acid solution to effect dealumination. This effectively results in a
  • the method of this invention is not limited to any ' particular zeolite and in general may be employed with all metallosilicates, particularly the aluminosilicates whether or
  • Typical zeolites include ZSM-4 (Omega), ZSM-5; ZSM-11, ZSM-12, ZSM-20, ZSM-23, ZSM-35, ZSM-48, ZSM-50, Beta, X, Y and L as well as ferrierite, mordenite, dachiardite, clinoptilollte, offretite, erionite, gmelinite and chabazite.
  • 30 zeolites utilized herein can be replaced by a wide variety of other cations employing techniques well known in the art. Typical replacing cations including hydronium, ammonium, alkyl ammonium and metal cations. Suitable metal cations include metals such as rare earth metals, as well as metals of Groups IIA and B of the Periodic Table, e.g., zinc, and Group VIII of the Periodic Table, e.g., platinum and palladium.
  • Typical ion-exchange techniques call for contacting the selected zeolite with a salt of the desired replacing cation.
  • a wide variety of salts can be employed, particular preference is given to chlorides, nitrates and sulfates.
  • Representative ion-exchange techniques are disclosed in a wide variety of patents including U.S. Patent Nos. 3,140,249; 3,140,251; and 3,140,253.
  • the zeolite is then preferably washed with water and dried at a temperature of 65-315°C (150-600°F) and thereafter calcined in air, or other inert gas, at a temperature of 260-815°C (500-1500°F) for 1 to 48 hours or more.
  • Catalysts of improved selectivity and other beneficial properties can be obtained by subjecting the zeolite to treatment with steam at elevated temperatures ranging from 260 to 650°C (500 to 1200°F) and preferably from 400 to 540°C (750 to 1000°F).
  • the treatment can be accomplished in an atmosphere of 100% steam or in an atmosphere consisting of steam or ammonia and some other gas which is essentially inert to the zeolites.
  • a similar treatment can be accomplished at lower temperatures and elevated pressure, e.g., from 180 to 370°C (350° to about 700°F) at from 1000-20000 kPa (10 to 200 atmospheres).
  • the zeolite can be treated with reagents prior to steaming and with organics still contained from synthesis to remove alumina from the outside surface, or calcined in air or inert atmosphere to remove the organics and then ion exchanged to the ammonium form or other desired metal exchanged form.
  • Processes for dealuminizing Y are well known in the art, i.e., see Rabo, Zeolite Chemistry and Catalysis, ACS Monograph 171(1976) Chapter 4.
  • the binder material used herein can be selected from among any of the low acidity refractory oxides of metals of Groups IVA and IVB of the Periodic Table of the Elements. Particularly useful are the oxides of silicon, germanium, titanium and zirconium with silica being especially preferred. Combinations of such oxides with other oxides are also useful provided that at least about 40 weight percent, and preferably at least 50 weight percent, of the total oxide is one or a combination of the aforesaid Group IVA and/or Group IVB metal oxides.
  • mixtures of oxides which can be used to provide the binder material herein include silica-alumina, silica-magnesia, silica-zirconia, silica-thoria, silica-beryllia, silica-titania, titania-zirconia, silica-alumina-thoria, silica-alumina- zirconia, silica-alumina-magnesia and silica-magnesia-zirconia.
  • the low acidity refractory oxide contains at least an extrusion-facilitating amount of the oxide in colloidal form, preferably with water as the dispersant.
  • at least part of the low acidity refractory oxide is added in dry particulate form, e.g. amorphous precipitated silica, so as to control the moisture content of the binder/zeolite/water mixture at a level to ensure satisfactory extrusion.
  • the moisture content of the mixture does not exceed 50%, and preferably is at least 40%, by weight. No alkali metal base or basic salt is added to the mixture.
  • the colloidal Group IVA and or Group IVB metal oxide component of the binder can represent anywhere from 1 to 90 weight percent or more of the total binder.
  • amounts of colloidal silica ranging from 2 to 60 weight percent, preferably 5 to 50 weight percent, of the total binder generally provide entirely acceptable results.
  • the relative proportions of zeolite and low acidity refractory oxide binder can vary widely, with the zeolite content ranging from between 1 to 99 weight percent, and more usually in the range of from 4 to 90 weight percent, of the total extrudate (dry basis).
  • Extrudates of 1/16 inch (1.6mm) obtained in accordance with this invention typically have a crush strength of from 5 to 24 pounds (2 - 11kg) when the crushing force is applied over a 1/8 inch (3.2mm) length. This is equivalent to a crush strength range of 40 to 192 lb/linear inch (700 - 3430kg/m).
  • the low acidity refractory oxide-bound extrudates of this invention are also characterized by a high porosity, i.e., between 0.43 to l.cc/gram (measured by mercury porosimeter and helium absorption) .
  • the extrudates of this invention can find utility in a wide variety of processes which are both catalytic and noncatalytic. Quite obviously, the materials can be used as sorbents. Additionally, the materials can be used as catalysts for a wide variety of organic conversions. Moreover, since a low acidity refractory oxide, such as silica, has low catalytic activity, the incorporation of a zeolite in the silica can lead to some unusual catalytic effects.
  • the low acidity refractory oxide can also be used as a support for a catalytic material, e.g., a hydrogenation component such as platinum, palladium, cobalt, molybdenum, iron, tungsten, nickel or mixtures of the same.
  • the catalytic metals in the form of their oxides or salts can also be added to the low acidity refractory oxide during the mulling step with pH adjustment, if necessary, to stabilize the colloidal oxide component of the mixture.
