WO2007006047A2 - Process for the preparation of catalyst compositions comprising zeolite and non-zeolitic component - Google Patents

Process for the preparation of catalyst compositions comprising zeolite and non-zeolitic component Download PDF

Info

Publication number
WO2007006047A2
WO2007006047A2 PCT/US2006/026500 US2006026500W WO2007006047A2 WO 2007006047 A2 WO2007006047 A2 WO 2007006047A2 US 2006026500 W US2006026500 W US 2006026500W WO 2007006047 A2 WO2007006047 A2 WO 2007006047A2
Authority
WO
WIPO (PCT)
Prior art keywords
zeolite
zeolitic component
boehmite
aluminium
zeolitic
Prior art date
Application number
PCT/US2006/026500
Other languages
French (fr)
Other versions
WO2007006047A3 (en
Inventor
Dennis Stamires
Paul O'connor
Erik Jeroen Laheij
Original Assignee
Albemarle Netherlands Bv
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 Albemarle Netherlands Bv filed Critical Albemarle Netherlands Bv
Priority to JP2008519746A priority Critical patent/JP2008544853A/en
Priority to CA002613490A priority patent/CA2613490A1/en
Priority to EP06786595A priority patent/EP1899057A2/en
Publication of WO2007006047A2 publication Critical patent/WO2007006047A2/en
Publication of WO2007006047A3 publication Critical patent/WO2007006047A3/en

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
    • 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
    • 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
    • B01J29/08—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
    • B01J29/40—Crystalline aluminosilicate zeolites; Isomorphous compounds thereof of the pentasil type, e.g. types ZSM-5, ZSM-8 or ZSM-11, as exemplified by patent documents US3702886, GB1334243 and US3709979, respectively
    • B01J29/42—Crystalline aluminosilicate zeolites; Isomorphous compounds thereof of the pentasil type, e.g. types ZSM-5, ZSM-8 or ZSM-11, as exemplified by patent documents US3702886, GB1334243 and US3709979, respectively containing iron group metals, noble metals or copper
    • B01J29/46—Iron group metals or copper
    • 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
    • B01J29/80—Mixtures of different zeolites
    • 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
    • C—CHEMISTRY; METALLURGY
    • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10G—CRACKING HYDROCARBON OILS; PRODUCTION OF LIQUID HYDROCARBON MIXTURES, e.g. BY DESTRUCTIVE HYDROGENATION, OLIGOMERISATION, POLYMERISATION; RECOVERY OF HYDROCARBON OILS FROM OIL-SHALE, OIL-SAND, OR GASES; REFINING MIXTURES MAINLY CONSISTING OF HYDROCARBONS; REFORMING OF NAPHTHA; MINERAL WAXES
    • C10G49/00—Treatment of hydrocarbon oils, in the presence of hydrogen or hydrogen-generating compounds, not provided for in a single one of groups C10G45/02, C10G45/32, C10G45/44, C10G45/58 or C10G47/00
    • C10G49/02—Treatment of hydrocarbon oils, in the presence of hydrogen or hydrogen-generating compounds, not provided for in a single one of groups C10G45/02, C10G45/32, C10G45/44, C10G45/58 or C10G47/00 characterised by the catalyst used
    • C10G49/08—Treatment of hydrocarbon oils, in the presence of hydrogen or hydrogen-generating compounds, not provided for in a single one of groups C10G45/02, C10G45/32, C10G45/44, C10G45/58 or C10G47/00 characterised by the catalyst used containing crystalline alumino-silicates, e.g. molecular sieves
    • 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
    • B01J21/00—Catalysts comprising the elements, oxides, or hydroxides of magnesium, boron, aluminium, carbon, silicon, titanium, zirconium, or hafnium
    • B01J21/16—Clays or other mineral silicates
    • 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
    • B01J2229/10—After treatment, characterised by the effect to be obtained
    • B01J2229/20—After treatment, characterised by the effect to be obtained to introduce other elements in the catalyst composition comprising the molecular sieve, but not specially in or on the molecular sieve itself
    • 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
    • B01J23/00—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00
    • B01J23/007—Mixed salts
    • 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
    • B01J29/40—Crystalline aluminosilicate zeolites; Isomorphous compounds thereof of the pentasil type, e.g. types ZSM-5, ZSM-8 or ZSM-11, as exemplified by patent documents US3702886, GB1334243 and US3709979, respectively

