WO1996009889A1 - Catalyseurs et additifs contenant un liant des terres rares - Google Patents

Catalyseurs et additifs contenant un liant des terres rares Download PDF

Info

Publication number
WO1996009889A1
WO1996009889A1 PCT/US1995/010613 US9510613W WO9609889A1 WO 1996009889 A1 WO1996009889 A1 WO 1996009889A1 US 9510613 W US9510613 W US 9510613W WO 9609889 A1 WO9609889 A1 WO 9609889A1
Authority
WO
WIPO (PCT)
Prior art keywords
rare earth
composition
particles
binder
alumina
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.)
Ceased
Application number
PCT/US1995/010613
Other languages
English (en)
Inventor
Ranjit Kumar
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.)
WR Grace and Co Conn
WR Grace and Co
Original Assignee
WR Grace and Co Conn
WR Grace and Co
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 WR Grace and Co Conn, WR Grace and Co filed Critical WR Grace and Co Conn
Priority to EP95929629A priority Critical patent/EP0783368A1/fr
Priority to AU33323/95A priority patent/AU3332395A/en
Priority to JP8511746A priority patent/JPH10506571A/ja
Priority to KR1019970702056A priority patent/KR970706063A/ko
Publication of WO1996009889A1 publication Critical patent/WO1996009889A1/fr
Anticipated expiration legal-status Critical
Ceased legal-status Critical Current

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
    • B01J23/00—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00
    • B01J23/10—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of rare earths
    • 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
    • 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
    • B01J2229/42—Addition of matrix or binder particles

