WO2012069526A1 - Procédé de fabrication de zéolites zsm-5 supportées - Google Patents

Procédé de fabrication de zéolites zsm-5 supportées Download PDF

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Publication number
WO2012069526A1
WO2012069526A1 PCT/EP2011/070782 EP2011070782W WO2012069526A1 WO 2012069526 A1 WO2012069526 A1 WO 2012069526A1 EP 2011070782 W EP2011070782 W EP 2011070782W WO 2012069526 A1 WO2012069526 A1 WO 2012069526A1
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Prior art keywords
zeolite
alumina
catalyst
binder
vinyl acetate
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PCT/EP2011/070782
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German (de)
English (en)
Inventor
Götz BURGFELS
Manfred Frauenrath
Friedrich Schmidt
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Süd-Chemie AG
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Publication of WO2012069526A1 publication Critical patent/WO2012069526A1/fr

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    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J29/00—Catalysts comprising molecular sieves
    • B01J29/04—Catalysts comprising molecular sieves having base-exchange properties, e.g. crystalline zeolites
    • B01J29/06—Crystalline aluminosilicate zeolites; Isomorphous compounds thereof
    • B01J29/40—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
    • 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
    • B01J21/02—Boron or aluminium; Oxides or hydroxides thereof
    • B01J21/04—Alumina
    • 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
    • B01J35/00—Catalysts, in general, characterised by their form or physical properties
    • B01J35/40—Catalysts, in general, characterised by their form or physical properties characterised by dimensions, e.g. grain size
    • 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
    • B01J35/00—Catalysts, in general, characterised by their form or physical properties
    • B01J35/50—Catalysts, in general, characterised by their form or physical properties characterised by their shape or configuration
    • 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
    • B01J35/00—Catalysts, in general, characterised by their form or physical properties
    • B01J35/50—Catalysts, in general, characterised by their form or physical properties characterised by their shape or configuration
    • B01J35/51—Spheres
    • 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
    • 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
    • B01J37/0018—Addition of a binding agent or of material, later completely removed among others as result of heat treatment, leaching or washing,(e.g. forming of pores; protective layer, desintegrating by heat)
    • 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
    • B01J37/02—Impregnation, coating or precipitation
    • B01J37/0215—Coating
    • 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
    • B01J37/02—Impregnation, coating or precipitation
    • B01J37/0215—Coating
    • B01J37/0219—Coating the coating containing organic compounds
    • 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
    • B01J37/02—Impregnation, coating or precipitation
    • B01J37/0215—Coating
    • B01J37/0221—Coating of particles
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J37/00—Processes, in general, for preparing catalysts; Processes, in general, for activation of catalysts
    • B01J37/02—Impregnation, coating or precipitation
    • B01J37/0215—Coating
    • B01J37/0225—Coating of metal substrates
    • 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
    • B01J37/02—Impregnation, coating or precipitation
    • B01J37/024—Multiple impregnation or coating
    • B01J37/0246—Coatings comprising a zeolite
    • 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
    • B01J37/04—Mixing
    • 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
    • B01J37/08—Heat treatment
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C1/00—Preparation of hydrocarbons from one or more compounds, none of them being a hydrocarbon
    • C07C1/20—Preparation of hydrocarbons from one or more compounds, none of them being a hydrocarbon starting from organic compounds containing only oxygen atoms as heteroatoms
    • 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
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C2521/00—Catalysts comprising the elements, oxides or hydroxides of magnesium, boron, aluminium, carbon, silicon, titanium, zirconium or hafnium
    • C07C2521/02—Boron or aluminium; Oxides or hydroxides thereof
    • C07C2521/04—Alumina
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C2529/00—Catalysts comprising molecular sieves
    • C07C2529/04—Catalysts comprising molecular sieves having base-exchange properties, e.g. crystalline zeolites, pillared clays
    • C07C2529/06—Crystalline aluminosilicate zeolites; Isomorphous compounds thereof
    • C07C2529/40—Crystalline aluminosilicate zeolites; Isomorphous compounds thereof of the pentasil type, e.g. types ZSM-5, ZSM-8 or ZSM-11
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
    • Y02P20/00—Technologies relating to chemical industry
    • Y02P20/50—Improvements relating to the production of bulk chemicals
    • Y02P20/52—Improvements relating to the production of bulk chemicals using catalysts, e.g. selective catalysts
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
    • Y02P30/00—Technologies relating to oil refining and petrochemical industry
    • Y02P30/20—Technologies relating to oil refining and petrochemical industry using bio-feedstock
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
    • Y02P30/00—Technologies relating to oil refining and petrochemical industry
    • Y02P30/40—Ethylene production