Definitions

  • the present invention relates to a process for the preparation of shaped catalyst compositions comprising a zeolite and a non-zeolitic component.
  • WO 01/12570 discloses the preparation of shaped bodies comprising zeolite and non-zeolitic compounds (boehmite and anionic clay) by a) preparing a precursor mixture comprising an aluminium compound, a magnesium source, and zeolite, b) shaping the precursor mixture to obtain shaped bodies, and c) aging to obtain shaped bodies containing anionic clay, zeolite, and boehmite, the boehmite being formed from an excess of aluminium compound during the aging step.
  • the advantage of having zeolite present during the formation of the non-zeolitic component is that the zeolite and the non-zeolitic component are more homogeneously dispersed within the resulting shaped body than when using the generally known method referred to above.
  • the non-zeolitic reaction to obtain the non-zeolitic compound generally occurs via the water phase.
  • the shaped bodies will contain individual precursor particles at fixed positions in the body and interaction of these particles with water is therefore limited. Further, the fixation of the precursor particles in a shaped body will also limit their contact with other precursor particles, which has a negative effect on the formation of non-zeolitic components from two different precursors.
  • shaped bodies comprising homogeneously dispersed zeolite and non-zeolitic component can be prepared wherein the yield of non- zeolitic component is significantly higher.
  • the process according to the present invention comprises the steps of a) aging a precursor mixture comprising zeolite and one or more precursors of the non-zeolitic component to obtain a composition comprising zeolite and non- zeolitic component, and b) shaping the composition comprising zeolite and non-zeolitic component to form shaped bodies.
  • the final product is a shaped body comprising zeolite and non-zeolitic component.
  • the zeolite acts as a spacer embedded within the non-zeolitic component, thereby creating porosity and accessibility in the shaped body.
  • the zeolite is surrounded by and in close contact with the non-zeolitic component. In other words, the zeolite is coated with the non-zeolitic component.
  • Preferred zeolites to be used in the process according to the present invention are pentasil zeolites (e.g.ZSM-5, zeolite beta), faujasite zeolites (e.g. zeolite X and Y), zeolite A, mordenite, chabazite, chinoptalozite, erionite, MCM-type materials (e.g. MCM-41), VIP-5, ITQ-21 , SAPOs, ALPOs, and/or aluminasilicates according to pre-published US patent application No. US/0048737 A1.
  • the zeolites may be ultrastabilized (e.g. USY), flash-calcined, treated with organo-silicate, organo-borate, or organo-titanate, and/or optionally exchanged with alkaline earth metals, transition metals, and/or rare-earth metals.
  • both a faujasite zeolite and a pentasil zeolite are used.
  • the process according to the invention allows both zeolites to be in intimate contact with the non-zeolitic component (i.e. the matrix), resulting in enhanced production of light olefins when the shaped bodies are used as FCC catalyst or additive.
  • the process according to the invention allows the faujasite zeolite and the active matrix (the primary cracking ingredient) to be in intimate contact (e.g. in NNN arrangement) or, even better, to be attached to the pentasil-type zeolite (the secondary cracking ingredient).
  • Such a structural arrangement of primary and secondary ingredients results in enhancement of the light olefins' yields in the FCC process.
  • non-zeolitic component is used for compounds which the person skilled in the art of catalysis does not regard as having a zeolitic structure.
  • non-zeolitic components include boehmite, anionic clays (e.g. hydrotalcites), cationic clays (e.g. smectites), and aluminium phosphate gels.
  • a preferred non-zeolitic compound is boehmite.
  • boehmite refers to alumina hydrates which exhibit X-ray diffraction (XRD) patterns close to that of aluminum oxide-hydroxide [AIO(OH)] (naturally occurring boehmite or diaspore), although they may contain different amounts of water of hydration and have different surface areas, pore volumes, and specific densities, and different thermal characteristics upon thermal treatment.
  • XRD patterns of different types of boehmite exhibit the characteristic boehmite [AIO(OH)] peaks, although the sharpness and the precise location of these peaks depend on the degree of crystallinity, the crystal size, and the amount of imperfections.
  • boehmite aluminas there are two categories of boehmite aluminas: quasi-crystalline boehmites (also called pseudo-boehmites or gelatinous boehmites) and micro- crystalline boehmites.
  • Quasi-crystalline boehmites usually have higher surface areas, larger pores and pore volumes, and lower specific densities than micro- crystalline boehmites. They disperse easily in water or acids, have a smaller crystal size, and contain a larger number of water molecules of hydration. As a result of their smaller crystal sizes and their higher crystal imperfection, quasi-crystalline boehmites show broader XRD peaks than micro-crystalline boehmites.
  • quasi-crystalline boehmites for the purpose of this specification we define quasi-crystalline boehmites as having (020) peak widths at half-length of the maximum intensity of 1.5° or greater than 1.5° 2-theta. Boehmites having a (020) peak width at half-length of the maximum intensity smaller than 1.5° 2-theta are considered micro-crystalline boehmites. For copper radiation, the (020) reflection appears at about 14° 2-theta.
  • Some typical, commercially available quasi-crystalline boehmites are Condea Pural®, Catapal®, and Versal® products.
  • a typical commercially available micro- crystalline boehmite is Condea's P-200®.
  • the crystallinity of the boehmite obtained in the product resulting from the process of the invention depends on the pH and the temperature of the precursor mixture during aging. With a higher temperature and pH, the crystallinity of the resulting boehmite increases.
  • Suitable boehmite precursors to be added to the precursor mixture of step a) of the process according to the invention are the aluminium compounds listed below. It is also possible to use two or more of these aluminium compounds as boehmite precursors.
  • anionic clays have a crystal structure consisting of positively charged layers built up of specific combinations of divalent and trivalent metal hydroxides between which there are anions and water molecules.
  • Hydrotalcite is an example of a naturally occurring anionic clay, in which the trivalent metal is aluminium, the divalent metal is magnesium, and the predominant anion is carbonate; meixnerite is an anionic clay wherein the trivalent metal is aluminium, the divalent metal is magnesium, and the predominant anion is hydroxyl.
  • Synonyms of the term "anionic clay” are hydrotalcite-like material and layered double hydroxide.
  • Cationic clays are layered structures with cations between the layers.
  • the layers of cationic clays are built up of trivalent and tetravalent metals and, optionally, divalent metals.
  • a preferred class of cationic clays are smectite-type materials. Smectite-type materials comprise divalent, trivalent, and tetravalent metals in the layers, e.g. Mg, Al 1 and Si.
  • a divalent and a trivalent metal compound in order to obtain anionic clay as the non-zeolitic component, at least two precursors of the non-zeolitic component are required: a divalent and a trivalent metal compound.
  • the formation of a cationic clay as the non-zeoltic component requires at least a trivalent and a tetravalent and, optionally, a divalent metal compound as precursors.
  • Suitable divalent metal compounds include compounds of magnesium, zinc, nickel, copper, iron, cobalt, manganese, calcium, barium, and combinations thereof.
  • Suitable zinc, nickel, copper, iron, cobalt, manganese, calcium, and barium compounds are the respective oxides, hydroxides, carbonates, acetates, formates, nitrates, and chlorides.
  • Suitable magnesium compounds include magnesium oxides or hydroxides such as MgO, Mg(OH) 2 , hydromagnesite, magnesium salts such as magnesium acetate, magnesium formate, magnesium hydroxy acetate, magnesium carbonate, magnesium hydroxy carbonate, magnesium bicarbonate, magnesium nitrate, and magnesium chloride, and magnesium-containing clays such as dolomite, saponite, and sepiolite.
  • Preferred divalent metal compounds are oxides and hydroxides, as these materials are relatively inexpensive. Moreover, these materials do not leave anions in the product which either have to be washed out or will be emitted as environmentally harmful gases upon heating.
  • Suitable tetravalent metal compounds include silicon compounds, such as sodium (meta)silicate or water glass, stabilized silica sols, silica gels, polysilicic acid, tetra ethylortho silicate, fumed silicas, precipitated silicas, and mixtures thereof.
  • Suitable trivalent metal compounds include compounds of aluminium, gallium, indium, iron, chromium, vanadium, cobalt, manganese, cerium, niobium, lanthanum, and mixtures thereof.
  • Suitable gallium, indium, iron, chromium, vanadium, cobalt, cerium, niobium, lanthanum, and manganese compounds are the respective oxides, hydroxides, carbonates, nitrates, chlorides, chlorohydrates, and alkoxides.
  • Preferred trivalent metal compounds are oxides and hydroxides, as these materials are relatively inexpensive. Moreover, these materials do not leave anions in the product which either have to be washed out or will be emitted as environmentally harmful gases upon heating.
  • Suitable aluminium compounds include aluminium alkoxide, aluminium hydroxides prepared by precipitation of soluble aluminium salts such as aluminium sulphate, aluminium nitrate, aluminium chloride, and sodium aluminate, (pseudo)boehmite, thermally treated aluminium trihydrate such as flash calcined aluminium trihydrate (Alcoa Cp® alumina), amorphous gel alumina, aluminium trihydrate such as gibbsite, BOC, and bayerite, and mixtures thereof.
  • Preferred aluminium compounds are (thermally treated) aluminium trihydrate and amorphous gel alumina, as these materials are relatively inexpensive. Moreover, these materials do not leave anions in the product which either have to be washed out or will be emitted as environmentally harmful gases upon heating. Some of these aluminium compounds can act as a seed for the formation of boehmite. Especially when aluminium trihydrate is used as boehmite-precursor, seeds are desired.
  • Suitable seeds are the known seeds to make boehmite such as commercially available boehmite (Catapal®, Condea Versal®, P-200® etc.), amorphous seeds, milled boehmite seeds, boehmite prepared from sodium aluminate solutions, and thermally treated aluminium trihydrate seeds, e.g. FC- ATH seeds.
  • boehmite such as commercially available boehmite (Catapal®, Condea Versal®, P-200® etc.), amorphous seeds, milled boehmite seeds, boehmite prepared from sodium aluminate solutions, and thermally treated aluminium trihydrate seeds, e.g. FC- ATH seeds.
  • the precursor mixture contains two or more precursors of the non-zeolitic component, it is possible to obtain more than one non-zeolitic component.
  • the precursors of the non-zeolitic component are an aluminium compound and a divalent metal compound, either anionic clay is the sole non- zeolitic compound formed, or a mixture of boehmite and anionic clay is formed; the outcome will depend on the aluminium-to-divalent metal ratio and the process conditions.
  • the precursor mixture may contain additional components, metal additives, phosphorus-containing compounds, boron-containing compounds, kaolin, acids, bases, etc.
  • Suitable metal additives are compounds comprising rare earth metals (e.g. Ce, La), Group Vl metals, Group VIII metals (Pd, Pt), alkaline earth metals (for instance Ca, Mg, and Ba), and/or transition metals (for example Rh, Nb, Co, Mn, Fe, Ti, Cr, Zr, Cu, Ni, Zn, Mo, W, V, Sn).
  • rare earth metals e.g. Ce, La
  • Group Vl metals Group VIII metals (Pd, Pt)
  • alkaline earth metals for instance Ca, Mg, and Ba
  • transition metals for example Rh, Nb, Co, Mn, Fe, Ti, Cr, Zr, Cu, Ni, Zn, Mo, W, V, Sn.
  • Examples of phosphorus-containing compounds are phosphoric acid, ammonium phosphates, and sodium phosphates. Together with aluminium-containing compounds, aluminium phosphates can be formed. With the above metal additives, this can lead to the formation of doped aluminium phosphates such as La-doped aluminium phosphate, Ce-doped aluminium phosphate, Zn-doped aluminium phosphate, or Mg-doped aluminium phosphate. These additives can be added to the precursor mixture separately, or they can be added by way of the precursors of the non-zeolitic compound doped with one or more of these additives.
