EP2978528A1 - Passivation d'un catalyseur zéolithique dans un lit fluidisé - Google Patents

Passivation d'un catalyseur zéolithique dans un lit fluidisé

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Publication number
EP2978528A1
EP2978528A1 EP14706827.4A EP14706827A EP2978528A1 EP 2978528 A1 EP2978528 A1 EP 2978528A1 EP 14706827 A EP14706827 A EP 14706827A EP 2978528 A1 EP2978528 A1 EP 2978528A1
Authority
EP
European Patent Office
Prior art keywords
catalyst
silicon compound
fluidized bed
zeolite
gas
Prior art date
Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
Withdrawn
Application number
EP14706827.4A
Other languages
German (de)
English (en)
Inventor
Mathias Feyen
Bernd Bastian SCHAACK
Ulrich Müller
Thomas Heidemann
Veronika Will
Rainer Senk
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
BASF SE
Original Assignee
BASF SE
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Filing date
Publication date
Application filed by BASF SE filed Critical BASF SE
Priority to EP14706827.4A priority Critical patent/EP2978528A1/fr
Publication of EP2978528A1 publication Critical patent/EP2978528A1/fr
Withdrawn legal-status Critical Current

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Classifications

    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C2/00—Preparation of hydrocarbons from hydrocarbons containing a smaller number of carbon atoms
    • C07C2/76—Preparation of hydrocarbons from hydrocarbons containing a smaller number of carbon atoms by condensation of hydrocarbons with partial elimination of hydrogen
    • 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
    • B01J29/405—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 rare earth elements, titanium, zirconium, hafnium, zinc, cadmium, mercury, gallium, indium, thallium, tin or lead
    • 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
    • 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
    • B01J29/40—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
    • B01J29/48—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 arsenic, antimony, bismuth, vanadium, niobium tantalum, polonium, chromium, molybdenum, tungsten, manganese, technetium or rhenium
    • 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
    • B01J29/90—Regeneration or reactivation
    • 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
    • B01J33/00—Protection of catalysts, e.g. by 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
    • B01J38/00—Regeneration or reactivation of catalysts, in general
    • B01J38/04—Gas or vapour treating; Treating by using liquids vaporisable upon contacting spent catalyst
    • B01J38/10—Gas or vapour treating; Treating by using liquids vaporisable upon contacting spent catalyst using elemental hydrogen
    • 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
    • B01J2229/12—After treatment, characterised by the effect to be obtained to alter the outside of the crystallites, e.g. selectivation
    • B01J2229/123—After treatment, characterised by the effect to be obtained to alter the outside of the crystallites, e.g. selectivation in order to deactivate outer surface
    • 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
    • B01J2229/18—After treatment, characterised by the effect to be obtained to introduce other elements into or onto the molecular sieve itself
    • B01J2229/186—After treatment, characterised by the effect to be obtained to introduce other elements into or onto the molecular sieve itself not in framework positions
    • 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
    • B01J2229/32—Reaction with silicon compounds, e.g. TEOS, siliconfluoride
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C2527/00—Catalysts comprising the elements or compounds of halogens, sulfur, selenium, tellurium, phosphorus or nitrogen; Catalysts comprising carbon compounds
    • C07C2527/24—Nitrogen compounds
    • 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
    • C07C2529/42—Crystalline aluminosilicate zeolites; Isomorphous compounds thereof of the pentasil type, e.g. types ZSM-5, ZSM-8 or ZSM-11 containing iron group metals, noble metals or copper
    • C07C2529/46—Iron group metals or copper
    • 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
    • C07C2529/48—Crystalline aluminosilicate zeolites; Isomorphous compounds thereof of the pentasil type, e.g. types ZSM-5, ZSM-8 or ZSM-11 containing arsenic, antimony, bismuth, vanadium, niobium, tantalum, polonium, chromium, molybdenum, tungsten, manganese, technetium or rhenium
    • 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
    • Y02P20/00—Technologies relating to chemical industry
    • Y02P20/50—Improvements relating to the production of bulk chemicals
    • Y02P20/584—Recycling of catalysts