Definitions

  • the invention relates to a process for the preparation of
  • the invention relates to catalysts which can be prepared by such a method, as well as the use of the catalysts in the conversion of methanol or other oxygen-containing compounds in
  • Olefins especially propylene, with high propylene selectivity and stability.
  • Catalysts with ZSM-5 structure are i.a. from the
  • US 3,702,886 and DE-A-28 22 725 are known. Therein are selected from an aluminum source, a silicon source, an alkali source, a template, e.g. a tetrapropylammonium compound, and water produces aluminosilicate crystallites the size of which is, i.a. through the
  • Crystallization temperature and the concentration of the template is controlled as a nucleating agent.
  • ZSM-5 zeolites are described as catalysts for hydrocarbon conversion.
  • the aluminosilicate primary crystallites are combined with binders to form agglomerates.
  • Hydrocarbons used in alkylaryl hydrocarbons are Hydrocarbons used in alkylaryl hydrocarbons.
  • Monolithic catalyst supports consisting of a ceramic support and a catalytically active material applied thereto, e.g. a zeolite are also disclosed in USRE34853.
  • EP 0 369 364 and EP 1 424 128 also describe the use of ZSM-5 zeolites as catalysts in processes for the conversion of methanol to olefins, e.g. Methanol-to-propylene (MTP).
  • MTP Methanol-to-propylene
  • EP 1 424 128 achieves conversions with improved propylene selectivity (up to 36.1% by weight of propylene).
  • the present invention solves this problem by immobilizing active zeolite catalysts with ZSM-5 structure on active or inactive surfaces.
  • the immobilization causes a shortening of the residence time of the educts and a shortening of the diffusion paths on the catalyst surfaces and thus an increase in the
  • Propylene selectivity is also used for Avoiding or reducing the undesired formation phase in hydride transfer reactions, in the recycled naphthenes to undesirable aromatics and propylene to undesirable propane
  • the catalysts used in the process of the invention are characterized in particular by a high selectivity with respect to the conversion of methanol into propylene.
  • the process for producing the immobilized ZSM-5 zeolite catalysts is carried out by coating support materials with the active zeolite catalyst.
  • the individual starting materials and process steps are explained in more detail below.
  • a ZSM-5 type H zeolite has proved to be particularly suitable, as described for example in the
  • Molar ratio Si: Al in the H-zeolite is usually 10 - 400: 1, preferably 25 -300: 1, more preferably
  • the H-zeolite is in the form of agglomerates of primary crystallites.
  • the primary crystallites have a mean diameter in the
  • the size of the agglomerates is not particularly limited, preferably
  • Primary crystallite size is as described in EP 1 424 128.
  • the BET surface area of the H-zeolite is preferably 300 to 600 m 2 / g, determined according to DIN 66 131.
  • the powdery H-zeolite is dried and optionally subjected to an intermediate calcination. Subsequently, the H-zeolite, after optional slurrying with water, mixed with a binder and an adhesive. The binder and adhesive added H-zeolite is then brought into contact with the carrier material in a suitable coater.
  • inorganic oxides preferably inorganic oxides, preferably
  • Zirconia or silica as well as mixtures thereof, as well as amorphous aluminosilicates and non-oxidic binders such as
  • Example aluminum phosphates, aluminum nitrate can be used
  • Alumina binder which is preferably obtained by hydrolysis of Aluminiumtrialkylen or Aluminiumalkoholaten, or is used in the form of peptisable alumina hydrate. Very particular preference is given to peptisable as a binder
  • Alumina hydrate used More preferably, at least 95% of the particles of the peptisable alumina hydrate (based on the average diameter) -S 55 ⁇ .
  • binders include i.a. Aluminum nitrate,
