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WO2014154509A1 - Passivation d'un catalyseur zélithique pour la déshydro-aromatisation - Google Patents

Passivation d'un catalyseur zélithique pour la déshydro-aromatisation Download PDF

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Publication number
WO2014154509A1
WO2014154509A1 PCT/EP2014/055266 EP2014055266W WO2014154509A1 WO 2014154509 A1 WO2014154509 A1 WO 2014154509A1 EP 2014055266 W EP2014055266 W EP 2014055266W WO 2014154509 A1 WO2014154509 A1 WO 2014154509A1
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WIPO (PCT)
Prior art keywords
catalyst
silicon
zeolite
weight
dehydroaromatization
Prior art date
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Ceased
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PCT/EP2014/055266
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German (de)
English (en)
Inventor
Mathias Feyen
Bernd Bastian SCHAACK
Ulrich Müller
Thomas Heidemann
Veronika Will
Rainer Senk
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BASF SE
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BASF SE
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Publication of WO2014154509A1 publication Critical patent/WO2014154509A1/fr
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    • 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
    • B01J29/061—Crystalline aluminosilicate zeolites; Isomorphous compounds thereof containing metallic elements added to the 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
    • 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
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    • 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
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    • 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
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    • B01J37/0027—Powdering
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    • B01J37/0201—Impregnation
    • B01J37/0205—Impregnation in several steps
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    • B01J38/10—Gas or vapour treating; Treating by using liquids vaporisable upon contacting spent catalyst using elemental hydrogen
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    • 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
    • C10G45/00—Refining of hydrocarbon oils using hydrogen or hydrogen-generating compounds
    • C10G45/58—Refining of hydrocarbon oils using hydrogen or hydrogen-generating compounds to change the structural skeleton of some of the hydrocarbon content without cracking the other hydrocarbons present, e.g. lowering pour point; Selective hydrocracking of normal paraffins
    • C10G45/60—Refining of hydrocarbon oils using hydrogen or hydrogen-generating compounds to change the structural skeleton of some of the hydrocarbon content without cracking the other hydrocarbons present, e.g. lowering pour point; Selective hydrocracking of normal paraffins characterised by the catalyst used
    • C10G45/64—Refining of hydrocarbon oils using hydrogen or hydrogen-generating compounds to change the structural skeleton of some of the hydrocarbon content without cracking the other hydrocarbons present, e.g. lowering pour point; Selective hydrocracking of normal paraffins characterised by the catalyst used containing crystalline alumino-silicates, e.g. molecular sieves
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    • 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
    • C10G45/00—Refining of hydrocarbon oils using hydrogen or hydrogen-generating compounds
    • C10G45/58—Refining of hydrocarbon oils using hydrogen or hydrogen-generating compounds to change the structural skeleton of some of the hydrocarbon content without cracking the other hydrocarbons present, e.g. lowering pour point; Selective hydrocracking of normal paraffins
    • C10G45/66—Refining of hydrocarbon oils using hydrogen or hydrogen-generating compounds to change the structural skeleton of some of the hydrocarbon content without cracking the other hydrocarbons present, e.g. lowering pour point; Selective hydrocracking of normal paraffins with moving solid particles
    • 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
    • C10G45/00—Refining of hydrocarbon oils using hydrogen or hydrogen-generating compounds
    • C10G45/58—Refining of hydrocarbon oils using hydrogen or hydrogen-generating compounds to change the structural skeleton of some of the hydrocarbon content without cracking the other hydrocarbons present, e.g. lowering pour point; Selective hydrocracking of normal paraffins
    • C10G45/68—Aromatisation of hydrocarbon oil fractions
    • 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
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    • 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
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    • B01J2229/30—After treatment, characterised by the means used
    • B01J2229/32—Reaction with silicon compounds, e.g. TEOS, siliconfluoride
    • B—PERFORMING OPERATIONS; TRANSPORTING
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    • B—PERFORMING OPERATIONS; TRANSPORTING
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    • 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)
    • 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
    • C07C2521/06—Silicon, titanium, zirconium or hafnium; Oxides or hydroxides thereof
    • C07C2521/08—Silica
    • 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
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    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C2529/00—Catalysts comprising molecular sieves
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    • C07C2529/46—Iron group metals or copper
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
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    • C07C2529/04—Catalysts comprising molecular sieves having base-exchange properties, e.g. crystalline zeolites, pillared clays
    • C07C2529/06—Crystalline aluminosilicate zeolites; Isomorphous compounds thereof
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    • 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
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    • 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
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    • C10G2400/30—Aromatics
    • 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
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    • 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
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Definitions