Definitions

  • the present invention relates to a process for the preparation of a passivated catalyst comprising a zeolite and at least one active metal, which is characterized in that
  • the catalyst is kept in a fluidized bed and
  • Benzene can be prepared from methane or other lower alkanes by dehydration, as described e.g. in WO 2009/124960.
  • the alkanes are heated at high temperatures, e.g. from 300 to 1000 ° C, reacted on a catalyst.
  • the catalyst may be in the reactor e.g. be present as a fixed bed or fluidized bed.
  • catalysts are used for the dehydroaromatization whose surface has been passivated with the aid of a silicon compound to form a silicon layer.
  • the passivation of zeolite catalysts with the aid of silicon compounds is also known from WO 2007/080240 and WO 2005/014169.
  • the active metals of the catalyst are introduced after passivation;
  • the passivation can be carried out with liquid or gaseous passivating agent.
  • the catalyst is treated in a fixed bed with a stream of nitrogen, to which tetraethoxysilane is added as a passivating agent.
  • WO 2007/080240 does not describe dehydroaromatizations.
  • the object of the present invention was therefore a simplified process for the passivation of catalysts and a simplified and improved process for dehydroaromatization using a passivated catalyst.
  • coke formation and deposition during dehydroaromatization should be reduced. Accordingly, the method defined above was found. Also found was a dehydroaromatization process using such a passivated catalyst.
  • the catalyst contains a zeolite.
  • Zeolites are naturally occurring or artificially produced microporous substances having a three-dimensional framework structure of neutral Si04 tetrahedra and negatively charged AlO 4 tetrahedra and optionally further metal / oxygen compounds in the form of tetrahedra. Preference is given to zeolites which consist of more than 80% by weight, particularly preferably more than 95% by weight, of neutral SiC tetrahedra and negatively charged AIC tetrahedra.
  • composition of the unit cell a distinction is made between different basic types, which are characterized by 3 letters according to an international nomenclature of the international zeolite association, e.g. MFI, EUO, MTT.
  • the MFI type of structure is a 10-ring zeolite, i. the circumference of the pores corresponds to a ring of 10 atoms in total Si, Al and optionally other metal; these 10 atoms are bridged by oxygen.
  • zeolites of the structural type MFI are e.g. TS-1 or ZSM-5 known. Most preferably it is ZSM-5.
  • the pore diameter of the ZSM-5 is generally about 5.5 angstroms uniformly.
  • the ZSM-5 consists mainly of Si04 tetrahedra and contains only small amounts of negatively charged aluminum tetrahedra.
  • the ratio Si / Al preferably corresponds to a ratio of SiO 2 to Al 2 O 3 of 10: 1 to 200: 1.
  • Cations to the negatively charged aluminum tetrahedra are generally hydrogen (acid H form) or alkali cations or ammonium cations. This is preferably a zeolite in the H form.
  • the zeolite may also contain small amounts of alkali metal cations in the H form, preferably the content of alkali metal cations is less than 1% by weight, in particular less than 0.1% by weight and more preferably less than 0.01% by weight.
  • % Synthetic zeolites can be prepared from an aqueous solution containing a Si compound (Si source, eg any silica such as pyrogenic or precipitated Silka, water glass, silica gel, silanes or siloxanes), an aluminum compound (Al source, eg aluminum hydroxide), a so-called Templat and optionally further additives, in particular for adjusting the pH, contains, are prepared.
  • Si source eg any silica such as pyrogenic or precipitated Silka, water glass, silica gel, silanes or siloxanes
  • Al source eg aluminum hydroxide
  • Templat eg aluminum hydroxide
  • optionally further additives in particular for adjusting the pH, contains
  • Suitable templates are e.g. Allyltripropylammonium hydroxide or tetrapropylammonium hydroxide.
  • the catalyst preferably contains a binder in addition to the zeolite.
  • Suitable binders are Si-containing binders, e.g. colloidal silica, polysiloxanes or mixtures thereof.
  • the zeolite is first mixed with the binder.
  • zeolite and binder are mixed in the form of liquid preparations (solutions or dispersions).
  • the proportion of the binder may be e.g. 5 to 200 parts by weight per 100 parts by weight, in particular 10 to 100 parts by weight per 100 parts by weight of zeolite.