  • the low acidity refractory oxide-bound zeolite extrudates of the invention find utility in catalytic cracking, typically under conditions including a temperature of at least 315°C (600°F), generally 400.-600°C (750°-1100°F), and pressures between 100 and 1500 kPa (atmospheric and 200 psig).
  • the cracking can be conducted in the presence of hydrogen, preferably with the hydrogen partial pressure being no greater than 7000 kPa.
  • This example illustrates the preparation of an alumina-bound USY catalyst to provide a basis for comparison with silica-bound USY catalysts prepared in accordance with the method of this invention (Examples 2-6).
  • Examples 2-6 On a dry basis, 65 weight parts of USY zeolite (Z-14US, W.R. Grace) were intimately admixed with 35 weight parts finely divided alpha alumina monohydrate (Kaiser SA) and an extrudable mass was obtained by mulling. The moisture content of the mix was adjusted to 46-48 weight percent by addition of deionized water. After additional mulling, the resulting paste was extruded using a 2" (5cm) Bonnot extruder to yield 1/16" (1.6mm) diameter extrudates.
  • extrudates were subsequently dried at 121°C (250°F) for 18 hours in air and then calcined at 540°C (1000°F) for 3 hours in air flowing at 3 or 5 v/v/min. Heating rates of 2 or 3°C/min (3 or 5°F/min) were used. Examples 2-6
  • the extrudate was washed and dried at 121°C (250°F) in air and subsequently calcined at 540°C (1000°F) for 3 hours in dry flowing air. This procedure was repeated three times so that the acidity of the catalyst (as measured by the alpha test) increased to a level of 250 to 300 and the sodium content was reduced from 1.8-1.9 to 0.1-0.2 wt %.
  • the calcinations were performed in a relatively anhydrous environment to preclude any significant steaming of the catalyst.
  • zeolite beta on a dry basis in the form of a powder was mulled with 35 wt parts of combined amorphous precipitated silica (HiSil 233 EP) and colloidal silica to produce a homogeneous mix. To facilitate admixture, the moisture content of the mix was adjusted to 45-49 weight percent by adjusting the amount of deionized water added. Two different amounts of colloidal Si0 2 were added to obtain extrudable mixes while maintaining a 65/35 zeolite/binder weight ratio. The resulting mixes were extruded to yield 1.6mm (1/16") diameter extrudates.
  • HiSil 233 EP amorphous precipitated silica
  • colloidal silica colloidal silica
  • extrudates were dried at 121°C (250°F) for 18 hours and were subsequently calcined at 540°C (1000°F) for 3 hours in nitrogen flowing at 3 or 5 v/v/min. This was followed by a 3 hour calcination at 1000°F (540°C) in air flowing at 3 or 5 v/v/min.
  • each extrudate was exchanged twice at room temperature for 1 hour with a 5 ml/g circulating IN ammonium nitrate solution. After washing the extrudate was then calcined at 540°C (1000°F) for 3 hours in air flowing at 3 or 5 v/v/min.
  • silica-bound ZSM-5 extrudates (Examples 11 and 12) were prepared substantially as described in Examples 8 and 9.
  • the physical properties of the silica-bound ZSM-5 extrudates and those of a commercial alumina-bound ZSM-5 extrudate (Example 10) are set forth in Table 3 as follows:
  • silica-bound catalysts prepared by the extrusion method of this invention retain their structural integrity upon calcination and ammonium exchange.
  • An important advantage of silica-bound zeolite catalysts is that the extrudates can be acid treated without losing their structural integrity.
  • the silica-bound USY catalyst of Example 3 was steamed for 10 hours at 540°C (1000°F) to reduce the alpha activity from 255 to 50-60 and to reduce the unit cell size from 24.52 to 24.35 Angstroms.
  • the steamed extrudate (Example 13) was then treated for 4 hours in a IN HN03 solution at 55oC or 85oC (Examples 14-17).
  • a sodium exchanged zeolite Y (NaY) was extruded with silica in a 65/35 zeolite binder ratio.
  • This extrudate was prepared by mixing, on a dry basis, 65 weight parts of NaY with 17.5 weight parts amorphous precipitated silica (HiSil 233 EP) and 17.5 weight parts of colloidal silica (HS-30). After mulling and water addition as appropriate, the resulting homogenous mixture paste was extruded to 1/16" diameter extrudate. The extrudate was dried at 121°C. 1 gram of this catalyst was calcined at 538°C for four hours under high nitrogen purge such that in-situ steaming of the material was avoided. The calcined silica bound catalyst was analyzed by x-ray diffraction along with the uncalcined silica bound catalyst.
  • X-ray diffraction data was collected at the Brookhaven National Laboratory, National Synchrotron Light Source on the - X13A powder diffractometer.
  • the diffractbmeter employs parallel beam geometry with a Ge(lll) incident beam monochromater and a Ge(220) analyzer crystal. Data was obtained with a 2-theta step scan of 0.01 degrees, 2 second count times per step, a theta scan of 2 degrees per step, and an x-ray wavelength of 1.3208 Angstroms.
  • the 2-theta zero and x-ray wavelength were calibrated with a National Bureau of Standards silicon metal standard.
  • D-spacings were obtained ' from the measured data with a second derivative peak search algorithm.
  • the lattice parameters were refined with a standard least-squares refinement program.
  • a zeolite beta/silica mix was prepared with a 65/35 weight ratio as in examples 8 and 9 but using only colloidal silica as the low acidity, refractory oxide source.
  • zeolite beta crystals ash content 75.5%
  • colloidal silica Lidox HS-30
  • Example 19 The process of Example 19 was repeated but with ratio of the zeolite beta (ash content 75.5%) to colloidal silica (ash content 30%) increased to 82.5/17.5 to produce mixtures in which the moisture content was at a level suitable for extrusion.
  • ratio of the zeolite beta (ash content 75.5%) to colloidal silica (ash content 30%) increased to 82.5/17.5 to produce mixtures in which the moisture content was at a level suitable for extrusion.
  • Table 5 Table 5 Physical Properties of Silica-Bound Zeolite Beta