  • Alumina and alumina hydrate especially finely divided alumina (such as Pural SB®, manufactured by Sasol),
  • alumina hydrate water-soluble, highly dispersed and pure alumina hydrate (boehmite) (such as Disperal P2®, manufacturer Sasol), and colloidally dispersed alumina hydrate (such as Alumina Sol TM AS-200 manufacturer Nissan Chemical), preferably Disperal P2® or Alumina Sol TM AS-200 , Due to the even distribution of
  • Alumina in the solvent is particularly high
  • Alumina hydrate for use in the process of the present invention.
  • supported catalysts obtained with the aid of these binders show particularly good mechanical stability.
  • adhesives are preferably copolymers, such as
  • plasticizer-free, aqueous dispersion of a vinyl acetate-ethylene copolymer Preferably, dispersions with a
  • Solid content in the range of 35 to 62 wt .-% used.
  • support material any suitable support materials which are customary in the prior art can be used as support material, such as, for example,
  • Microstructured reactors ceramic supports, metallic supports, support alloys, carbon supports, etc. Examples of
  • Microstructure reactors are e.g. Heat exchanger surfaces
  • Ceramic carriers are e.g. Oxide ceramics, silicon oxides, aluminum oxides,
  • Aluminosilicates cordierite, etc. Particularly preferred are the
  • Aluminas and aluminosilicates carriers are Aluminas and aluminosilicates carriers.
  • Metallic supports such as e.g. Aluminum, nickel, tin, zinc, etc., as well
  • Carrier alloys such as nickel-containing stainless steels, can be used with or without washcoat.
  • the carbon carriers used are, for example, activated carbon, carbon black, graphite or carbide.
  • the support materials can be used in a variety of forms, e.g. as metallic or ceramic honeycomb body or
  • Particularly preferred support materials are aluminas and / or aluminosilicates. These are preferably in spherical or
  • Tablet form in particular in spherical form before.
  • Specific examples thereof are e.g. DD443 beads (CHALCO / SALCO 126®), CTR T126 tablets (Süd-Chemie AG), Alumina beads 2.5 / 210 (Sasol) and K-306 aluminosilicate beads (Süd-Chemie AG).
  • the average diameter of the carrier balls is preferably 1 to 10 mm, particularly preferably 1.5 to 7 mm, in particular 2 to 5 mm. Tablets are preferably used in comparable orders of magnitude. It is further preferred if the tablets have a
  • the use of carrier beads or tablets of the specified minimum size is particularly advantageous to a decrease in the selectivity and activity in the
  • the relevant coating devices of the prior art can be used.
  • the relevant coating devices of the prior art can be used.
  • the relevant coating devices of the prior art can be used.
  • the relevant coating devices of the prior art can be used.
  • the proportions of H zeolite, binder, adhesive and carrier are preferably selected so that the final supported ZSM-5 zeolite has optimum activity and stability, and
  • the zeolite mass is from 20 to 40% by weight, preferably from 25 to 35% by weight and especially about 30% by weight, based on the total mass of zeolite, binder and carrier.
  • the binder is in the finished
  • Catalyst in an amount of 5 to 20 wt .-%, preferably 8 to 15 wt .-% and in particular about 10 wt .-% before, based on the zeolite mass.
  • the adhesive is used in an amount of 5 to 25% by weight, preferably 10 to 20% by weight, and more preferably about 15% by weight, based on the zeolite mass.
  • the residence time of the charge in the coater is not particularly limited. As a rule, it is about 1 to 3 hours depending on the carrier material used.
  • the coated support is then dried and optionally calcined.
  • the finished supported zeolite can be used advantageously in methanol-to-olefin (CMO) or methanol-to-propylene (MTP) process or generally for the conversion of oxygen-containing compounds to olefins, where it is characterized by its high propylene selectivity especially for MTP method is suitable.
  • CMO methanol-to-olefin
  • MTP methanol-to-propylene