  • a shaping step can be carried out;
  • the mixture is processed according to the processes known to those skilled in the art into shaped bodies.
  • the shaping processes to be mentioned are, for example, spraying of a suspension containing the zeolite or the catalyst mass into powders, tabletting, pressing in the moist or dry state and extrusion. Two or more of these methods can also be combined.
  • Auxiliaries such as pore formers and pasting agents or else other additives known to the person skilled in the art can be used for shaping.
  • Possible pasting agents are those compounds which improve the mixing, kneading and flow properties.
  • these are preferably organic, in particular hydrophilic polymers such as cellulose, cellulose derivatives such as methylcellulose, starch such as potato starch, wallpaper pastes, acrylates, polyacrylates, polymethacrylates, polyvinyl alcohols, polyvinyl pyrrolidone, polyisobutylene, polytetrahydrofuran, polyglycol ethers, fatty acid compounds, wax emulsions , Water or mixtures of two or more of these compounds.
  • hydrophilic polymers such as cellulose, cellulose derivatives such as methylcellulose, starch such as potato starch, wallpaper pastes, acrylates, polyacrylates, polymethacrylates, polyvinyl alcohols, polyvinyl pyrrolidone, polyisobutylene, polytetrahydrofuran, polyglycol ethers, fatty acid compounds, wax emulsions , Water or mixtures of two or more of these compounds.
  • pore formers which can be dispersed, suspended or emulsified in water or aqueous solvent mixtures are, for example, polyalkylene oxides, polystyrene, polyacrylates, polymethacrylates, polyolefins, polyamides, polyesters, carbohydrates, cellulose, cellulose derivatives, for example methylcellulose, sugar natural fibers, Pulp, graphite or mixtures of two or more of these compounds.
  • Pore formers and / or pastes are classified according to the Forming preferably removed by at least one suitable drying and / or calcining step from the resulting shaped body.
  • the resulting shaped articles may be powders having a desired distribution of the powder size or shaped articles having a uniform, defined geometry.
  • the catalysts may be spherical (hollow or full), cylindrical (hollow or full), ring-, satin-, star-, honeycomb- or tablet-shaped.
  • extrudates are for example in strand, Trilob, Quatrolob, star or hollow cylindrical shape in question.
  • the catalyst mass to be molded can be extruded, calcined and the extrudates thus obtained broken and processed into chips or powder.
  • the grit can be separated into different sieve fractions.
  • a preferred sieve fraction has the grain size 0.25 to 0.5 mm.
  • a powder in particular by spray drying, is produced from the mixture of binder and zeolite.
  • the catalyst contains at least one catalytically active metal.
  • the catalyst contains a plurality of catalytically active metals.
  • metals is here understood to mean metals in elemental form but also in the form of metal ions or central atoms of complex compounds. In particular, it is metal ions, which are present as salts.
  • the catalytically active metals may be any metals of the periodic table.
  • the catalyst contains one or more active metals selected from Mo, Mn, Cr, Zr, V, Zn, Cu, Ni, Fe, W, Ga, Ge and Co.
  • the catalyst particularly preferably contains one or more active metals selected from Mo, Ni, Cu, Fe, Zn.
  • the catalyst contains Mo and additionally one or more metals.
  • the catalyst contains Mo and additionally one or more metals selected from Fe, Cu, Ni, Zn.
  • the catalyst prepared according to all process steps a) to c) 1 to 20 wt.%, Particularly preferably 3 to 20 wt.% Of active metals, based on the total weight of the catalyst.
  • the catalyst contains, by all process steps, 1 to 15% by weight of molybdenum (Mo), in particular 3 to 12% by weight of Mo and 0 to 10% by weight, based on preferably 0.5 to 5 wt.%
  • Mo molybdenum
  • Other active metals for example those mentioned above, preferably Fe, Cu, Ni, Zn.
  • the active metals may be incorporated in the catalyst before or after passivation with the silicon compound, e.g. they can be applied in advance to the zeolite or to the mixture of zeolite and binder, or the molded article produced therefrom, in particular powder. You can also be applied only after the passivation of the catalyst with the silicon compound. This subsequent application of the active metals is customary in order to avoid that the active metals are passivated.