Definitions

  • the prior art discloses various methods for improving the catalytic cracking activity and selectivity of catalytic cracking catalysts in the presence of V where a rare earth component is added to the catalyst.
  • U.S. Pat. 3,930,987 describes a process wherein cracking catalyst composite particles (comprising a zeolite in a matrix) are impregnated with a solution of rare earth salts. Various soluble rare earth salts may be used to prepare the catalysts.
  • U.S. Pat. 4,515,683 discloses a method for passivating vanadium on catalytic cracking catalysts wherein lanthanum is nonionically precipitated on the catalyst prior to ordinary use. In a preferred embodiment, lanthanum is precipitated by the addition of ammonium hydroxide or oxalic acid to a catalyst which has been previously impregnated with a rare-earth chloride solution.
  • 4,921,824 discloses a catalytic cracking catalyst which contains separate and discrete particles of lanthanum oxide.
  • the lanthanum oxide particles are added as separate particles along with the catalyst particles during the cracking process.
  • the lanthanum oxide additive may include an inert matrix such as clay, silica and/or a metal oxide.
  • U.S. Pats. 5,194,413 and 5,248,642 disclose cracking catalysts and additives which contain an inorganic rare earth oxide and/or oxychloride dispersed as discrete particles in clay/alumina and or reacted metakaolin matrix. The catalysts are particularly active for the cracking of metal-containing hydrocarbon feedstocks.
  • the invention provides improved cracking catalyst and additive compositions that are highly effective for controlling the adverse effects of metals such as vanadium wherein those compositions are characterized by the presence of a rare earth compound binder material.
  • the invention encompasses compositions especially useful in catalytic cracking wherein zeolitic cracking catalyst particles and/or other particles are bound by rare earth compound binder.
  • the rare earth compounds contained in the binder are preferably selected from the group consisting of oxides, oxychlorides, oxycarbonates, and mixtures thereof.
  • the invention encompasses the use of a rare earth compound binder in combination with an auxiliary binder material.
  • the auxiliary binder is preferably selected from the group consisting of peptized alumina and colloidal silica.
  • the invention encompasses the compositions containing high surface area filler particles in combination with a rare earth compound binder material.
  • Preferred high surface area particles are silica xerogels and silica hydrogels.
  • the invention also encompasses methods for preparing compositions containing the rare earth compound binder materials of the invention wherein a rare earth acid sol or rare earth salt solution is combined with the desired paniculate material and is subsequently converted into the desired rare earth compound material
  • the invention further encompasses improved methods for catalytic cracking of hydrocarbons using the compositions of the invention.
  • Figures 1 to 4 are graphic plots of catalytic cracking data which illustrate the performance of compositions of the invention.
  • Figure 5 is a schematic cross section of a rare earth compound binder- containing composition contemplated by the invention
  • the invention encompasses compositions characterized by the presence of a rare earth compound binder material and one or more particulate materials bound by the rare earth compound binder.
  • the compositions of the invention are especially useful in catalytic cracking processes where a hydrocarbon feedstock to be cracked contains significant amounts of vanadium, however the compositions may be used in other processes.
  • the rare earth compound binder material preferably comprises rare earth compound(s) selected from the group consisting of oxides, oxychlorides, oxycarbonates and mixtures thereof. Most preferably, the rare earth compound material consists essentially of the these rare earth compounds.
  • the rare earth metal in the compound(s) may be any rare earth metal or mixture thereof.
  • the rare earth metal is selected from the group consisting of lanthanum, neodymium, cerium and mixtures thereof. Most preferably, the rare earth metal consists essentially of lanthanum.
  • the rare earth compound phase is derived from a rare earth acid sol, however the rare earth compound phase may also be derived from a rare earth compound solution (e.g. a rare earth salt such as rare earth chloride). Most preferably, the rare earth compound phase consists essentially of lanthanum compounds derived from a rare earth acid sol.
  • an auxiliary binder may be used in combination with the rare earth binder.
  • the auxiliary binder may be any sol or colloidal component which acts with the rare earth compound binder to improve the attrition resistance of the metals passivation component.
  • Preferred auxiliary binders are selected from the group consisting of silica sol (colloidal silica) and alumina sol (preferably peptized alumina).
  • any auxiliary binder present is at a level of 50 wt.% (oxide basis) or less based on the total weight of rare earth binder and auxiliary binder. More preferably, the auxiliary binder forms about 40 wt.% of the total binder weight (most preferably, about 1/3 or less of the total binder weight).
  • Figure 5 provides a schematic illustration of one possible composition of the invention. This illustration is presented to clarify the discussion below regarding various possible components of the compositions. It should be noted that the relative sizes of the various components depicted in Figure 5 is not to scale. Further, the particles have been depicted as spherical for ease of illustration. The particles may be irregularly shaped.
  • the binder material 2 may be homogeneous or heterogeneous.
