WO2009124902A1 - Catalyseur de déhydroaromatisation d'hydrocarbures aliphatiques, contenant un liant à teneur en silicium - Google Patents

Catalyseur de déhydroaromatisation d'hydrocarbures aliphatiques, contenant un liant à teneur en silicium Download PDF

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Publication number
WO2009124902A1
WO2009124902A1 PCT/EP2009/054078 EP2009054078W WO2009124902A1 WO 2009124902 A1 WO2009124902 A1 WO 2009124902A1 EP 2009054078 W EP2009054078 W EP 2009054078W WO 2009124902 A1 WO2009124902 A1 WO 2009124902A1
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zeolite
catalyst
mixture
catalyst according
drying
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PCT/EP2009/054078
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German (de)
English (en)
Inventor
Joana Coelho Tsou
Frank Kiesslich
Bilge Yilmaz
Sebastian Ahrens
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Basf Se
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Priority to DE112009000581T priority Critical patent/DE112009000581A5/de
Publication of WO2009124902A1 publication Critical patent/WO2009124902A1/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
    • B01J29/70—Crystalline aluminosilicate zeolites; Isomorphous compounds thereof of types characterised by their specific structure not provided for in groups B01J29/08 - B01J29/65
    • B01J29/78—Crystalline aluminosilicate zeolites; Isomorphous compounds thereof of types characterised by their specific structure not provided for in groups B01J29/08 - B01J29/65 containing arsenic, antimony, bismuth, vanadium, niobium, tantalum, polonium, chromium, molybdenum, tungsten, manganese, technetium or rhenium
    • B01J29/7876—MWW-type, e.g. MCM-22, ERB-1, ITQ-1, PSH-3 or SSZ-25
    • 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
    • B01J29/064—Crystalline aluminosilicate zeolites; Isomorphous compounds thereof containing iron group metals, noble metals or copper
    • B01J29/068—Noble metals
    • 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
    • B01J29/076—Crystalline aluminosilicate zeolites; Isomorphous compounds thereof 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
    • B01J29/04—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
    • 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
    • B01J21/00—Catalysts comprising the elements, oxides, or hydroxides of magnesium, boron, aluminium, carbon, silicon, titanium, zirconium, or hafnium
    • B01J21/06—Silicon, titanium, zirconium or hafnium; Oxides or hydroxides thereof
    • B01J21/08—Silica
    • 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
    • B01J2229/16—After treatment, characterised by the effect to be obtained to increase the Si/Al ratio; Dealumination
    • 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
    • B01J2229/10—After treatment, characterised by the effect to be obtained
    • B01J2229/20—After treatment, characterised by the effect to be obtained to introduce other elements in the catalyst composition comprising the molecular sieve, but not specially in or on the molecular sieve itself
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J2229/00—Aspects of molecular sieve catalysts not covered by B01J29/00
    • B01J2229/30—After treatment, characterised by the means used
    • B01J2229/42—Addition of matrix or binder particles
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • 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
    • B01J29/44—Noble metals
    • 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
    • B01J29/70—Crystalline aluminosilicate zeolites; Isomorphous compounds thereof of types characterised by their specific structure not provided for in groups B01J29/08 - B01J29/65
    • B01J29/72—Crystalline aluminosilicate zeolites; Isomorphous compounds thereof of types characterised by their specific structure not provided for in groups B01J29/08 - B01J29/65 containing iron group metals, noble metals or copper
    • B01J29/74—Noble metals
    • B01J29/7476—MWW-type, e.g. MCM-22, ERB-1, ITQ-1, PSH-3 or SSZ-25
    • 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
    • B01J35/60—Catalysts, in general, characterised by their form or physical properties characterised by their surface properties or porosity
    • B01J35/61—Surface area
    • B01J35/615—100-500 m2/g
    • 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