  • the methods for applying the metals described below apply equally regardless of whether the active metals are applied to the zeolite, the mixture of zeolite and binder, or the molded article produced therefrom, in particular or powder or before or after passivation.
  • the active metals can be applied wet-chemically or dry-chemically.
  • the active metal can be applied in the form of aqueous, organic or organic-aqueous solutions of its salts or complexes by impregnating the zeolite or catalyst with the appropriate solution.
  • the solvent may also be supercritical CO 2.
  • the impregnation can be carried out by the incipient wetness method, in which the porous volume of the zeolite is filled up with approximately the same volume of impregnating solution and, optionally after maturation, the support is dried. You can also work with an excess of solution, the volume of this solution is greater than the porous volume of the zeolite. In this case, the zeolite is mixed with the impregnating solution and stirred for a sufficient time.
  • the catalyst is dried at about 80 to 130 ° C usually for 4 to 20 hours in vacuo or in air.
  • the elements Mn, Cr, Zr, V, Zn, Cu, Ni, Fe, W, Ga, Ge and Co are preferably applied wet-chemically.
  • the metal salts used are preferably the nitrates, such as copper nitrate, nickel nitrate, iron nitrate and cobalt nitrate, but also others, which are known to the person skilled in the art for the wet Chemical application known salts can be used.
  • halides in particular chloride, acetate, alkaline carbonates, formate, tartrate, acetate, complexes with ligands such as acetylacetonate, amino alcohols, EDTA, carboxylates such as oxalate and citrate and Hydroxycarbonklaresalze.
  • the solution to which the active metal or metals are applied contains at least one complexing agent.
  • the complexing agent is selected from the group acetylacetonate, amino alcohols, EDTA, carboxylates such as oxalate and citrate and Hydroxycarbonklaresalze. Particular preference is given to using EDTA.
  • the active metal may be e.g. be deposited at higher temperatures from the gas phase by deposition on the zeolite, or the catalyst. In the case of molybdenum, this is suitable e.g. gaseous Mo (CO) 6.
  • the catalyst is kept in a fluidized bed and passivated in the fluidized bed with a silicon compound.
  • silicon compound is meant here a compound which contains at least one silicon atom.
  • the catalytic reaction takes place at the acidic sites in the pores of the catalyst.
  • These acidic centers can be passivated by reaction with a silicon compound and formation of a polymeric silicon layer, generally a silicon dioxide layer.
  • Suitable silicon compounds are, in particular, those which are formed by polycondensation or polyaddition, e.g. can be converted at elevated temperature into polymeric silicon compounds, in particular those having a basic structure of silica.
  • non-polymeric silicon compounds having a molecular weight of less than 5000 g / mol, in particular less than 1000 g / mol and particularly preferably less
  • the silicon compounds have at least one molecular diameter larger than the diameter of the pores of the zeolites used.
  • the silicon-containing compounds have at least a diameter greater than 5.5 angstroms.
  • Silanes, siloxanes or silazanes, in particular silanes, may be mentioned as suitable silicon compounds.
  • Silanes are silane (SiH 4 ) and its derivatives, ie compounds in which at least one hydrogen is replaced by another substituent.
  • Suitable organic groups are, for example, alkyl groups, aryl groups, alkoxy groups or aroxy groups. At least two of the organic groups are preferably those which, when dehydrated to form a polymeric compound, condense a Si-O-Si basic structure.
  • Particular preference is given to silanes having 2 to 4 alkoxy groups, these preferably being C 1 -C 10 -alkoxy groups or C 1 -C 4 -alkoxy groups.
  • tetraalkoxysilanes such as tetramethoxysilane or tetraethoxysilane.
  • Siloxanes are compounds containing two oxygen atoms linked by oxygen atoms.
  • the two Si atoms are substituted by H atoms or organic groups.
  • the above statements on the silanes apply correspondingly to the organic groups.
  • the siloxanes contain at least two organic groups which undergo a condensation reaction; in particular, these are alkoxy groups listed above.
  • Silazanes are compounds having two Si atoms of the basic structure connected via a nitrogen group
  • the radicals R are organic groups; Alkyl groups or alkoxy groups.