  • the present invention relates to a process for the preparation of a catalyst for the dehydroaromatization, which is characterized in that a) a catalyst comprising a zeolite and at least one catalytically active metal, b) with a silicon passivated compound is passivated and
  • Benzene can be prepared from methane or other lower alkanes or alkenes by dehydroaromatization, e.g. in WO 2009/124960 is described.
  • the alkanes are heated at high temperatures, e.g. from 300 to 1000 ° C, reacted at a catalyst.
  • high temperatures e.g. from 300 to 1000 ° C
  • He must remain active for as long as possible at these high temperatures and ensure the highest possible conversion with the highest possible selectivity. It is easy at these high temperatures for the formation of carbon in the form of coke, which deposits on the catalyst.
  • acidic sites on the catalyst surface favor the formation of carbon and its deposition.
  • 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 catalysts, in particular 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 only after passivation. Also in the examples of
  • 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 starting material of the process according to process step a) is a catalyst which contains a zeolite and catalytically active metals.
  • 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, more preferably more than 95% by weight, of neutral Si0 4 tetrahedra and negatively charged Al0 4 tetrahedra.
  • 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 (acidic H form) or alkali cations or ammonium cations.
  • 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 particularly 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 fumed or precipitated Silka, water glass, silica gel, silanes or siloxanes), an aluminum compound (Al source, eg aluminum hydroxide), a so-called template and if appropriate, further additives, in particular for adjusting the pH, are prepared.
  • Si source eg any silica such as fumed or precipitated Silka
  • Al source eg aluminum hydroxide
  • the template is an organic compound that serves as a placeholder for the pores.
  • the solution is heated, forming a solid from the constituents.
  • the organic compound (template) is finally removed by calcination (heating to very high temperatures), only now are the pores contained in the solid body freely accessible.
  • Suitable templates are e.g. Allyltripropylammonium hydroxide or tetrapropylammonium hydroxide.
  • the catalyst used according to the invention in step a) 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 methods known in the art to form 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, such as example, methyl cellulose, sugar natural fibers, pulp, graphite or mixtures of two or more of these compounds.
  • Pore formers and / or pasting agents are preferably removed after deformation by at least one suitable drying and / or calcining step from the resultant 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 may be used, for example, in extruded, trilobium, quatrolob, star or hollow cylindrical form.
  • 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 used according to a) contains at least one catalytically active metal.
  • the catalyst contains a plurality of catalytically active metals.
  • metals is understood here 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.
  • Catalyst 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 prepared according to all process steps a) to c) contains 1 to 15 wt.% Molybdenum (Mo), in particular 3 to 12 wt.% Mo and 0 to 10 wt.%, Preferably 0.5 to 5 %
  • active metals for example those mentioned above, preferably Fe, Cu, Ni, Zn.
  • the catalyst already contains active metals prior to passivation in process step b).
  • the active metals can be applied wet-chemically or dry-chemically to the zeolite or the powder of zeolite and binder.
  • 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 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 to the zeolite.
  • the metal salts used here are preferably the nitrates, such as copper nitrate, nickel nitrate, iron nitrate and cobalt nitrate, but other salts known to the person skilled in the art for wet-chemical application can also 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 which applies the active metal or metals to the zeolite contains at least one complexing agent.
  • the Complexing agents selected from the group acetylacetonate, amino alcohols, EDTA, carboxylates such as oxalate and citrate and hydroxycarboxylic acid salts. Particular preference is given to using EDTA.
  • the active metal can be applied, for example, at higher temperatures from the gas phase by deposition on the zeolite.
  • molybdenum for example, gaseous Mo (CO) 6 is suitable for this purpose.
  • the catalyst according to a) is passivated in process step b) with a silicon-containing compound.
  • the catalytic reaction takes place at the acidic sites in the pores of the catalyst.
  • These acidic sites 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. at elevated temperature in polymeric silicon compounds, especially those having a basic structure of silica, can be converted.
  • 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 greater 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 may be mentioned in particular as suitable silicon compounds.
  • Silanes are silane (SihU) and its derivatives, ie compounds in which at least one hydrogen is replaced by another substituent.
  • silanes in which one to four H atoms are substituted by organic groups, halogens or hydroxyl groups.
  • 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 condense an Si-O-Si basic structure with elimination of water to form a polymeric compound.
  • Particular preference is given to silanes having 2 to 4 alkoxy groups, these are preferably around 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 first contacted with the silicon compound.
  • the catalyst may e.g. with the liquid silicon compound or a liquid preparation of the silicon compound, e.g. a solution in a suitable solvent (impregnation).