  • the invention is not limited by the following
  • binders were used in the examples: aluminum nitrate, Pural SB® (manufacturer Sasol, finely divided alumina binder), Disperal P2® (manufacturer Sasol, water-soluble, highly dispersed and pure alumina hydrate (boehmite)) and Alumina Sol TM AS-200 (manufacturer Nissan Chemical, colloidally dispersed alumina hydrate, hereinafter abbreviated as Alumina Sol TM).
  • the adhesive used was one
  • plasticizer-free, aqueous dispersion of a vinyl acetate-ethylene copolymer plasticizer-free, aqueous dispersion of a vinyl acetate-ethylene copolymer.
  • the following carriers were used: aluminum oxides and / or aluminosilicates in spherical or tablet form. Specific examples thereof include DD443 beads (CHALCO, diameter: 3 - 5 mm), CTR T126 tablets (Süd-Chemie AG, tablet diameter: 4.5 mm; 4.5 mm), Alumina balls 2.5 / 210 (Sasol, diameter: 2.5 mm) and
  • the coating was carried out in an Innojet Aircoater 025® from
  • Example 2 50 g of H zeolite powder of the ZSM-5 type were weighed into a beaker, slurried with about 500 ml of deionized water (conductivity ⁇ 20 S / cm) and stirred briefly at room temperature. While stirring, 50 grams of Alumina-Sol TM binder were added to the suspension. Thereafter, with stirring, 15 g of the adhesive were added and the suspension stirred for a further 60 minutes at room temperature.
  • the balls were dried for 60 minutes at 90 ° C. in a Retsch TG200® in the fluidized bed. 162g of coated Sasol alumina beads were obtained. 83 g of the coated spheres were in a recirculating high temperature oven of RT at l ° C / min. heated to 550 ° C. At 550 ° C, the balls were calcined for 5 hours. At 6 ° C / min, the spheres were cooled to RT. There were obtained 79 g of coated spheres after calcination.
  • H zeolite powder of the ZSM-5 type were weighed into a beaker, slurried with about 500 ml of deionized water (conductivity ⁇ 20 S / cm) and stirred briefly at room temperature. While stirring, the suspension was mixed with 37 g of Alumina-Sol TM binder. Thereafter, with stirring, 11 g of the adhesive were added and the suspension stirred for a further 60 minutes at room temperature.
  • An Innojet Aircoater 025® was filled with 70 g of K-306 aluminosilicate beads. The coating process was started and the beads were coated with the suspension for about 2.0 hours. For this purpose, the following parameters were set for coating:
  • H zeolite powder of the ZSM-5 type were weighed into a beaker, slurried with about 600 ml of deionized water (conductivity ⁇ 20 S / cm) and stirred briefly at room temperature. While stirring, 58 grams of Alumina-Sol TM binder were added to the suspension. Thereafter, with stirring, 17 g of the adhesive were added and the
  • An Innojet Aircoater 025® was filled with 115 g of CTR-T126 tablets. The coating process was started and the beads were coated with the suspension for about 2.5 hours. For this purpose, the following parameters were set for coating:
  • the tablets were not dried after coating. 188 g of coated CTR-T126 tablets were obtained. 10.8 g of the tablets were placed in a recirculating high-temperature oven of RT at 1 ° C./min. to 200 ° C, then from 200 ° C at 0.5 ° C / min. to 300 ° C, then from 300 ° C at l ° C / min. heated to 550 ° C. At 550 ° C the balls were calcined for 5h. At 1 ° C./min, the tablets were cooled to RT. There were 10.2 g coated tablets after the
  • H zeolite powder of the ZSM-5 type were weighed into a beaker, slurried with about 1000 ml of deionized water (conductivity ⁇ 20 S / cm) and stirred briefly at room temperature. While stirring, the suspension was mixed with 80 g of Alumina-Sol TM binder. Thereafter, with stirring, 24 g of the adhesive were added and the
  • An Innojet Aircoater 025® was filled with 150g DD443 balls. The coating process was started and the beads were coated with the suspension for about 3.5 hours.