Landscapes

  • Chemical & Material Sciences (AREA)
  • Engineering & Computer Science (AREA)
  • Materials Engineering (AREA)
  • Organic Chemistry (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Crystallography & Structural Chemistry (AREA)
  • Catalysts (AREA)

Abstract

Dans un procédé de préparation d'un catalyseur à zéolithe lié avec un oxyde réfractaire de faible acidité, on réalise un mélange sensiblement homogène de zéolithe, d'eau et d'un liant d'oxyde réfractaire à faible acidité, contenant au moins une quantité facilitant l'extrusion dudit liant à l'état colloïdal pour offrir une masse extrudable, le mélange étant sensiblement exempt de base de métal alkalin ajoutée et/ou de sel basique. La masse extrudable est ensuite extrudée, séchée et calcinée pour produire un matériau d'une résistance à l'écrasement similaire à celle d'un matériau contenant de l'alumine à titre de liant.
PCT/US1988/001446 1987-05-01 1988-05-02 Procede permettant de preparer un catalyseur a zeolithe lie avec un oxyde refractaire de faible acidite WO1988008329A1 (fr)

Priority Applications (1)

Application Number Priority Date Filing Date Title
DK731588A DK731588A (da) 1987-05-01 1988-12-30 Fremgangsmaade til fremstilling af en zeolit-katalysator, der er bundet til et ildfast oxid med lavt syreindhold

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
US4463987A 1987-05-01 1987-05-01
US044,639 1987-05-01

Publications (1)

Publication Number Publication Date
WO1988008329A1 true WO1988008329A1 (fr) 1988-11-03

Family

ID=21933481

Family Applications (1)

Application Number Title Priority Date Filing Date
PCT/US1988/001446 WO1988008329A1 (fr) 1987-05-01 1988-05-02 Procede permettant de preparer un catalyseur a zeolithe lie avec un oxyde refractaire de faible acidite