  • the binder 2 may contain a fine paniculate material 4 in addition to a continuous rare earth compound phase 6 so long as that fine paniculate 4 does not interfere with the ability of the binder 2 to bind the desired (larger) paniculate material 8 which is also present in the overall composition 10.
  • the binder 2 may be a combination of rare earth compound binder and auxiliary binder(s). If any fine paniculate material 4 is present in the binder 2, preferably that material is itself a rare earth compound or an oxide from which the auxiliary binder is derived. Most preferably, the fine paniculate material 4 comprises a rare earth compound selected from the group consisting of oxides, oxychlorides, oxycarbonates and mixtures thereof. Other compounds (in addition to any auxiliary binder) may be present in the rare earth compound phase 6 in minor amounts as long as they do not adversely affect the perfor ance of the overall composition with respect to cracking of metal-containing feedstocks.
  • the paniculate phase may include particles of any material which does not adversely affect the performance of the rare earth compound phase with respect to V and/or Ni nor the performance of the overall catalytic cracking process.
  • compositions of the invention can be used in at least the following modes: a. as an additive particle added to catalytic cracking reactor separately or as a physical admixture with cracking catalyst particles, b. as an additive incorporated into a cracking catalyst particle, or c. as a catalytic cracking catalyst particle having a rare earth compound binder phase.
  • the paniculate bound in the composition preferably comprises a non- zeolitic material selected from the group consisting of clays (such as kaolin), alumina, silica, and other non-zeolitic filler materials.
  • the filler particles are alumina particles.
  • the filler particles may have some functionality beyond simply adding less expensive bulk to the composition.
  • the bound particles may comprise or consist essentially of additional rare earth compound particles adapted to provide additional metal passivation.
  • High surface area filler particles may be incorporated into the compositions of the invention to improve the metals passivation performance.
  • Preferred high surface area filler particles are silica xerogels and hydrogels, however any suitable high surface area particles may be used. If desired, mixtures of diverse particles can be used as the bound paniculate phase. Where the composition of the invention is itself used as a paniculate cracking catalyst (mode c.
  • the paniculate material (bound by the rare earth compound material) preferably comprises a zeolitic cracking catalyst (e.g. a zeolite Y).
  • a zeolitic cracking catalyst e.g. a zeolite Y
  • any known cracking catalyst may be incorporated into the composition of the invention. If desired, other paniculate materials can also be incorporated into the composition along with the zeolitic cracking catalyst.
  • the total amount of binder phase (rare earth and any auxiliary binder) in the composition is preferably about 10-75 wt.% based on the total dry weight of the composition.
  • the composition is used as an additive (mode a. or b. above)
  • the composition more preferably contains about 20-60 wt.% of the binder phase.
  • the composition is itself used as a cracking catalyst (mode c. above)
  • the composition more preferably contains about 10-25 wt.% of the binder phase.
  • the balance of the composition would be paniculate components bound by the binder phase.
  • the relative proportions of the bound paniculate components may be varied depending on the intended use of the composition (e.g. mode a. vs. mode c).
  • the bound paniculate components preferably comprise about 0-90 parts by wt. clay, more preferably about 40 to 80 parts; about 0- 80 parts alumina, more preferably about 20 to 70 parts; and 0-50 parts by weight zeolite (molecular sieve), more preferably about 0 to 20 parts.
  • the amount and type of zeolite present in the composition should be such that the resulting composition is an effective cracking catalyst.
  • the rare earth-containing compositions of the invention may be incorporated into commercial zeolite-containing fluid cracking catalysts (FCC) particles.
  • FCC catalysts are OCTACAT*, ORION*, SUPER-D*, DA* and XP* catalysts manufactured and sold by the Davison Chemical Division of W. R. Grace & Co -Conn.
  • FCC catalysts typically comprise a zeolite (molecular sieve) such as type X, Y, ultrastable Y (USY), rare earth-exchanged Y (REY), Beta, and/or ZSM-5 dispersed in silica, alumina or silica-alumina clay matrix.
  • zeolites are disclosed in U.S.
  • the FCC catalyst may be prepared in accordance with any known method such as those disclosed in U.S. Pats. 3,957,689, 4,499,197, 4,542,118 and 4,458,023 or Canadian Pat. 967,136 The disclosures of these various patents are incorporated herein by reference.
  • the rare earth binder-containing compositions preferably form about 5 to 25 wt.% of the FCC particles, more preferably about 5 to 15 wt.%. Similar proportions of the compositions of the invention are also preferred where the compositions of the invention are used as separate paniculate admixtures in conjunction with FCC particles.
  • compositions of the invention are not limited to any specific method of manufacture, processes using rare earth salt solutions or acid sols of rare earth metal compounds are preferred.
  • a discussion of rare earth sols can be found in U.S. Pat. 3,024,199 the disclosure of which is incorporated herein by reference.
  • the rare earth binder-containing compositions of the invention are obtained by a method comprising: (a) mixing a rare earth compound sol or rare earth salt solution with the particles to be bound to form a mixture,