  • a suitable solvent e.g. a suitable solvent
  • silazanes such as hexamethylsilazane
  • organic solvents preferably polar solvents such as tetrahydrofuran suitable.
  • the silicon compound may also 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.
  • the silicon compound is mixed with other gases, e.g. Inert gas such as nitrogen or noble gas or the gaseous starting materials of the later reaction, e.g. Methane or natural gas, brought into contact with the catalyst.
  • gases e.g. Inert gas such as nitrogen or noble gas or the gaseous starting materials of the later reaction, e.g. Methane or natural gas, brought into contact with the catalyst.
  • this other gas may be contacted with the silicon compound at temperatures below the boiling point of the silicon compound and take up the silicon compound to saturation.
  • the gas mixtures preferably contain 0.01 to 10% by volume, in particular 0.1 to 2% by volume, of the silicon compound.
  • the catalyst can be present as a fixed bed or fluidized bed in the treatment with the gaseous silicon compound in a suitable apparatus, for example also the reactor used for a later dehydroaromatization. In a preferred embodiment of the present invention, the catalyst is present as a fluidized bed.
  • the catalyst treated with the silicon compound is then optionally dried to remove solvent. Such drying may be necessary when impregnating the catalyst with a liquid silicon compound or a liquid preparation of the silicon compound. The drying may e.g. in a separate process step prior to further reacting the silicon compound to a polymeric silicon layer at temperatures of from 20 to 150 ° C and optionally under reduced pressure, e.g. done under vacuum.
  • the reaction of the silicon compound to form a polymeric silicon layer is preferably carried out at elevated temperature.
  • the reaction to the polymeric silicon layer may be 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 Si-containing compound or of the reaction product obtained therefrom after a final calcination.
  • the above quantity is related only to the Si atom of the silicon-containing compound, because the content of the silicon introduced by the silicon compound does not change even in the further reaction 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.
  • C1-C4 aliphatic educt stream It is preferably the dehydroaromatization of a C1 -C4 aliphatic educt stream to benzene and optionally higher aromatics.
  • the C1-C4 aliphatic compounds may be, for example, 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. Preferably, the catalyst is contacted for activation with a gas of appropriate temperature. A previous activation may e.g. with a C1 -C4 alkane, e.g. Methane, ethane, propane, butane or a mixture thereof, preferably methane, take place.
  • a C1 -C4 alkane e.g. Methane, ethane, propane, butane or a mixture thereof, preferably methane
  • 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 at activation is 100 to 4000 h-1, preferably 500 to 2000 h-1.
  • 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 supply of the reactant stream into the reactor can be carried out, for example, with a GHSV (gas hourly space velocity) of 100 to 10,000 h-1, preferably 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 aliphates, 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 passivation; As a result, the life is increased and the time intervals between necessary regeneration of the catalyst significantly extended.
  • the application of active metal prior to passivation provides process advantages, e.g.
  • the active catalyst can be passivated directly in the dehydroaromatization reactor, thus saving a previous, separate dehydroaromatization process step.
  • H-ZSM-5 As the zeolite, ZSM-5 in the H-form (H-ZSM-5) was used.
  • an ammonium exchange exchange of residual alkali cations for ammonium cations and expulsion of ammonium as ammonia).
  • H-ZSM-5 19 kg of H-ZSM-5 were added to a solution of 19 kg of ammonium nitrate in 170 liters of water and stirred at 80 ° C for 2 hours. After cooling, the suspension was filtered in a filter press and washed with water. The process was repeated once more and the filter cake finally dried overnight at 120 ° C.
  • the obtained H-ZSM-5 was milled in the form of a 50% aqueous suspension in an agitating mill until the D50 value of the particle size distribution was ⁇ 3 ⁇ m, that is to say that more than 50% by weight of the zeolite particles had a diameter ⁇ 3 ⁇ had.
  • the aqueous mixture of H-ZSM-5 and binder was spray dried in a sputter dryer (Niro) using nitrogen as a sputtering gas.
  • the spray-dried catalyst particles were then further dried overnight at 120 ° C and then calcined in air at 500 ° C for 4 hours.
  • the catalyst obtained 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 was also soaked with solution 2 until the whole solution was taken up; the impregnated catalyst was again dried at 120 ° C. for 16 h) and then calcined (at 3 ° C. to 500 ° C. and after reaching 500 ° C. for 4 hours).
  • the catalyst thus treated contained 6.0% molybdenum and 1% nickel. passivation:
  • the resulting gas mixture was introduced into the heated to about 100 ° C fluidized bed reactor; the gas flow formed a stable fluidized bed.
  • the treatment of the fluidized bed with the gas flow was stopped and removed the catalyst from the reactor.
  • the catalyst treated in this way was again dried at 120 ° C. for 16 hours and calcined (at 3 ° C. to 500 ° C. and after reaching 500 ° C. for 4 hours).
  • 200 g of the above-prepared, spray-dried catalyst were passivated as described in the example with hexamethylsilazane in a fluidized bed reactor, then dried and calcined.
  • the catalyst was also soaked with solution 2 until the whole solution was taken up; the impregnated catalyst was again dried at 120 ° C. for 16 h) and then calcined (3 hours at 500 ° C. and 4 hours at 500 ° C.).
  • the catalyst thus treated contained 5.9% molybdenum and 0.95% nickel.
  • 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).
  • Each series included approximately 10 reaction cycles and 10 regeneration cycles.