Country Status (6)

Country Link
EP (1) EP0312584A4 (fr)
JP (1) JPH01503127A (fr)
AU (1) AU606421B2 (fr)
NZ (1) NZ224450A (fr)
WO (1) WO1988008329A1 (fr)
ZA (1) ZA883091B (fr)

Cited By (10)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
EP0313276A1 (fr) * 1987-10-22 1989-04-26 Mobil Oil Corporation Procédé d'hydrodéparaffinage catalytique
WO1990008120A1 (fr) * 1989-01-12 1990-07-26 Mobil Oil Corporation Procede de conversion d'olefines en alcools et/ou en ethers
EP0387289A1 (fr) * 1987-11-17 1990-09-19 Mobil Oil Corp Procede catalytique de reformage.
EP0403966A1 (fr) * 1989-06-20 1990-12-27 VAW Aluminium AG Catalyseur moulé à base d'aluminosilicate et procédé pour sa préparation
WO1991010509A1 (fr) * 1990-01-12 1991-07-25 Henkel Kommanditgesellschaft Auf Aktien Utilisation de sol d'acide silicique colloidal comme adjuvant pour catalyseurs
EP0481689A1 (fr) * 1990-10-16 1992-04-22 Ube Industries, Ltd. Procédé pour avoir le contrôle du degré de dispersion du composé actif d'un catalyseur solide du type métal/support
US5120693A (en) * 1991-03-25 1992-06-09 Uop Bonded adsorbent agglomerates
EP0553562A1 (fr) * 1992-01-31 1993-08-04 Mobil Oil Corporation Procédé pour la désalumination d'une zéolite bêta
EP0644801A1 (fr) * 1992-06-02 1995-03-29 Mobil Oil Corporation Catalyseurs lies a un oxyde refractaire de faible acidite
US5407881A (en) * 1992-06-25 1995-04-18 Sumitomo Chemical Co., Ltd. Process for increasing the strength of a zeolite molding

Families Citing this family (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US6709570B1 (en) * 1999-09-27 2004-03-23 Shell Oil Company Method for preparing a catalyst
FR3129301A1 (fr) * 2021-11-22 2023-05-26 IFP Energies Nouvelles Materiau comprenant une silice mise en forme par extrusion avec un liant phosphopotassique ou phosphate de cesium presentant des proprietes mecaniques ameliorees et son procede de preparation

Citations (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US3518206A (en) * 1968-05-17 1970-06-30 Du Pont Supported catalysts composed of substrate coated with colloidal silica and catalyst
US4582815A (en) * 1984-07-06 1986-04-15 Mobil Oil Corporation Extrusion of silica-rich solids

Family Cites Families (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
DE1164995B (de) * 1961-10-25 1964-03-12 Bayer Ag Verfahren zur Herstellung gebundener Molekularsiebe
DD203068A1 (de) * 1976-12-13 1983-10-12 Leuna Werke Veb Verfahren zur herstellung von zeolithaltigen hydrospaltkatalysatoren mit verbesserter porenstruktur
US4507396A (en) * 1983-08-18 1985-03-26 Chevron Research Company Solid body preparation and formation by agglomeration in an immiscible solvent
AU5100285A (en) * 1984-12-24 1986-07-03 Mobil Oil Corp. Zeolite catalyst composition having improved stability

Patent Citations (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US3518206A (en) * 1968-05-17 1970-06-30 Du Pont Supported catalysts composed of substrate coated with colloidal silica and catalyst
US4582815A (en) * 1984-07-06 1986-04-15 Mobil Oil Corporation Extrusion of silica-rich solids

Non-Patent Citations (1)

* Cited by examiner, † Cited by third party
Title
See also references of EP0312584A4 *