  • step (c) calcining the mixture particles to obtain particles which themselves comprise the particles added in step (a) bound by a rare earth compound phase.
  • the rare earth compound sol or salt solution may be formed by any conventional method.
  • a rare earth sol is used, it is preferably obtained by peptizing a slurry of rare earth compound material with a monobasic acid.
  • the monobasic acid(s) is preferably added to an aqueous slurry of the rare earth compound material to be peptized.
  • the peptizing reaction is then allowed to occur.
  • the slurry can be heated to accelerate the peptization.
  • the peptization is conducted at about 20°-90°C.
  • the peptization can be carried out for whatever time is necessary to form a sol which is capable of forming the desired rare earth binder phase.
  • the peptization is allowed to proceed for about 5 minutes to 2 hours.
  • the solids content of the initial slurry is preferably about 5-20 wt.%.
  • the amount of the acid used is preferably an amount which is sufficient to peptize all the initial rare earth compound material.
  • the mole ratio of acid to rare earth compound in the initial slurry preferably ranges from about 1-4.
  • agitation may be employed to facilitate forming the initial slurry and/or the resulting sol. It may be possible in some instances to add expedients such as dispersants to the initial slurry or the rare earth sol.
  • peptized alumina is used as an auxiliary binder, preferably it is formed by adding alumina to the rare earth compound-monobasic acid mixture wherein an excess of monobasic acid has been used (i.e., beyond that needed to simply peptize the rare earth compound.)
  • the peptized alumina may be partially or fully peptized.
  • the initial rare earth compound material may contain any rare earth compounds capable of forming a sol and of forming the desired rare earth compounds in the calcined end product.
  • the rare earth compounds to be peptized are selected from the group consisting of oxides, carbonates, hydroxides, oxychlorides and mixtures thereof.
  • the rare earth elements in the compounds to be peptized are selected from the group consisting of lanthanum, neodymium, cerium and mixtures thereof.
  • the rare earth compounds consist essentially of lanthanum compounds.
  • the monobasic acid may be any organic or inorganic acid capable of peptizing the initial rare earth compound material.
  • the monobasic acid may be selected to alter the composition of the rare earth compound phase obtained after calcination (compared to the composition of the initial rare earth material) or may be selected such that little or no difference in the make up of the rare earth compounds occurs between the initial rare earth compound material to be peptized and the rare earth compound phase after calcination.
  • the use of hydrochloric acid will typically result in the formation of rare earth oxychloride in the calcined product whereas the use of nitric acid will typically result in the formation of rare earth oxide in the calcined product.
  • the monobasic acid is selected from the group consisting of formic acid, acetic acid, hydrochloric acid, and nitric acid.
  • Formic acid is generally preferred.
  • a rare earth salt solution is used, it is preferably formed by simply dissolving the desired rare earth salt(s) in water.
  • concentration of salt in the solution is preferably such that the mixture resulting from step (a) can be spray dried to yield a composition with the desired amount of rare earth binder.
  • Prefened rare earth salts are selected from the group consisting of rare earth chlorides and nitrates.
  • the rare earth sol (or solution) is combined with a paniculate material.
  • the mixing may be performed by any conventional means.
  • the sol (or solution) and paniculate material are subjected to milling
  • the consistency of the resulting mixture is preferably such that the mixture can be formed into particles by spray drying.
  • the amount of sol (or solution) in the mixture should be sufficient enough so that the rare earth phase will act as a binder for the paniculate material in the calcined particle.
  • the rare earth sol (or solution) and paniculate material are combined such that the resulting mixture contains about 15 to 75 wt.% of the rare earth compounds (measured as the rare earth compounds present in the initial rare earth compound material) based on the total weight of the rare earth compounds and the paniculate material.
  • auxiliary binder it is preferably added to the mixture before the mixture is formed into particles.
  • the auxiliary binder may be formed by peptizing in the same mixture as the rare earth sol by subsequent addition in the presence of excess monobasic acid.
  • the mixture from step (a) may be formed into particles by any known method.
  • the mixture is formed into particles by spray drying.
  • the mixture preferably has a solids content of about 10 to 30 weight percent If necessary, the solids content of the sol-particle mixture can be altered by addition or removal of liquid
  • the spray drying is preferably conducted at a temperature of about 160 to 190°C to obtain particles having a size range of 10 to 150 microns (mm).
  • the spray dried particles are then calcined
  • the calcining is preferably performed at a temperature of 400 to 800°C for about 1 hour
  • the rare earth compounds are reacted to form the desired rare earth phase composition and to transform the spray dried particles into dense, attrition-resistant particles containing a paniculate phase bound by a rare earth compound phase
  • the calcining conditions can be used to influence the composition of the resulting rare earth phase
  • the calcination can be conducted in the presence of steam to promote formation of rare earth oxide