  • the precursor mixture is aged.
  • aging refers to treatment of the suspension at thermal or hydrothermal conditions for about 30 minutes to about 72 hours.
  • hydrothermal means in the presence of water (or steam) at temperatures above about 100 0 C and pressures above atmospheric, e.g. autogenous pressure.
  • Thermal means at temperatures between about 15°C and 100 0 C and atmospheric pressure.
  • the preferred aging temperature ranges from 25°C to 375°C, preferably from 50 0 C to 200 0 C, and most preferably from 100 0 C to 175°C.
  • the aging time preferably is at least about 30 minutes, more preferably at least about 45 minutes, and even more preferably at least about 1 hour; the aging time preferably is not more than about 72 hours, more preferably not more than about 24 hours, and even more preferably not more than about 6 hours.
  • milling is defined as any method that results in reduction of the particle size. Such a particle size reduction can at the same time result in the formation of reactive surfaces and/or heating of the particles.
  • Instruments that can be used for milling include ball mills, high-shear mixers, colloid mixers, and electrical transducers that can introduce ultrasound waves into a slurry.
  • Low-shear mixing i.e. stirring that is performed essentially to keep the ingredients in suspension, is not regarded as
  • the process is preferably conducted in a continuous fashion. More preferably, this is done in an apparatus comprising two or more conversion vessels, like the apparatus according to non-prepublished patent application No. PCT/EP 02/04938.
  • zeolite and an aluminium compound are mixed with water in a feed preparation vessel, after which the mixture is continuously pumped through two or more conversion vessels, in which aging takes place.
  • Additional components can be added to the precursor mixture before or during aging, i.e. in the preparation vessel or in one of the conversion vessels.
  • zeolite and aluminium compound are aged in a first conversion vessel to form a composition comprising zeolite and boehmite, while in the second conversion vessel a magnesium compound is added and the mixture is aged to form a composition comprising zeolite, and boehmite and Mg-Al anionic clay as the non-zeolitic components.
  • Another example concerns the variation of the micro-crystalline boehmite to quasi- crystalline boehmite ratio in the resulting product.
  • the precursor mixture comprising aluminium compound and zeolite is added to the first preparation vessel.
  • the pH and the temperature are such that mainly micro- crystalline boehmite is formed.
  • an additional amount of aluminium compound is added to the second conversion vessel, in which the pH and the temperature are more favourable for quasi-crystalline boehmite formation.
  • This additional amount of aluminium compound will be converted to quasi-crystalline boehmite, resulting in a composition comprising zeolite, quasi-crystalline boehmite, and micro-crystalline boehmite.
  • compositions can be prepared, containing, e.g., different types of boehmite, anionic clay, and/or smectite.
  • the mixture comprising zeolite and non-zeolitic component is shaped to form shaped bodies, optionally with the help of binders and/or fillers.
  • Suitable shaping methods include spray-drying, pelletizing, granulation, extrusion (optionally combined with kneading), beading, or any other conventional shaping method used in the catalyst and absorbent fields or combinations thereof.
  • the amount of liquid present in the mixture to be shaped should be adapted to the specific shaping step to be conducted. It might be advisable to partially remove the liquid present in the mixture and/or to add an additional or another liquid, and/or to change the pH of the mixture to make the mixture gellable and thus suitable for shaping.
  • Additives commonly used in the different shaping methods e.g. extrusion additives, may be added to the mixture.
  • a magnesium compound can be added before or during this rehydration step, which may result in the formation of a composition comprising zeolite, boehmite, and Mg- Al anionic clay
  • the final product can be combined with other catalyst ingredients, such as binders, fillers (e.g. clay such as kaolin, titanium oxide, zirconia, silica, silica-alumina, bentonite, etcetera), zeolites other than those already present in the composition, etc. It is also possible to add additional metal additives - e.g. rare earth metals, transition metals, and/or noble metals - to the shaped body by impregnation or ion- exchange.
  • binders e.g. clay such as kaolin, titanium oxide, zirconia, silica, silica-alumina, bentonite, etcetera
  • zeolites other than those already present in the composition, etc.
  • additional metal additives e.g. rare earth metals, transition metals, and/or noble metals - to the shaped body by impregnation or ion- exchange.
  • the resulting catalyst composition can suitably be used in FCC processes, in hydroprocessing, Fischer Tropsch synthesis, alkylation processes, hydrocracking, alkylation, isomerization, etc.
  • An aqueous slurry containing 25 wt% solids is prepared by high-shear mixing of gibbsite, MgO (Mg/AI mole ratio 0.5), and RE-Y.
  • the amount of RE-Y is about 10 wt% (based on total solids content) of RE-Y. After mixing, the average particle size is about 3 microns.
  • One portion of this slurry is aged at 185°C for 2 hours.
  • the aged portion is spray- dried.
  • X-ray diffraction shows that the composition aged at 185°C contained Mg-Al anionic clay, RE-Y, and micro-crystalline boehmite.
  • Example 1 is followed, except that instead of gibbsite, flash-calcined gibbsite is used.
  • composition prepared by aging at 85°C contains Mg-Al anionic clay, RE-Y, and quasi-crystalline boehmite, whereas the composition aged at 185°C contains Mg-Al anionic clay, RE-Y, and micro-crystalline boehmite.
  • Example 2 is followed, except that 4 wt% Zn(NO 3 ) 2 (based on total solids content) is added to the slurry.
  • composition prepared by aging at 85°C contains Zn-doped Mg-Al anionic clay, RE-Y, and Zn-doped quasi-crystalline boehmite, whereas the composition aged at 185 0 C contains Zn-doped Mg-Al anionic clay, RE-Y, and Zn-doped micro- crystalline boehmite.
  • Example 4
  • Example 3 is followed, except that instead of Zn(NO 3 ) 2) 6 wt% of La(NO 3 ) 3 (based on total solids content) is added to the slurry.
  • composition prepared by aging at 85°C contains La-doped anionic clay, RE-Y, La-doped quasi-crystalline boehmite, whereas the composition aged at 185°C contains La-doped anionic clay, RE-Y, and La-doped micro-crystalline boehmite.
  • Example 5 Example 1 is followed, except that instead of gibbsite a 50/50 mixture of gibbsite and flash-calcined gibbsite is used, the Mg/AI mole ratio was 0.25, and 5 wt% Ce(NOs) 3 (based on total solids content) is added to the slurry.
  • gibbsite a 50/50 mixture of gibbsite and flash-calcined gibbsite is used, the Mg/AI mole ratio was 0.25, and 5 wt% Ce(NOs) 3 (based on total solids content) is added to the slurry.
  • composition prepared by aging at 85°C contains Ce-doped anionic clay, RE-Y, and Ce-doped quasi-crystalline boehmite, whereas the composition aged at 185°C contains Ce-doped anionic clay, RE-Y, and Ce-doped micro-crystalline boehmite.
  • An aqueous slurry containing 25 wt% solids is prepared by high-shear mixing of flash-calcined gibbsite, MgO (Mg/AI mole ratio 0.25), 8 wt% RE-Y, 6 wt% Ce(NO 3 ) 3 , and 15 wt% kaolin (all based on total solids content).
  • This slurry is aged at 85°C for 18 hours; another portion is aged at 185°C for 2 hours. The aged portions are spray-dried.
  • X-ray diffraction shows that the composition prepared by aging at 85°C contains anionic clay, kaolin, RE-Y, and Ce-doped quasi-crystalline boehmite, whereas the composition aged at 185°C contains hydrotalcite, kaolin, RE-Y, and Ce-doped micro-crystalline boehmite.
  • the compositions are tested for cracking activity, sulphur reduction in gasoline and diesel, and SO X /NO X removal of FCC regenerator exhaust gases.
  • Example 6 is followed, except that the spray-dried product is calcined at 550 0 C for 4 hours, followed by rehydration in an aqueous solution containing 4 wt% of ammonium vanadate. The resulting product is filtered and dried.
  • a slurry is prepared by high-shear mixing of flash-calcined gibbsite, MgO (Mg/AI mole ratio 0.25), 15 wt% of iron-exchanged ZSM-5, and 4 wt% vanadyl sulphate.
  • This slurry is aged at 85°C for 18 hours; another portion is aged at 185°C for 2 hours. The aged portions are spray-dried. The total amount of gibbsite and MgO was such that the final dried product contains about 90 wt% gibbsite and MgO.
  • Example 9 An aqueous slurry with 28 wt% solids is prepared by mixing finely ground gibbsite, MgO (Mg/AI mole ratio 2.3), 8 wt% RE-USY. The slurry is homogenized in a colloid mill.
  • This slurry is aged at 85°C for 18 hours; another portion is aged at 185°C for 2 hours. The aged portions are spray-dried.
  • An aqueous slurry comprising 70 wt% of flash-calcined gibbsite (Alcoa CP-3®) and about 30 wt% RE-USY (wt% based on total solids content) is prepared.
  • the slurry is homogenized by high-shear mixing.
  • the pH of the slurry is adjusted to about 5.
  • the slurry is aged at 165°C for one hour.
  • XRD indicates the formation of a composition comprising quasi-crystalline boehmite and RE-USY.
  • the composition is flash-calcined, slurried in water, and spray-dried to form microspheres.
  • the microspheres are slurried in a suspension comprising MgO (Mg/AI ratio in suspension was 1) and aged at 85°C for 18 hours. During aging, the pH is adjusted to 9.5 using ammonium hydroxide.
  • the resulting product contains RE-USY, quasi-crystalline boehmite, and Mg-Al anionic clay.
  • Example 10 is followed, except that the spray-drying step is performed not before but after aging at 85°C.
  • the resulting product contains RE-USY, quasi-crystalline boehmite, and Mg-Al anionic clay.
  • Example 10 is followed, except that after aging at 165°C MgO is added to the slurry.
  • the resulting Mg/AI ratio is 1 ; the pH is adjusted to about 9.
  • the resulting slurry is aged at 165°C for another hour, followed by flash- calcination, re-slurrying in water, and spray-drying.
  • the resulting product contained RE-USY, quasi-crystalline boehmite, and Mg-Al anionic clay.
  • An aqueous slurry is prepared comprising 60 wt% fine-particle gibbsite and about 40 wt% RE-Y (wt% based on total solids content).
  • the slurry is milled in a colloid mill and flash-calcined.
  • the flash-calcined product is re-slurried in water, with the pH set at about 5 using formic acid, and rehydrated at 165°C for one hour, and the slurry contains 25 wt% solids.
  • MgO is added to the slurry (Mg/AI was about 1), the pH is adjusted to 9.5, and the slurry is aged at 85°C for 18 hours. The final mixture is spray-dried.
  • XRD indicates the formation of a composition comprising RE-Y, anionic clay, and boehmite.
  • Example 14 An aqueous slurry is prepared comprising 60 wt% fine-particle gibbsite and about 40 wt% RE-Y (wt% based on total solids content). The slurry is milled in a colloid mil! and flash-calcined. The flash-calcined product is re-slurried in water, with the pH set at about 5 using nitric acid, and rehydrated at 165°C for one hour.
  • the product comprises RE-Y, boehmite, and silica.
  • An aqueous slurry containing 70 wt% USY zeolite and 30 wt% ZSM-5 (all based on total solids content) is high-shear mixed and flash-calcined. After flash-calcination the product is re-slurried and high-shear mixed in a suspension comprising 35 wt% of flash-calcined gibbsite and 10 wt% of nickel nitrate.
  • An aqueous slurry containing 70 wt% USY zeolite and 30 wt% ZSM-5 (all based on total solids content) is high-shear mixed and finally flash-calcined.
  • the product is re-slurried and high-shear mixed in a suspension comprising flash-calcined gibbsite, MgO (Mg/AI molar ratio 0.5), and 10 wt% of nickel nitrate.
  • the total amount of MgO and flash-calcined gibbsite is about 40 wt% of the amount of the two zeolites.
  • the resulting mixture is aged at 165°C for one hour at a pH of 9.5.
  • the slurry is dewatered and extruded to form pellets.
  • the pellets are finally calcined and impregnated with 6 wt% of cobalt nitrate.
  • Example 17 A slurry comprising thermally stabilized REY, ground gibbsite, and magnesium oxide is prepared. This slurry has a solids content of 28 wt% and a Mg/AI molar ratio of 2.3. The slurry is milled in a colloid mill.
  • the slurry is aged at 85°C for 18 hours. Next the aged slurry is spray-dried to form microspheres. The microspheres are calcined and subsequently rehydratated in an aqueous slurry at 85°C for 8 hours.
  • the resulting composition comprises zeolite REY and Mg-Al anionic clay as the non-zeolitic compound.