  • Suitable silazanes are e.g. Hexaalkylsilazanes, e.g. Hexa-C1-C10-alkylsilazanes. Mention may be made of hexamethylsilazane by way of example:
  • the catalyst is kept in a fluidized bed during passivation.
  • the catalyst is generally first introduced as a fixed bed in a reactor and flowed from below with gas, which is called carrier gas here.
  • the flow of the carrier gas is increased until the fluidized bed is formed.
  • the gas flow is adjusted so that a stable fluidized bed is formed, ie in particular that the fluidized bed is not discharged but remains at the desired height.
  • the silicon compound can now preferably be applied to the catalyst in gaseous form.
  • the silicon compound can be heated to temperatures above its boiling point and brought into contact with the catalyst in the fluidized bed.
  • the silicon compound is brought into contact with the catalyst in the fluidized bed in admixture with other gases, preferably the carrier gas.
  • the gas which is preferably simultaneously the carrier gas, may be inert gas such as nitrogen or noble gases or the gaseous starting materials of the later reaction, for example methane or natural gas.
  • the gas is an inert gas, more preferably it is nitrogen or helium.
  • the gas may be contacted in advance with the silicon compound and so take up the silicon compound, preferably until saturation of the carrier gas stream with the silicon compound, and then brought into contact with the fluidized bed of the catalyst.
  • the silicon compound does not need to be heated to its boiling point.
  • the vapor pressure at room temperature is already sufficient for the gas or carrier gas to absorb sufficient silicon compound.
  • the gas or carrier gas preferably contains 0.01 to 10% by volume, in particular 0.1 to 2% by volume, of the silicon compound.
  • the catalyst thus treated with the silicon compound in a fluidized bed can then be removed from the reactor and optionally dried.
  • the drying may e.g. in a separate process step before the further reaction of the silicon compound to a polymeric silicon layer at temperatures of 20 to 150 ° C and optionally under reduced pressure, e.g. done under vacuum.
  • the conversion of the silicon compound to a polymeric silicon layer is preferably carried out at elevated temperature.
  • the conversion to the polymeric silicon layer may e.g. at temperatures of 100 to 800 ° C, in particular 200 to 700 ° C, particularly preferably 300 to 700 ° C take place (calcination).
  • the temperature is usually increased slowly over a longer period and maintained the maximum temperature reached over a longer period of time. It may be e.g. Total trading for a period of 2 to 20 hours.
  • the finally obtained surface-passivated catalyst preferably has a content of 0.001 to 5% by weight, particularly preferably 0.01 to 1% by weight of the silicon compound or of the reaction product obtained therefrom after a final calcination.
  • the above quantity is based only on the Si atom of the silicon compound, since the content of the silicon introduced by the silicon compound does not change in the further implementation of this silicon compound.
  • the catalyst obtained by the above production method is preferably used as a catalyst for dehydroaromatization.
  • the catalyst is used for the dehydroaromatization of alkanes and alkenes.
  • the C1 - C4 aliphatic may be e.g. be methane, ethane, propane, n-butane, i-butane, ethene, propene, 1- and 2-butene or isobutene.
  • the dehydroaromatization is a process for the preparation of benzene from methane or mixtures of aliphatics consisting of more than 70% by weight, more preferably more than 90% by weight, based on the total amount of aliphatic, of methane ,
  • natural gas can be used as the methane or mixture of aliphatics.
  • gaseous compounds which do not dehydroaromatize e.g. Hydrogen, water, carbon monoxide, carbon dioxide, nitrogen or noble gases.
  • Inert gases such as nitrogen or noble gases are used to reduce the partial pressure.
  • Other gases such as carbon monoxide or carbon dioxide, may reduce coke formation.
  • the concentration of oxidizing agents such as oxygen or nitrogen oxides in the educt stream should preferably be below 5% by weight, preferably below 1% by weight, more preferably below 0.1% by weight. Most preferably, the mixture is free of oxygen and nitrogen oxides.
  • the catalyst may optionally be activated in advance. Activation is generally carried out at lower temperatures than those of the later reaction and a defined temperature / time curve to complete as completely as possible chemical reactions in or on the catalyst. By such activation, if necessary, the activity of the catalyst can be increased.