  • the calcined particles preferably possess the following catalytic and physical properties
  • the Davison Index (DI) is determined as follows
  • a sample of catalyst is analyzed to determine the 0 to 20 micron size content The sample is then subjected to a 1 hour test in a Fluid Catalyst Attrition Apparatus using a hardened steel jet cup having a precision bored orifice. An air flow of 21 liters a minute is used The Davison Index is calculated as follows
  • compositions are preferably used in FCC processes conducted at cracking reaction temperatures of 500 to 600°C and regeneration temperatures of 600 to 850°C using hydrocarbon feedstocks that may contain up to 100 ppm or more of V and Ni.
  • the presence of the compositions of the invention during the FCC process passivates the adverse effects of metals such as vanadium and decreases the formation of hydrogen and coke. It is believed that use of the compositions of the invention will permit the successful use of FCC regeneration catalysts that contain as much as 10,000 to 20,000 ppm V.
  • La 2 O 3 was first slurried in water at about 25°C. The solid content of the slurry was from about 8-15 percent. Samples of the La 2 O 3 slurry were combined with various amounts of formic acid while the slurry was intensely mixed. After the addition of the formic acid, the mixing was continued for about 10 minutes. The resulting sols possessed a HC00H La 2 O? mole ratio of 1.0, 1.5, 2.0 and 3.0 respectively.
  • Example 1 The sols of Example 1 were each combined with kaolin particles as follows. 25 wt.% La 2 O 3 and 75 wt.% kaolin (Samples 1, 2 & 3) 50 wt.% La 2 O 3 and 50 wt.% kaolin (Samples 4, 5 & 6)
  • the solids content (total of La compound (calculated on an oxide basis) and kaolin) of the resulting mixtures ranged from 14-25 wt.% as indicated in Table I.
  • the mixtures were milled, spray dried, and calcined in a muffle furnace for 1 hour at 593°C (1 100°F).
  • composition 25% La 2 O 3 -75% Clay 50% La 2 O 3 -50% Clay (wt.%)
  • Blends were impregnated with V as follows: Calcine the sample for 1 hour at 216°C (400°F); then, raise the temperature to
  • One cycle consists of a 10 minute purge with N 2 , 10 minute stream of 5% propylene in air, and 10 minute purge of N 2 followed by a 10 minute exposure to an air stream containing 4000 ppm SO 2 and 10 minute purge of N 2 .
  • Example 3 The FCC/ Additive mixtures of Example 3 were evaluated for the catalytic cracking of a gas-oil feedstock. MAT evaluation was conducted using the procedure set forth in ASTM 3907. The kinetic conversion, coke selectivity, hydrogen selectivity and hydrogen/methane selectivity were determined at various catalyst/oil (cat/oil) ratios expressed as wt.% and conversion levels. The resulting data for Blends A, B, and C is summarized in Figures 1, 2, 3 and 4. The letter labels on the curves correspond to the respective blends.
  • a lanthanum oxide slurry was prepared by vigorously mixing 1579 g of La 2 O 3 in 13.4 kg of water. 942 g of formic acid solution (45 wt.% formic acid) was added to the slurry followed by vigorous mixing for 15 minutes. 1059 g of kaolin clay and 843 g of alumina (VERSAL 900 from LaRoche Chemical Co.) and 800 g of water were added to the slurry. The resulting slurry was then mixed in a high shear mixer, then milled in a DRAIS mill, and spray dried. The spray dried material was then calcined for 1 hour at 593 °C in a muffle furnace. The resulting product had an average particle size of 58 ⁇ m, average bulk density of 0.85, 32 m 2 /g surface area, and a DI of 8.
  • Example 7 An aqueous rare earth chloride solution containing approximately 60 wt.% La on an oxide basis was combined with kaolin clay and water to form a slurry having a solids content of about 10 wt.%. The slurry was milled, spray dried, and calcined at 649 °C for 1 hour in a muffle furnace to yield a composition containing 25 wt.% RE 2 O 3 and 75 wt.% kaolin. The composition had an attrition index of about 8, an average bulk density of 0.92 and an average particle size of 46 ⁇ m.
  • aqueous rare earth chloride solution containing approximately 60 wt.% La on an oxide basis was combined with kaolin clay, water and colloidal silica (LUDOX brand) to form a slurry having a solids content of about 10 wt.%.
  • the slurry was milled, spray dried, and calcined at 649 °C for 1 hour in a muffle furnace.
  • the composition had an attrition index of about 4, an average bulk density of 1.04 and an average particle size of 77 ⁇ m.
  • Example 9 An aqueous rare earth chloride solution containing approximately 60 wt.% La on an oxide basis was combined with kaolin clay, silica ID xerogel, and water to form a slurry having a solids content of about 10 wt.%.
  • the slurry was milled (Prater mill), spray dried and calcined at 649 °C for 1 hour in a muffle furnace to yield a composition containing 40 wt.% RE 2 O 3 , 35 wt.% kaolin, and 25 wt.% xerogel.
  • the composition had an attrition index of about 11, an average bulk density of 0.85 and an average particle size of 64 ⁇ m.
  • Example 10 In order to demonstrate the utility of the materials (traps) of examples 7-9 for trapping vanadium in FCC operation, the following study was carried out: a 100 g (on a dry basis) blend was prepared by mixing one of the traps prepared above with an ORION 822 (GRACE-Davison) FCC catalyst at a weight ratio of 1 part trap to 9 parts FCC catalyst. An unblended, 100 g of FCC catalyst was taken as a base case.
  • ORION 822 GRACE-Davison
  • each of the above deactivated samples was divided into two fractions - approximately 10 weight % of sink (metals trap) and approximately 90 weight % of float (FCC catalyst) fractions - by means of so-called "sink-float" or density separation, using tetrabromoethane having a density of 2.96 g/ml, tetrachloroethane having a density of 1.58 g/ml, and a centrifuge.
  • V- PUF vanadium pick-up factor