Abstract

Process for the preparation of shaped catalyst compositions comprising zeolite and a non-zeolitic component comprising the steps of (a) aging a precursor mixture comprising zeolite and one or more precursor(s) of the non-zeolitic component to obtain a composition comprising zeolite and non-zeolitic component, and (b) shaping the composition comprising zeolite and non-zeolitic component to form shaped bodies. This process enables the production of shaped bodies comprising homogeneously dispersed zeolite and non-zeolitic component.

Description

PROCESS FOR THE PREPARATION OF CATALYST COMPOSITIONS COMPRISING ZEOLITE AND A NON-ZEOLITIC COMPONENT
The present invention relates to a process for the preparation of shaped catalyst compositions comprising a zeolite and a non-zeolitic component.
It is generally known to prepare such compositions by mixing zeolite and a non- zeolitic component, followed by shaping this mixture to form particles.
WO 01/12570, on the other hand, discloses the preparation of shaped bodies comprising zeolite and non-zeolitic compounds (boehmite and anionic clay) by a) preparing a precursor mixture comprising an aluminium compound, a magnesium source, and zeolite, b) shaping the precursor mixture to obtain shaped bodies, and c) aging to obtain shaped bodies containing anionic clay, zeolite, and boehmite, the boehmite being formed from an excess of aluminium compound during the aging step.
The advantage of having zeolite present during the formation of the non-zeolitic component is that the zeolite and the non-zeolitic component are more homogeneously dispersed within the resulting shaped body than when using the generally known method referred to above.
However, shaping the precursor mixture before aging, i.e. before the formation of the final amount of non-zeolitic component, generally results in relatively low yields of the non-zeolitic compound. One reason for this low yield is the fact that the
(crystallization) reaction to obtain the non-zeolitic compound generally occurs via the water phase. After shaping, the shaped bodies will contain individual precursor particles at fixed positions in the body and interaction of these particles with water is therefore limited. Further, the fixation of the precursor particles in a shaped body will also limit their contact with other precursor particles, which has a negative effect on the formation of non-zeolitic components from two different precursors.
It has now been found that shaped bodies comprising homogeneously dispersed zeolite and non-zeolitic component can be prepared wherein the yield of non- zeolitic component is significantly higher.
The process according to the present invention comprises the steps of a) aging a precursor mixture comprising zeolite and one or more precursors of the non-zeolitic component to obtain a composition comprising zeolite and non- zeolitic component, and b) shaping the composition comprising zeolite and non-zeolitic component to form shaped bodies.
The final product is a shaped body comprising zeolite and non-zeolitic component. The zeolite acts as a spacer embedded within the non-zeolitic component, thereby creating porosity and accessibility in the shaped body. The zeolite is surrounded by and in close contact with the non-zeolitic component. In other words, the zeolite is coated with the non-zeolitic component.
Preferred zeolites to be used in the process according to the present invention are pentasil zeolites (e.g.ZSM-5, zeolite beta), faujasite zeolites (e.g. zeolite X and Y), zeolite A, mordenite, chabazite, chinoptalozite, erionite, MCM-type materials (e.g. MCM-41), VIP-5, ITQ-21 , SAPOs, ALPOs, and/or aluminasilicates according to pre-published US patent application No. US/0048737 A1. If desired, the zeolites may be ultrastabilized (e.g. USY), flash-calcined, treated with organo-silicate, organo-borate, or organo-titanate, and/or optionally exchanged with alkaline earth metals, transition metals, and/or rare-earth metals.
In a preferred embodiment, both a faujasite zeolite and a pentasil zeolite are used. The process according to the invention allows both zeolites to be in intimate contact with the non-zeolitic component (i.e. the matrix), resulting in enhanced production of light olefins when the shaped bodies are used as FCC catalyst or additive. The process according to the invention allows the faujasite zeolite and the active matrix (the primary cracking ingredient) to be in intimate contact (e.g. in NNN arrangement) or, even better, to be attached to the pentasil-type zeolite (the secondary cracking ingredient). Such a structural arrangement of primary and secondary ingredients results in enhancement of the light olefins' yields in the FCC process.
Within this specification, the term "non-zeolitic component" is used for compounds which the person skilled in the art of catalysis does not regard as having a zeolitic structure. Examples of such non-zeolitic components include boehmite, anionic clays (e.g. hydrotalcites), cationic clays (e.g. smectites), and aluminium phosphate gels.
A preferred non-zeolitic compound is boehmite. The term "boehmite" refers to alumina hydrates which exhibit X-ray diffraction (XRD) patterns close to that of aluminum oxide-hydroxide [AIO(OH)] (naturally occurring boehmite or diaspore), although they may contain different amounts of water of hydration and have different surface areas, pore volumes, and specific densities, and different thermal characteristics upon thermal treatment. The XRD patterns of different types of boehmite exhibit the characteristic boehmite [AIO(OH)] peaks, although the sharpness and the precise location of these peaks depend on the degree of crystallinity, the crystal size, and the amount of imperfections.
Broadly, there are two categories of boehmite aluminas: quasi-crystalline boehmites (also called pseudo-boehmites or gelatinous boehmites) and micro- crystalline boehmites. Quasi-crystalline boehmites usually have higher surface areas, larger pores and pore volumes, and lower specific densities than micro- crystalline boehmites. They disperse easily in water or acids, have a smaller crystal size, and contain a larger number of water molecules of hydration. As a result of their smaller crystal sizes and their higher crystal imperfection, quasi-crystalline boehmites show broader XRD peaks than micro-crystalline boehmites.
For the purpose of this specification we define quasi-crystalline boehmites as having (020) peak widths at half-length of the maximum intensity of 1.5° or greater than 1.5° 2-theta. Boehmites having a (020) peak width at half-length of the maximum intensity smaller than 1.5° 2-theta are considered micro-crystalline boehmites. For copper radiation, the (020) reflection appears at about 14° 2-theta. Some typical, commercially available quasi-crystalline boehmites are Condea Pural®, Catapal®, and Versal® products. A typical commercially available micro- crystalline boehmite is Condea's P-200®.
The crystallinity of the boehmite obtained in the product resulting from the process of the invention depends on the pH and the temperature of the precursor mixture during aging. With a higher temperature and pH, the crystallinity of the resulting boehmite increases.
Suitable boehmite precursors to be added to the precursor mixture of step a) of the process according to the invention are the aluminium compounds listed below. It is also possible to use two or more of these aluminium compounds as boehmite precursors.
Other types of non-zeolitic components are anionic clays and cationic clays. Anionic clays have a crystal structure consisting of positively charged layers built up of specific combinations of divalent and trivalent metal hydroxides between which there are anions and water molecules. Hydrotalcite is an example of a naturally occurring anionic clay, in which the trivalent metal is aluminium, the divalent metal is magnesium, and the predominant anion is carbonate; meixnerite is an anionic clay wherein the trivalent metal is aluminium, the divalent metal is magnesium, and the predominant anion is hydroxyl. Synonyms of the term "anionic clay" are hydrotalcite-like material and layered double hydroxide.
Cationic clays are layered structures with cations between the layers. The layers of cationic clays are built up of trivalent and tetravalent metals and, optionally, divalent metals. A preferred class of cationic clays are smectite-type materials. Smectite-type materials comprise divalent, trivalent, and tetravalent metals in the layers, e.g. Mg, Al1 and Si.
So, in order to obtain anionic clay as the non-zeolitic component, at least two precursors of the non-zeolitic component are required: a divalent and a trivalent metal compound. The formation of a cationic clay as the non-zeoltic component requires at least a trivalent and a tetravalent and, optionally, a divalent metal compound as precursors.