  • the catalyst is contacted for activation with a gas of appropriate temperature.
  • a prior activation can, for example, with a C1 -C4 alkane, such as methane, ethane, propane, butane or a mixture thereof, preferably methane, take place.
  • the activation can be carried out at a temperature of 250 to 650 ° C, preferably at 350 to 550 ° C, and a pressure of 0.5 to 100 bar, preferably at 1 to 50 bar, in particular 1 to 10 bar.
  • the GHSV Gas Hourly Space Velocity
  • the GHSV Gas Hourly Space Velocity
  • the catalyst can also be activated with a gas stream containing H2; the H2 gas stream may additionally contain inert gases such as N2, He, Ne and Ar.
  • activation takes place with a C 1 -C 4 -alkane, if appropriate in a mixture with hydrogen.
  • the activation is carried out with methane, optionally in admixture with hydrogen.
  • the dehydroaromatization of C 1 -C 4 -aliphatic compounds can be carried out in the presence of the above-described catalysts at from 400 to 1000 ° C., preferably from 500 to 900 ° C., more preferably from 600 to 800 ° C., in particular from 650 to 800 ° C. , at a pressure of 0.5 to 100 bar, preferably at 1 to 50 bar, more preferably at 1 to 30 bar, in particular 1 to 10 bar, are performed.
  • the feed of the educt stream into the reactor can e.g. with a GHSV (Gas Hourly Space Velocity) of 100 to 10,000 h-1, preferably from 200 to 3000 h-1.
  • GHSV Gas Hourly Space Velocity
  • the catalysts can be regenerated with decreasing activity by customary methods known to those skilled in the art. Particularly suitable is the regeneration of the catalysts with hydrogen.
  • reaction can be stopped and the catalyst can be regenerated with hydrogen.
  • reaction cycle and the regeneration cycle can alternate, and the reactant stream and hydrogen can be passed alternately over the catalyst.
  • hydrogen can be added to the reactant stream so that regeneration takes place simultaneously with the reaction.
  • the educt stream in the regeneration phase may contain more than 10% by volume, in particular more than 30% by volume and more preferably more than 50% by volume of hydrogen.
  • reactors for carrying out the dehydroaromatization e.g. Tubular or tubular reactors suitable.
  • the catalyst prepared according to the invention can be present in these reactors as a fixed bed or fluidized bed.
  • the dehydroaromatization of C1 to C4 aliphatics in particular of methane, can be carried out with high yields and selectivities.
  • high yields and selectivities of benzene are achieved.
  • the deposition of coke on the catalyst is significantly reduced by the process according to the invention for passivation; As a result, the life is increased and the time intervals between necessary regeneration of the catalyst significantly extended. Examples
  • a catalyst of zeolite H-ZSM-5 and a polysiloxane was used as a binder.
  • the catalyst was present as a powder with a particle size of 45 ⁇ - 200 ⁇ . After drying and calcining, the catalyst contained 78% by weight of H-ZSM-5, the remainder being SiO 2 formed from the binder.
  • the catalyst thus prepared was used in the Example and Comparative Example described below.
  • the catalyst thus treated was dried in a drying oven under vacuum at 35 ° C. for 4 hours and then calcined (3 hours at 500 ° C. and 4 hours at 500 ° C.).
  • the fluidized bed of the catalyst was formed.
  • the gas mixture simultaneously served as carrier gas for the fluidized bed.
  • the temperature in the fluidized bed was about 100 ° C.
  • the gas flow of 30 standard liters (NL) / hr was maintained for one hour.
  • the catalyst thus treated was dried at 120 ° C for 16 hours and then calcined
  • a methane stream was passed through the reactor at a flow rate of 100 standard liters (NL) / h, during which the temperature was slowly increased to the reaction temperature (700 ° C.) (during which the catalyst is activated, the Mo oxide that is contained is converted to molybdenum) carbidinstrument).
  • the flow rate was calculated for normal pressure and normal temperature.
  • reaction cycle The reaction was then carried out with a mixture of CH4 / He (90:10) at a flux of 20 NL / h.
  • the temperature in the reactor was 700 ° C and the pressure 2.5 bar.
  • One reaction cycle lasted 10 h.
  • the catalysts were regenerated by introducing hydrogen at 4 bar and 750 ° C for 5 hours (regeneration cycle).