Landscapes

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

Abstract

Des additifs et des catalyseurs de craquage catalytique comprenant un liant des terres rares conviennent particulièrement aux procédés de craquage catalytique pour charges de départ hydrocarburées à teneur métallique élevée. On peut utiliser ces catalyseurs et additifs conjointement avec des catalyseurs de craquage au zéolite afin d'accroître la sélectivité/l'activité catalytique, en particulier pour des charges de départ hydrocarburées contenant du vanadium. Ce liant des terres rares est de préférence dérivé d'un sol acide des terres rares.
PCT/US1995/010613 1994-09-29 1995-08-21 Catalyseurs et additifs contenant un liant des terres rares Ceased WO1996009889A1 (fr)

Priority Applications (4)

Application Number Priority Date Filing Date Title
EP95929629A EP0783368A1 (fr) 1994-09-29 1995-08-21 Catalyseurs et additifs contenant un liant des terres rares
AU33323/95A AU3332395A (en) 1994-09-29 1995-08-21 Rare earth binder-containing additives and catalysts
JP8511746A JPH10506571A (ja) 1994-09-29 1995-08-21 希土類結合剤含有添加剤および触媒
KR1019970702056A KR970706063A (ko) 1994-09-29 1995-08-21 희토류 결합제 함유 첨가제 및 촉매(rare earth binder-containing additives and catalysts)

Applications Claiming Priority (4)

Application Number Priority Date Filing Date Title
US31532094A 1994-09-29 1994-09-29
US48641695A 1995-06-07 1995-06-07
US08/315,320 1995-06-07
US08/486,416 1995-06-07

Publications (1)

Publication Number Publication Date
WO1996009889A1 true WO1996009889A1 (fr) 1996-04-04

Family

ID=26979826

Family Applications (1)

Application Number Title Priority Date Filing Date
PCT/US1995/010613 Ceased WO1996009889A1 (fr) 1994-09-29 1995-08-21 Catalyseurs et additifs contenant un liant des terres rares

Country Status (7)

Country Link
EP (1) EP0783368A1 (fr)
JP (1) JPH10506571A (fr)
KR (1) KR970706063A (fr)
AU (1) AU3332395A (fr)
CA (1) CA2201373A1 (fr)
TW (1) TW321610B (fr)
WO (1) WO1996009889A1 (fr)

Cited By (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO2002083304A3 (fr) * 2001-04-13 2003-06-05 Grace W R & Co Catalyseur a base de zeolite a activite de conversion cinetique ultra-elevee
CN116969479A (zh) * 2023-06-05 2023-10-31 大连理工大学 一种低温活化高岭土的制备方法及应用

Citations (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
FR2448384A1 (fr) * 1979-02-07 1980-09-05 Ammonia Casale Sa Procede de fabrication d'un catalyseur active par cerium pour la synthese d'ammoniac
EP0256875A2 (fr) * 1986-08-15 1988-02-24 Mobil Oil Corporation Catalyseur de craquage, sa préparation et son application
US5248642A (en) * 1992-05-01 1993-09-28 W. R. Grace & Co.-Conn. Catalytic cracking catalysts and additives

Patent Citations (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
FR2448384A1 (fr) * 1979-02-07 1980-09-05 Ammonia Casale Sa Procede de fabrication d'un catalyseur active par cerium pour la synthese d'ammoniac
EP0256875A2 (fr) * 1986-08-15 1988-02-24 Mobil Oil Corporation Catalyseur de craquage, sa préparation et son application
US5248642A (en) * 1992-05-01 1993-09-28 W. R. Grace & Co.-Conn. Catalytic cracking catalysts and additives