Suitable divalent metal compounds include compounds of magnesium, zinc, nickel, copper, iron, cobalt, manganese, calcium, barium, and combinations thereof. Suitable zinc, nickel, copper, iron, cobalt, manganese, calcium, and barium compounds are the respective oxides, hydroxides, carbonates, acetates, formates, nitrates, and chlorides.
Suitable magnesium compounds include magnesium oxides or hydroxides such as MgO, Mg(OH)2, hydromagnesite, magnesium salts such as magnesium acetate, magnesium formate, magnesium hydroxy acetate, magnesium carbonate, magnesium hydroxy carbonate, magnesium bicarbonate, magnesium nitrate, and magnesium chloride, and magnesium-containing clays such as dolomite, saponite, and sepiolite.
Preferred divalent metal compounds are oxides and hydroxides, as these materials are relatively inexpensive. Moreover, these materials do not leave anions in the product which either have to be washed out or will be emitted as environmentally harmful gases upon heating.
Suitable tetravalent metal compounds include silicon compounds, such as sodium (meta)silicate or water glass, stabilized silica sols, silica gels, polysilicic acid, tetra ethylortho silicate, fumed silicas, precipitated silicas, and mixtures thereof.
Suitable trivalent metal compounds include compounds of aluminium, gallium, indium, iron, chromium, vanadium, cobalt, manganese, cerium, niobium, lanthanum, and mixtures thereof.
Suitable gallium, indium, iron, chromium, vanadium, cobalt, cerium, niobium, lanthanum, and manganese compounds are the respective oxides, hydroxides, carbonates, nitrates, chlorides, chlorohydrates, and alkoxides.
Preferred trivalent metal compounds are oxides and hydroxides, as these materials are relatively inexpensive. Moreover, these materials do not leave anions in the product which either have to be washed out or will be emitted as environmentally harmful gases upon heating.
Suitable aluminium compounds include aluminium alkoxide, aluminium hydroxides prepared by precipitation of soluble aluminium salts such as aluminium sulphate, aluminium nitrate, aluminium chloride, and sodium aluminate, (pseudo)boehmite, thermally treated aluminium trihydrate such as flash calcined aluminium trihydrate (Alcoa Cp® alumina), amorphous gel alumina, aluminium trihydrate such as gibbsite, BOC, and bayerite, and mixtures thereof.
Preferred aluminium compounds are (thermally treated) aluminium trihydrate and amorphous gel alumina, as these materials are relatively inexpensive. Moreover, these materials do not leave anions in the product which either have to be washed out or will be emitted as environmentally harmful gases upon heating. Some of these aluminium compounds can act as a seed for the formation of boehmite. Especially when aluminium trihydrate is used as boehmite-precursor, seeds are desired. Suitable seeds are the known seeds to make boehmite such as commercially available boehmite (Catapal®, Condea Versal®, P-200® etc.), amorphous seeds, milled boehmite seeds, boehmite prepared from sodium aluminate solutions, and thermally treated aluminium trihydrate seeds, e.g. FC- ATH seeds.
If the precursor mixture contains two or more precursors of the non-zeolitic component, it is possible to obtain more than one non-zeolitic component. For instance, if the precursors of the non-zeolitic component are an aluminium compound and a divalent metal compound, either anionic clay is the sole non- zeolitic compound formed, or a mixture of boehmite and anionic clay is formed; the outcome will depend on the aluminium-to-divalent metal ratio and the process conditions.
The precursor mixture may contain additional components, metal additives, phosphorus-containing compounds, boron-containing compounds, kaolin, acids, bases, etc.
Suitable metal additives are compounds comprising rare earth metals (e.g. Ce, La), Group Vl metals, Group VIII metals (Pd, Pt), alkaline earth metals (for instance Ca, Mg, and Ba), and/or transition metals (for example Rh, Nb, Co, Mn, Fe, Ti, Cr, Zr, Cu, Ni, Zn, Mo, W, V, Sn).
Examples of phosphorus-containing compounds are phosphoric acid, ammonium phosphates, and sodium phosphates. Together with aluminium-containing compounds, aluminium phosphates can be formed. With the above metal additives, this can lead to the formation of doped aluminium phosphates such as La-doped aluminium phosphate, Ce-doped aluminium phosphate, Zn-doped aluminium phosphate, or Mg-doped aluminium phosphate. These additives can be added to the precursor mixture separately, or they can be added by way of the precursors of the non-zeolitic compound doped with one or more of these additives.
The precursor mixture is aged. The term "aging" refers to treatment of the suspension at thermal or hydrothermal conditions for about 30 minutes to about 72 hours. In this context, "hydrothermal" means in the presence of water (or steam) at temperatures above about 1000C and pressures above atmospheric, e.g. autogenous pressure. "Thermal" means at temperatures between about 15°C and 1000C and atmospheric pressure.
The preferred aging temperature ranges from 25°C to 375°C, preferably from 500C to 2000C, and most preferably from 1000C to 175°C. The aging time preferably is at least about 30 minutes, more preferably at least about 45 minutes, and even more preferably at least about 1 hour; the aging time preferably is not more than about 72 hours, more preferably not more than about 24 hours, and even more preferably not more than about 6 hours.
Additionally, it is possible to mill the precursor mixture, or any of its ingredients, before addition to the precursor mixture. In this specification the term "milling" is defined as any method that results in reduction of the particle size. Such a particle size reduction can at the same time result in the formation of reactive surfaces and/or heating of the particles. Instruments that can be used for milling include ball mills, high-shear mixers, colloid mixers, and electrical transducers that can introduce ultrasound waves into a slurry. Low-shear mixing, i.e. stirring that is performed essentially to keep the ingredients in suspension, is not regarded as
"milling".
The process is preferably conducted in a continuous fashion. More preferably, this is done in an apparatus comprising two or more conversion vessels, like the apparatus according to non-prepublished patent application No. PCT/EP 02/04938. For example, zeolite and an aluminium compound are mixed with water in a feed preparation vessel, after which the mixture is continuously pumped through two or more conversion vessels, in which aging takes place.
Additional components can be added to the precursor mixture before or during aging, i.e. in the preparation vessel or in one of the conversion vessels. For example, zeolite and aluminium compound are aged in a first conversion vessel to form a composition comprising zeolite and boehmite, while in the second conversion vessel a magnesium compound is added and the mixture is aged to form a composition comprising zeolite, and boehmite and Mg-Al anionic clay as the non-zeolitic components.
Another example concerns the variation of the micro-crystalline boehmite to quasi- crystalline boehmite ratio in the resulting product. The precursor mixture comprising aluminium compound and zeolite is added to the first preparation vessel. In this vessel, the pH and the temperature are such that mainly micro- crystalline boehmite is formed. To the second conversion vessel, in which the pH and the temperature are more favourable for quasi-crystalline boehmite formation, an additional amount of aluminium compound is added. This additional amount of aluminium compound will be converted to quasi-crystalline boehmite, resulting in a composition comprising zeolite, quasi-crystalline boehmite, and micro-crystalline boehmite.
Using the same principles, several compositions can be prepared, containing, e.g., different types of boehmite, anionic clay, and/or smectite.
The mixture comprising zeolite and non-zeolitic component is shaped to form shaped bodies, optionally with the help of binders and/or fillers. Suitable shaping methods include spray-drying, pelletizing, granulation, extrusion (optionally combined with kneading), beading, or any other conventional shaping method used in the catalyst and absorbent fields or combinations thereof. The amount of liquid present in the mixture to be shaped should be adapted to the specific shaping step to be conducted. It might be advisable to partially remove the liquid present in the mixture and/or to add an additional or another liquid, and/or to change the pH of the mixture to make the mixture gellable and thus suitable for shaping. Additives commonly used in the different shaping methods, e.g. extrusion additives, may be added to the mixture.
Additional process steps can be applied. For instance, it is possible to flash-calcine the mixture containing zeolite and non-zeolitic component before the shaping step is applied. This (flash-)calcined product can then be rehydrated either before or after the shaping step.