Cited By (15)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
EP0313276A1 (fr) * 1987-10-22 1989-04-26 Mobil Oil Corporation Procédé d'hydrodéparaffinage catalytique
AU615679B2 (en) * 1987-10-22 1991-10-10 Mobil Oil Corporation Catalytic hydrodewaxing process
EP0387289A4 (en) * 1987-11-17 1990-12-05 Mobil Oil Corporation Catalytic reforming process
EP0387289A1 (fr) * 1987-11-17 1990-09-19 Mobil Oil Corp Procede catalytique de reformage.
WO1990008120A1 (fr) * 1989-01-12 1990-07-26 Mobil Oil Corporation Procede de conversion d'olefines en alcools et/ou en ethers
EP0403966A1 (fr) * 1989-06-20 1990-12-27 VAW Aluminium AG Catalyseur moulé à base d'aluminosilicate et procédé pour sa préparation
US5100853A (en) * 1989-06-20 1992-03-31 Vereinigte-Aluminium-Werke Ag Molded aluminosilicate catalyst and method for its preparation
WO1991010509A1 (fr) * 1990-01-12 1991-07-25 Henkel Kommanditgesellschaft Auf Aktien Utilisation de sol d'acide silicique colloidal comme adjuvant pour catalyseurs
US5294583A (en) * 1990-01-12 1994-03-15 Henkel Kommanditgesellschaft Auf Aktien Use of colloidal silica sol as an auxiliary for catalysts
EP0481689A1 (fr) * 1990-10-16 1992-04-22 Ube Industries, Ltd. Procédé pour avoir le contrôle du degré de dispersion du composé actif d'un catalyseur solide du type métal/support
US5120693A (en) * 1991-03-25 1992-06-09 Uop Bonded adsorbent agglomerates
EP0553562A1 (fr) * 1992-01-31 1993-08-04 Mobil Oil Corporation Procédé pour la désalumination d'une zéolite bêta
EP0644801A1 (fr) * 1992-06-02 1995-03-29 Mobil Oil Corporation Catalyseurs lies a un oxyde refractaire de faible acidite
EP0644801A4 (fr) * 1992-06-02 1995-07-26 Mobil Oil Corp Catalyseurs lies a un oxyde refractaire de faible acidite.
US5407881A (en) * 1992-06-25 1995-04-18 Sumitomo Chemical Co., Ltd. Process for increasing the strength of a zeolite molding

Also Published As

Publication number Publication date
EP0312584A1 (fr) 1989-04-26
ZA883091B (en) 1989-12-27
EP0312584A4 (fr) 1989-09-11
NZ224450A (en) 1990-04-26
AU1725988A (en) 1988-12-02
AU606421B2 (en) 1991-02-07
JPH01503127A (ja) 1989-10-26

Similar Documents

Publication Publication Date Title
US5053374A (en) Method for preparing a zeolite catalyst bound with a refractory oxide of low acidity
US4582815A (en) Extrusion of silica-rich solids
US5430000A (en) Method for preparing titania-bound zeolite catalysts
US4500422A (en) Catalysis over activated zeolites
US4427789A (en) Activation of zeolites
EP0674600B1 (fr) Preparation de zeolites d'aluminosilicate
US4605637A (en) Hydrothermal activation of acid zeolites with aluminum phosphates
KR100711041B1 (ko) 저산도의 내화성 산화물 결합 제올라이트 촉매의 제조방법
US4538015A (en) Catalysis over activated zeolites
US4517075A (en) Catalysis over activated zeolites
US4943545A (en) Activation of zeolites
US5785944A (en) Preparation of Y zeolite
US10112188B2 (en) Process for manufacture of a zeolite based catalyst for the conversion of methanol to olefins
EP0156595B1 (fr) Procédé pour préparer des particules discrètes à base de zéolithe
WO1988008329A1 (fr) Procede permettant de preparer un catalyseur a zeolithe lie avec un oxyde refractaire de faible acidite
US4837397A (en) Nobile metal containing catalysts of improved stability
US4500420A (en) Catalysis over activated zeolites
US4678766A (en) Enhancement of shape selectivity of zeolites
US4788169A (en) Low acidity alumina-bound zeolites containing tetrahedral boron, gallium, indium and/or thallium
US4538016A (en) Catalysis over activated zeolites
US4430314A (en) Method of preparing crystalline zeolite
US4837398A (en) Ammonium activation of zeolites in the presence of gaseous ammonia
EP0186395B1 (fr) Composition de catalyseur zéolitique ayant une stabilité améliorée
EP0191212B1 (fr) Modification de zéolites avec du fluorure d'ammonium
EP0295020A1 (fr) Activation d'une zéolite

Legal Events

Date Code Title Description
AK Designated states

Kind code of ref document: A1

Designated state(s): AU DK JP

AL Designated countries for regional patents

Kind code of ref document: A1

Designated state(s): AT BE DE FR GB IT NL SE

WWE Wipo information: entry into national phase

Ref document number: 1988904365

Country of ref document: EP

WWP Wipo information: published in national office

Ref document number: 1988904365

Country of ref document: EP

WWW Wipo information: withdrawn in national office

Ref document number: 1988904365

Country of ref document: EP