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Abstract

L'invention concerne un procédé de production d'un catalyseur pour la déshydro-aromatisation, caractérisé en ce que a) un catalyseur qui continent un zéolithe et au moins un métal d'action catalytique, b) est passivé à l'aide d'un composé contenant un silicium puis c) est éventuellement calciné.
PCT/EP2014/055266 2013-03-27 2014-03-17 Passivation d'un catalyseur zélithique pour la déshydro-aromatisation Ceased WO2014154509A1 (fr)

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Cited By (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US10556801B2 (en) 2015-02-12 2020-02-11 Basf Se Process for the preparation of a dealuminated zeolitic material having the BEA framework structure

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US4145315A (en) * 1976-12-23 1979-03-20 Mobil Oil Corporation Silica-modified zeolite catalyst
US6153798A (en) * 1997-07-23 2000-11-28 Mitsubishi Gas Chemical Co., Ltd. Catalysts for methanol conversion reactions
US20020072642A1 (en) * 2000-07-27 2002-06-13 Allison Joe D. Catalyst and process for aromatic hydrocarbons production form methane
US20030144565A1 (en) * 2002-01-28 2003-07-31 Conoco Inc. Non-oxidative conversion of gas to liquids
CN1830927A (zh) * 2006-04-13 2006-09-13 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
CN101602646A (zh) * 2009-07-24 2009-12-16 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
CN101607864A (zh) * 2009-07-24 2009-12-23 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
EP2140938A1 (fr) * 2007-06-29 2010-01-06 Meidensha Corporation Catalyseur pour l'aromatisation d'hydrocarbures inférieurs et procédé pour la production de composés aromatiques

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Publication number Priority date Publication date Assignee Title
US4145315A (en) * 1976-12-23 1979-03-20 Mobil Oil Corporation Silica-modified zeolite catalyst
US6153798A (en) * 1997-07-23 2000-11-28 Mitsubishi Gas Chemical Co., Ltd. Catalysts for methanol conversion reactions
US20020072642A1 (en) * 2000-07-27 2002-06-13 Allison Joe D. Catalyst and process for aromatic hydrocarbons production form methane
US20030144565A1 (en) * 2002-01-28 2003-07-31 Conoco Inc. Non-oxidative conversion of gas to liquids
CN1830927A (zh) * 2006-04-13 2006-09-13 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
EP2140938A1 (fr) * 2007-06-29 2010-01-06 Meidensha Corporation Catalyseur pour l'aromatisation d'hydrocarbures inférieurs et procédé pour la production de composés aromatiques
CN101602646A (zh) * 2009-07-24 2009-12-16 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
CN101607864A (zh) * 2009-07-24 2009-12-23 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

Cited By (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US10556801B2 (en) 2015-02-12 2020-02-11 Basf Se Process for the preparation of a dealuminated zeolitic material having the BEA framework structure

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