During rehydration it is possible to add one or more of the additional components outlined above as suitable to be added to the precursor mixture. For instance, a magnesium compound can be added before or during this rehydration step, which may result in the formation of a composition comprising zeolite, boehmite, and Mg- Al anionic clay
The final product can be combined with other catalyst ingredients, such as binders, fillers (e.g. clay such as kaolin, titanium oxide, zirconia, silica, silica-alumina, bentonite, etcetera), zeolites other than those already present in the composition, etc. It is also possible to add additional metal additives - e.g. rare earth metals, transition metals, and/or noble metals - to the shaped body by impregnation or ion- exchange.
The resulting catalyst composition can suitably be used in FCC processes, in hydroprocessing, Fischer Tropsch synthesis, alkylation processes, hydrocracking, alkylation, isomerization, etc. EXAMPLES
Example 1
An aqueous slurry containing 25 wt% solids is prepared by high-shear mixing of gibbsite, MgO (Mg/AI mole ratio 0.5), and RE-Y. The amount of RE-Y is about 10 wt% (based on total solids content) of RE-Y. After mixing, the average particle size is about 3 microns.
One portion of this slurry is aged at 185°C for 2 hours. The aged portion is spray- dried.
X-ray diffraction (XRD) shows that the composition aged at 185°C contained Mg-Al anionic clay, RE-Y, and micro-crystalline boehmite.
Example 2
Example 1 is followed, except that instead of gibbsite, flash-calcined gibbsite is used.
The composition prepared by aging at 85°C contains Mg-Al anionic clay, RE-Y, and quasi-crystalline boehmite, whereas the composition aged at 185°C contains Mg-Al anionic clay, RE-Y, and micro-crystalline boehmite.
Example 3
Example 2 is followed, except that 4 wt% Zn(NO3)2 (based on total solids content) is added to the slurry.
The composition prepared by aging at 85°C contains Zn-doped Mg-Al anionic clay, RE-Y, and Zn-doped quasi-crystalline boehmite, whereas the composition aged at 1850C contains Zn-doped Mg-Al anionic clay, RE-Y, and Zn-doped micro- crystalline boehmite. Example 4
Example 3 is followed, except that instead of Zn(NO3)2) 6 wt% of La(NO3)3 (based on total solids content) is added to the slurry.
The composition prepared by aging at 85°C contains La-doped anionic clay, RE-Y, La-doped quasi-crystalline boehmite, whereas the composition aged at 185°C contains La-doped anionic clay, RE-Y, and La-doped micro-crystalline boehmite.
Example 5 Example 1 is followed, except that instead of gibbsite a 50/50 mixture of gibbsite and flash-calcined gibbsite is used, the Mg/AI mole ratio was 0.25, and 5 wt% Ce(NOs)3 (based on total solids content) is added to the slurry.
The composition prepared by aging at 85°C contains Ce-doped anionic clay, RE-Y, and Ce-doped quasi-crystalline boehmite, whereas the composition aged at 185°C contains Ce-doped anionic clay, RE-Y, and Ce-doped micro-crystalline boehmite.
Example 6
An aqueous slurry containing 25 wt% solids is prepared by high-shear mixing of flash-calcined gibbsite, MgO (Mg/AI mole ratio 0.25), 8 wt% RE-Y, 6 wt% Ce(NO3)3, and 15 wt% kaolin (all based on total solids content).
One portion of this slurry is aged at 85°C for 18 hours; another portion is aged at 185°C for 2 hours. The aged portions are spray-dried.
X-ray diffraction (XRD) shows that the composition prepared by aging at 85°C contains anionic clay, kaolin, RE-Y, and Ce-doped quasi-crystalline boehmite, whereas the composition aged at 185°C contains hydrotalcite, kaolin, RE-Y, and Ce-doped micro-crystalline boehmite. After preparation, the compositions are tested for cracking activity, sulphur reduction in gasoline and diesel, and SOX/NOX removal of FCC regenerator exhaust gases.
Example 7
Example 6 is followed, except that the spray-dried product is calcined at 5500C for 4 hours, followed by rehydration in an aqueous solution containing 4 wt% of ammonium vanadate. The resulting product is filtered and dried.
Example 8
A slurry is prepared by high-shear mixing of flash-calcined gibbsite, MgO (Mg/AI mole ratio 0.25), 15 wt% of iron-exchanged ZSM-5, and 4 wt% vanadyl sulphate.
One portion of this slurry is aged at 85°C for 18 hours; another portion is aged at 185°C for 2 hours. The aged portions are spray-dried. The total amount of gibbsite and MgO was such that the final dried product contains about 90 wt% gibbsite and MgO.
Example 9 An aqueous slurry with 28 wt% solids is prepared by mixing finely ground gibbsite, MgO (Mg/AI mole ratio 2.3), 8 wt% RE-USY. The slurry is homogenized in a colloid mill.
One portion of this slurry is aged at 85°C for 18 hours; another portion is aged at 185°C for 2 hours. The aged portions are spray-dried.
Example 10
An aqueous slurry comprising 70 wt% of flash-calcined gibbsite (Alcoa CP-3®) and about 30 wt% RE-USY (wt% based on total solids content) is prepared. The slurry is homogenized by high-shear mixing. The pH of the slurry is adjusted to about 5. The slurry is aged at 165°C for one hour. XRD indicates the formation of a composition comprising quasi-crystalline boehmite and RE-USY.
The composition is flash-calcined, slurried in water, and spray-dried to form microspheres. The microspheres are slurried in a suspension comprising MgO (Mg/AI ratio in suspension was 1) and aged at 85°C for 18 hours. During aging, the pH is adjusted to 9.5 using ammonium hydroxide.
The resulting product contains RE-USY, quasi-crystalline boehmite, and Mg-Al anionic clay.
Example 11
Example 10 is followed, except that the spray-drying step is performed not before but after aging at 85°C.
The resulting product contains RE-USY, quasi-crystalline boehmite, and Mg-Al anionic clay.
Example 12
Example 10 is followed, except that after aging at 165°C MgO is added to the slurry. The resulting Mg/AI ratio is 1 ; the pH is adjusted to about 9.
The resulting slurry is aged at 165°C for another hour, followed by flash- calcination, re-slurrying in water, and spray-drying.
The resulting product contained RE-USY, quasi-crystalline boehmite, and Mg-Al anionic clay. Example 13
An aqueous slurry is prepared comprising 60 wt% fine-particle gibbsite and about 40 wt% RE-Y (wt% based on total solids content). The slurry is milled in a colloid mill and flash-calcined. The flash-calcined product is re-slurried in water, with the pH set at about 5 using formic acid, and rehydrated at 165°C for one hour, and the slurry contains 25 wt% solids.
MgO is added to the slurry (Mg/AI was about 1), the pH is adjusted to 9.5, and the slurry is aged at 85°C for 18 hours. The final mixture is spray-dried.
XRD indicates the formation of a composition comprising RE-Y, anionic clay, and boehmite.
Example 14 An aqueous slurry is prepared comprising 60 wt% fine-particle gibbsite and about 40 wt% RE-Y (wt% based on total solids content). The slurry is milled in a colloid mil! and flash-calcined. The flash-calcined product is re-slurried in water, with the pH set at about 5 using nitric acid, and rehydrated at 165°C for one hour.
To the resulting slurry, 10 wt% of sodium-free silicasol is added. The mixture is homogenized and spray-dried. The product comprises RE-Y, boehmite, and silica.
Example 15
An aqueous slurry containing 70 wt% USY zeolite and 30 wt% ZSM-5 (all based on total solids content) is high-shear mixed and flash-calcined. After flash-calcination the product is re-slurried and high-shear mixed in a suspension comprising 35 wt% of flash-calcined gibbsite and 10 wt% of nickel nitrate.
The resulting mixture is aged at 165°C for one hour at a pH of 6. The slurry is dewatered and extruded to form pellets. The pellets are calcined and impregnated with 6 wt% of cobalt nitrate. Example 16
An aqueous slurry containing 70 wt% USY zeolite and 30 wt% ZSM-5 (all based on total solids content) is high-shear mixed and finally flash-calcined. After flash- calcination the product is re-slurried and high-shear mixed in a suspension comprising flash-calcined gibbsite, MgO (Mg/AI molar ratio 0.5), and 10 wt% of nickel nitrate. The total amount of MgO and flash-calcined gibbsite is about 40 wt% of the amount of the two zeolites.
The resulting mixture is aged at 165°C for one hour at a pH of 9.5. The slurry is dewatered and extruded to form pellets. The pellets are finally calcined and impregnated with 6 wt% of cobalt nitrate.
Example 17 A slurry comprising thermally stabilized REY, ground gibbsite, and magnesium oxide is prepared. This slurry has a solids content of 28 wt% and a Mg/AI molar ratio of 2.3. The slurry is milled in a colloid mill.
The slurry is aged at 85°C for 18 hours. Next the aged slurry is spray-dried to form microspheres. The microspheres are calcined and subsequently rehydratated in an aqueous slurry at 85°C for 8 hours.
The resulting composition comprises zeolite REY and Mg-Al anionic clay as the non-zeolitic compound.