Cited By (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO2002083304A3 (fr) * 2001-04-13 2003-06-05 Grace W R & Co Catalyseur a base de zeolite a activite de conversion cinetique ultra-elevee
US6884744B2 (en) 2001-04-13 2005-04-26 W. R. Grace & Co.-Conn. Zeolite based catalyst of ultra-high kinetic conversion activity
KR100893954B1 (ko) * 2001-04-13 2009-04-20 더블유.알. 그레이스 앤드 캄파니-콘. 극도로 높은 동역학적 전환 활성의 제올라이트계 촉매
CN116969479A (zh) * 2023-06-05 2023-10-31 大连理工大学 一种低温活化高岭土的制备方法及应用

Also Published As

Publication number Publication date
KR970706063A (ko) 1997-11-03
CA2201373A1 (fr) 1996-04-04
AU3332395A (en) 1996-04-19
TW321610B (fr) 1997-12-01
JPH10506571A (ja) 1998-06-30
EP0783368A1 (fr) 1997-07-16

Similar Documents

Publication Publication Date Title
AU721054B2 (en) La/Nd-spinel compositions for metals passivation in FCC processes
US6673235B2 (en) FCC catalysts for feeds containing nickel and vanadium
US6916757B2 (en) High zeolite content and attrition resistant catalyst, methods for preparing the same and catalyzed processes therewith
JP2609502B2 (ja) ＦＣＣ用の金属不動態化／ＳＯｘ制御組成物
US20030089640A1 (en) FCC catalysts for feeds containing nickel and vanadium
US5304299A (en) Catalytic cracking catalysts and additives
US12599898B2 (en) Fluid catalytic cracking catalyst composition for enhanced butylenes yields with metal passivation functionality
US6613710B2 (en) Process for preparation of bi-functional fluid catalytic cracking catalyst composition
US5248642A (en) Catalytic cracking catalysts and additives
EP0497037A1 (fr) Catalyseurs en coque pour le FCC
US11207661B2 (en) Process to peptize alumina for fluidizable catalysts
JPH11564A5 (fr)
AU2002258677B2 (en) Bayerite alumina coated zeolite and cracking catalysts containing same
AU2002258677A1 (en) Bayerite alumina coated zeolite and cracking catalysts containing same
US5364516A (en) Catalytic cracking catalysts and additives
US20110017640A1 (en) Rare earth carbonate compositions for metals tolerance in cracking catalysts
EP0568170B1 (fr) Catalyseurs et additifs de craquage catalytique
EP0783368A1 (fr) Catalyseurs et additifs contenant un liant des terres rares
WO2008005155A2 (fr) Catalyseurs liés par du sulfate d'aluminium
JP4167123B2 (ja) 炭化水素流動接触分解用触媒組成物およびそれを用いた重質炭化水素の流動接触分解法
JPH0273886A (ja) ゼオライトｌ及びゼオライトｙの混合物を用いる炭化水素の接触分解
AU669543B2 (en) Catalytic cracking catalysts and additives

Legal Events

Date Code Title Description
AK Designated states

Kind code of ref document: A1

Designated state(s): AU CA CN JP KR MX SG

AL Designated countries for regional patents

Kind code of ref document: A1

Designated state(s): AT BE CH DE DK ES FR GB GR IE IT LU MC NL PT SE

DFPE Request for preliminary examination filed prior to expiration of 19th month from priority date (pct application filed before 20040101)
121 Ep: the epo has been informed by wipo that ep was designated in this application
ENP Entry into the national phase

Ref document number: 2201373

Country of ref document: CA

Ref country code: CA

Ref document number: 2201373

Kind code of ref document: A

Format of ref document f/p: F

WWE Wipo information: entry into national phase

Ref document number: 1019970702056

Country of ref document: KR

WWE Wipo information: entry into national phase

Ref document number: 1995929629

Country of ref document: EP

WWP Wipo information: published in national office

Ref document number: 1995929629

Country of ref document: EP

WWP Wipo information: published in national office

Ref document number: 1019970702056

Country of ref document: KR

WWR Wipo information: refused in national office

Ref document number: 1995929629

Country of ref document: EP

WWW Wipo information: withdrawn in national office

Ref document number: 1995929629

Country of ref document: EP

WWW Wipo information: withdrawn in national office

Ref document number: 1019970702056

Country of ref document: KR