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  • Organic Chemistry (AREA)
  • Engineering & Computer Science (AREA)
  • Materials Engineering (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Crystallography & Structural Chemistry (AREA)
  • Catalysts (AREA)
  • Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
  • Low-Molecular Organic Synthesis Reactions Using Catalysts (AREA)

Abstract

L'invention concerne un procédé de production d'un catalyseur passivé qui contient un zéolithe et au moins un métal actif, caractérisé en ce que - le catalyseur est maintenu dans un lit fluidisé et en ce que - il est passivé dans le lit fluidisé à l'aide d'un composé de silicium.
EP14706827.4A 2013-03-27 2014-02-26 Passivation d'un catalyseur zéolithique dans un lit fluidisé Withdrawn EP2978528A1 (fr)

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EP14706827.4A EP2978528A1 (fr) 2013-03-27 2014-02-26 Passivation d'un catalyseur zéolithique dans un lit fluidisé

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EP13161388 2013-03-27
EP14706827.4A EP2978528A1 (fr) 2013-03-27 2014-02-26 Passivation d'un catalyseur zéolithique dans un lit fluidisé
PCT/EP2014/053702 WO2014154429A1 (fr) 2013-03-27 2014-02-26 Passivation d'un catalyseur zéolithique dans un lit fluidisé

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US10556801B2 (en) 2015-02-12 2020-02-11 Basf Se Process for the preparation of a dealuminated zeolitic material having the BEA framework structure
US10724979B2 (en) * 2015-05-26 2020-07-28 Nitto Denko Corporation Gas sensor element
EP3468712A1 (fr) * 2016-06-10 2019-04-17 Exxonmobil Research And Engineering Company Catalyseurs à base de polymères d'organosilice et leurs procédés de production
CN109833897B (zh) * 2017-11-28 2022-05-31 中国科学院大连化学物理研究所 一种用于生产糠醇的催化剂及其制备和生产糠醇的方法
JP7038820B2 (ja) * 2017-11-30 2022-03-18 中国科学院大▲連▼化学物理研究所 分子篩触媒改質装置及び方法

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TWI234556B (en) * 1997-07-23 2005-06-21 Mitsubishi Gas Chemical Co Catalysts for methanol conversion reactions
KR20030031916A (ko) * 2000-07-27 2003-04-23 코노코필립스 컴퍼니 메탄으로부터 방향족 탄화수소를 제조하기 위한 촉매 및방법
US7019184B2 (en) * 2002-01-28 2006-03-28 Conocophillips Company Non-oxidative conversion of gas to liquids
CN100391915C (zh) * 2006-04-13 2008-06-04 中国科学院大连化学物理研究所 一种甲苯甲基化制对二甲苯催化剂的在线修饰方法
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CN101607864B (zh) * 2009-07-24 2013-05-22 中国海洋石油总公司 一种甲醇/二甲醚转化高产率制备对二甲苯的方法
CN101602646B (zh) * 2009-07-24 2012-10-03 中国海洋石油总公司 一种甲醇/二甲醚生产芳烃的方法及其专用反应装置

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KR20150135306A (ko) 2015-12-02
EA201591853A1 (ru) 2016-03-31
AU2014243377A1 (en) 2015-09-24
JP2016520415A (ja) 2016-07-14
WO2014154429A1 (fr) 2014-10-02
US20150353446A1 (en) 2015-12-10

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