Claims

1. Process for the preparation of a shaped catalyst composition comprising zeolite and a non-zeolitic component comprising the steps of: a) aging a precursor mixture comprising zeolite and one or more precursor(s) of the non-zeolitic component to obtain a composition comprising zeolite and non-zeolitic component, and b) shaping the composition comprising zeolite and non-zeolitic component to form shaped bodies.
2. Process according to claim 1 wherein the non-zeolitic component is selected from the group consisting of boehmite, anionic clay, cationic clay, and aluminium phosphate gel.
3. Process according to either one of the preceding claims wherein the precursor of the non-zeolitic component is an aluminium compound.
4. Process according to claim 3 wherein at least two different aluminium compounds are used as precursors of the non-zeolitic component.
5. Process according to any one of the preceding claims wherein the mixture is shaped by way of spray-drying.
6. Process according to any one of the preceding claims wherein metal additives are present in the precursor mixture.
7. Process according to any one of the preceding claims, followed by subjecting the shaped bodies to an impregnation or ion-exchange procedure.
8. Shaped catalyst composition obtainable by the process according to any one of the preceding claims.
PCT/US2006/026500 2005-07-01 2006-06-30 Process for the preparation of catalyst compositions comprising zeolite and non-zeolitic component WO2007006047A2 (en)