  • the balls were not dried after coating. 250 g of coated DD443 beads were obtained. 10.4g of the balls were placed in a recirculating high temperature RT oven at 1 ° C / min. to 200 ° C, then from 200 ° C at 0.5 ° C / min. to 300 ° C, then from 300 ° C at l ° C / min. heated to 550 ° C. At 550 ° C, the balls became 5 hours calcined. With l ° C / min, the balls were cooled to RT. 9.7 g of coated spheres were obtained after calcination.
  • H zeolite powder of the ZSM-5 type 50 g were weighed into a beaker, slurried with about 500 ml of deionized water (conductivity ⁇ 20 S / cm) and stirred briefly at room temperature. While stirring, the suspension was mixed with 7 g of Disperal P2® binder. Thereafter, 15 g of the adhesive were added with stirring and the
  • the balls were dried for 60 minutes at 90 ° C. in a Retsch TG200® in the fluidized bed.
  • 164 g of coated Sasol-Alumina beads were obtained, which were heated in a high-temperature circulating oven from RT at 1 ° C./min. to 200 ° C, then from 200 ° C at 0.5 ° C / min. to 300 ° C, then from 300 ° C at l ° C / min. to 550 ° C
  • An Innojet Aircoater 025® was filled with 150g DD443 balls. The coating process was started and the beads were coated with the suspension for about 2.5 hours.
  • nb * flocculation of the binder, therefore neither coating nor drop tests possible
  • a representative sample of the supported catalysts 1, 3 and 5 to 7 was taken in an amount of about 50 to 100 g each.
  • the sample was freed of adhering dust with a 1 mm sieve. In this case, the longer movement of the sample was kept as low as possible in order to avoid the abrasion and thus the influence on the result.
  • the pre-screened sample was dried for 3 hours at 120 ° C in a drying oven. The cooling to room temperature was then carried out in a desiccator with desiccant over 30 min.
  • a steel drum (diameter 254 mm, length 152 mm, with baffle of 50 mm height and 3 mm wall thickness) was cleaned with a hairbrush. The dried and pretreated sample was weighed to an accuracy of 0.01 g and transferred to the drum. The steel drum was closed with a lid and placed on a
  • Roll mill laid.
  • the steel drum was rotated at 60 +/- 5 revolutions per minute. After a total of 1800 revolutions, the rotation of the steel drum was stopped.
  • a rubber mallet was tapped several times on the steel drum to collect the fines on the bottom of the steel drum.
  • the lid was removed and the contents placed on a 1 mm sieve. The remaining fines from the lid and cylinder were brushed off with a hair brush and also placed on the sieve. The fines were sieved by gentle shaking.
  • the sieve residue (supported catalyst) was dried for 3 h at 120 ° C in a drying oven. The cooling to room temperature was then carried out in a desiccator with desiccant over 30 min. The dried sieve residue was weighed to an accuracy of 0.01 g.
  • the abrasion in% by weight was calculated according to the following formula:
  • a A initial weight, ie amount of dried supported catalyst used
  • Ball diameter can be the binding effect even better.
  • Alumina Sol TM is therefore considered to be a particularly suitable binder for the preparation of supported zeolite catalysts.

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

Abstract

L'invention concerne un procédé de fabrication de catalyseurs zéolites immobilisés, ainsi que des catalyseurs qui peuvent être fabriqués par un tel procédé, et l'utilisation des catalyseurs pour la conversion de méthanol ou d'autres composés à teneur en oxygène, en des oléfines, en particulier en propylène, ayant une sélectivité élevée vis-à-vis du propylène et une stabilité élevée.
PCT/EP2011/070782 2010-11-23 2011-11-23 Procédé de fabrication de zéolites zsm-5 supportées WO2012069526A1 (fr)

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
DE102010052258.9 2010-11-23
DE102010052258A DE102010052258A1 (de) 2010-11-23 2010-11-23 Verfahren zur Herstellung geträgerter ZSM-5-Zeolithe

Publications (1)

Publication Number Publication Date
WO2012069526A1 true WO2012069526A1 (fr) 2012-05-31

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