Priority Applications (3)

Application Number Priority Date Filing Date Title
JP2008519746A JP2008544853A (en) 2005-07-01 2006-06-30 Process for producing a catalyst composition comprising zeolite and non-zeolite components
CA002613490A CA2613490A1 (en) 2005-07-01 2006-06-30 Process for the preparation of catalyst compositions comprising zeolite and non-zeolitic component
EP06786595A EP1899057A2 (en) 2005-07-01 2006-06-30 Process for the preparation of catalyst compositions comprising zeolite and non-zeolitic component

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
US69629105P 2005-07-01 2005-07-01
US60/696,291 2005-07-01

Publications (2)

Publication Number Publication Date
WO2007006047A2 true WO2007006047A2 (en) 2007-01-11
WO2007006047A3 WO2007006047A3 (en) 2007-04-05

Family

ID=37605240

Family Applications (1)

Application Number Title Priority Date Filing Date
PCT/US2006/026500 WO2007006047A2 (en) 2005-07-01 2006-06-30 Process for the preparation of catalyst compositions comprising zeolite and non-zeolitic component

Country Status (5)

Country Link
EP (1) EP1899057A2 (en)
JP (1) JP2008544853A (en)
CN (1) CN101213018A (en)
CA (1) CA2613490A1 (en)
WO (1) WO2007006047A2 (en)

Cited By (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
EP2379225A2 (en) * 2008-12-24 2011-10-26 Chevron U.S.A., Inc. Zeolite supported cobalt hybrid fischer-tropsch catalyst
EP2415739A1 (en) * 2009-04-01 2012-02-08 Mitsui Chemicals, Inc. Process for producing olefin
WO2019140223A1 (en) * 2018-01-12 2019-07-18 Albemarle Corporation Fcc catalyst prepared by a process involving more than one silica material
WO2019140249A1 (en) * 2018-01-12 2019-07-18 Albemarle Corporation Fcc catalyst with enhanced mesoporosity, its preparation and use
US11427764B2 (en) * 2016-08-04 2022-08-30 Albemarle Corporation FCC catalyst with more than one silica, its preparation and use

Citations (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO2001012552A1 (en) * 1999-08-11 2001-02-22 Akzo Nobel N.V. Micro-crystalline boehmites containing additives and shaped particles and catalyst compositions comprising such micro-crystalline boehmite
WO2001012570A1 (en) * 1999-08-11 2001-02-22 Akzo Nobel N.V. Attrition resistant, shaped, crystalline anionic clay-containing bodies
WO2002064499A2 (en) * 2001-02-09 2002-08-22 Akzo Nobel N.V. Process for the preparation of anionic clay and boehmite-containing compositions, compositions containing anionic clay and boehmite and catalysts derived therefrom
WO2002068329A1 (en) * 2001-02-09 2002-09-06 Akzo Nobel N.V. Process for the preparation of anionic clay
WO2002072474A1 (en) * 2001-02-09 2002-09-19 Akzo Nobel N.V. In situ formed anionic clay-containing bodies

Patent Citations (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO2001012552A1 (en) * 1999-08-11 2001-02-22 Akzo Nobel N.V. Micro-crystalline boehmites containing additives and shaped particles and catalyst compositions comprising such micro-crystalline boehmite
WO2001012570A1 (en) * 1999-08-11 2001-02-22 Akzo Nobel N.V. Attrition resistant, shaped, crystalline anionic clay-containing bodies
WO2002064499A2 (en) * 2001-02-09 2002-08-22 Akzo Nobel N.V. Process for the preparation of anionic clay and boehmite-containing compositions, compositions containing anionic clay and boehmite and catalysts derived therefrom
WO2002068329A1 (en) * 2001-02-09 2002-09-06 Akzo Nobel N.V. Process for the preparation of anionic clay
WO2002072474A1 (en) * 2001-02-09 2002-09-19 Akzo Nobel N.V. In situ formed anionic clay-containing bodies

Cited By (10)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
EP2379225A2 (en) * 2008-12-24 2011-10-26 Chevron U.S.A., Inc. Zeolite supported cobalt hybrid fischer-tropsch catalyst
EP2379225A4 (en) * 2008-12-24 2012-12-05 Chevron Usa Inc Zeolite supported cobalt hybrid fischer-tropsch catalyst
EP2415739A1 (en) * 2009-04-01 2012-02-08 Mitsui Chemicals, Inc. Process for producing olefin
EP2415739A4 (en) * 2009-04-01 2014-01-08 Mitsui Chemicals Inc Process for producing olefin
US11427764B2 (en) * 2016-08-04 2022-08-30 Albemarle Corporation FCC catalyst with more than one silica, its preparation and use
US11926796B2 (en) 2016-08-04 2024-03-12 Ketjen Limited Liability Company FCC catalyst with more than one silica, its preparation and use
WO2019140223A1 (en) * 2018-01-12 2019-07-18 Albemarle Corporation Fcc catalyst prepared by a process involving more than one silica material
WO2019140249A1 (en) * 2018-01-12 2019-07-18 Albemarle Corporation Fcc catalyst with enhanced mesoporosity, its preparation and use
CN111565841A (en) * 2018-01-12 2020-08-21 雅宝公司 FCC catalysts with enhanced mesoporosity, their preparation and use
US11458456B2 (en) 2018-01-12 2022-10-04 Albemarle Corporation FCC catalyst prepared by a process involving more than one silica material

Also Published As

Publication number Publication date
JP2008544853A (en) 2008-12-11
EP1899057A2 (en) 2008-03-19
CA2613490A1 (en) 2007-01-11
CN101213018A (en) 2008-07-02
WO2007006047A3 (en) 2007-04-05

Similar Documents

Publication Publication Date Title
KR100972705B1 (en) Fcc catalyst for reducing the sulfur content in gasoline and diesel
US7208446B2 (en) Quasi-crystalline boehmites containing additives
EP1358128B1 (en) Process for the preparation of anionic clay
US7473663B2 (en) Process for the preparation of an additive-containing anionic clay
US20080039313A1 (en) Process for the Preparation of a Metal-Containing Composition
EP1761332B1 (en) Process for the preparation of an additive-containing anionic clay
WO2007006047A2 (en) Process for the preparation of catalyst compositions comprising zeolite and non-zeolitic component
US7008896B2 (en) Situ formed anionic clay-containing bodies
EP1358127B1 (en) In situ formed anionic clay-containing bodies
US6716785B2 (en) Composite and process for the in-situ preparation of a composite comprising a cationic clay and binder/matrix material
US20080308456A1 (en) Oxidic Metal Composition, Its Preparation And Use As Catalyst Composition
EP1899436A1 (en) Use of anionic clay in an fcc process
US6887457B2 (en) Process for the preparation of catalysts comprising a pentasil-type zeolite
CN1320960C (en) Process for the preparation of catalysts comprising a pentasil-type zeolite

Legal Events

Date Code Title Description
WWE Wipo information: entry into national phase

Ref document number: 200680023913.9

Country of ref document: CN

ENP Entry into the national phase in:

Ref document number: 2008519746

Country of ref document: JP

Kind code of ref document: A

ENP Entry into the national phase in:

Ref document number: 2613490

Country of ref document: CA

NENP Non-entry into the national phase in:

Ref country code: DE

WWE Wipo information: entry into national phase

Ref document number: 2006786595

Country of ref document: EP

WWE Wipo information: entry into national phase

Ref document number: 519/CHENP/2008

Country of ref document: IN