Definitions

  • the present invention relates to a catalyst for the dehydroaromatization of d-C 4 -Aliphaten, which is obtainable by treating twice a zeolite with NH 4 -containing mixtures.
  • the catalyst contains at least one silicon-containing binder and at least one metal selected from Mo, W, Re, Ir, Ru, Rh, Pt and Pd.
  • Another object of the present invention is a process for the preparation of the catalyst and a process for the dehydroaromatization of dC 4 -Aliphaten by reacting a Ci-C 4 -Aliphaten-containing mixture in the presence of the catalyst.
  • Aromatic hydrocarbons such as benzene, toluene, ethylbenzene, styrene, xylene and naphthalene are important intermediates in the chemical industry, whose demand is still increasing. As a rule, they are obtained by catalytic reforming of naphtha, which in turn is obtained from petroleum. Recent research shows that world oil reserves are more limited compared to natural gas reserves. Therefore, the production of aromatic hydrocarbons from educts that can be obtained from natural gas is now an economically interesting alternative.
  • the main component of natural gas is usually methane.
  • DHAM non-oxidative dehydroaromatization
  • H-ZSM-5 zeolites modified with molybdenum have been found to be particularly suitable.
  • Catalysts for the dehydroaromatization of methane occur.
  • the deactivation of the catalyst by coke deposits is a major problem.
  • the coke deposits also have an unfavorable effect on the material balance or the yield, since each molecule of starting material which is converted into coke is no longer available for the desired reaction to aromatics.
  • the coke selectivities achieved hitherto in the prior art are in most cases more than 20% based on the reacted aliphatics.
  • the object is achieved by a catalyst for the dehydroaromatization of aliphatic hydrocarbons containing at least one zeolite, at least one silicon-containing binder and at least one metal selected from the group Mo, W, Re, Ir, Ru, Rh, Pt and Pd, obtainable by the steps
  • the catalysts according to the invention are particularly suitable for the nonoxidative dehydroaromatization of C 1 -C 4 -aliphatics, ie for the preparation of aromatic hydrocarbon compounds such as benzene and toluene from these aliphatic compounds under non-oxidative conditions.
  • the reactant stream used can be used more economically, since less starting material is converted into harmful for the catalyst and the yield-reducing coke.
  • the low coke selectivity is accompanied by significantly higher conversions and / or higher benzene selectivities in the catalysts according to the invention, which leads to higher overall benzene yields.
  • Another great advantage of the catalysts of the invention is their good regenerability. Even after several reaction and regeneration cycles, the initial activity of the catalyst in the first cycle is usually reached again by the regeneration.
  • Non-oxidative conditions means that the concentration of oxidizing agents such as oxygen or nitrogen oxides in the starting material E below 5 wt .-%, preferably below 1 wt .-%, more preferably below 0.1 wt. -% lies. Most preferably, the mixture is free of oxygen. It is also particularly preferred that the concentration of oxidizing agents in mixture E be equal to or less than the concentration of oxidizing agents in the source from which the CrC 4 aliphates are derived.
  • the catalysts of the invention contain at least one zeolite.
  • Zeolites are aluminum silicates which are usually produced in the sodium form during their preparation. In the Na form, the excess negative charge due to the exchange of 4-valent Si atoms for 3-valent Al atoms in the crystal lattice is compensated by Na ions.
  • the zeolite can also contain other alkali metal and / or alkaline earth metal ions for charge balance.
  • the at least one zeolite contained in the catalysts preferably has a structure which is selected from the structural types pentasil and MWW and is particularly preferably selected from the structural types MFI, MEL, mixed structures of MFI and MEL and MWW.
  • zeolite of the ZSM-5 or MCM-22 type Very particular preference is given to using a zeolite of the ZSM-5 or MCM-22 type.
  • the names of the structure types of the zeolites correspond to the data in WM Meier, DH Olson and Baerlocher, "Atlas of Zeolite Structure Types", Elsevier, 3rd edition, Amsterdam 2001.
  • the synthesis of zeolites is known in the art and can be carried out, for example, starting from alkali aluminate, alkali silicate and amorphous SiO 2 under hydrothermal conditions Templated organic molecules are used to control the temperature and other experimental parameters of the type of channel systems formed in the zeolite.
  • Step I of the process according to which the catalyst according to the invention is obtainable consists in the conversion of the zeolite into the so-called H form.
  • a common and preferred method according to the present invention for converting the zeolite into the H form is a two-step process in which the alkali and / or alkaline earth ions are first exchanged for ammonium ions. When the zeolite is heated to about 400 to 500 ° C., the ammonium ion decomposes into volatile ammonia and into the proton remaining in the zeolite.
  • the zeolite is treated with an NH 4 -containing mixture.
  • the NH 4 -containing component of the NH 4 -containing mixture is an ammonium salt selected from the group consisting of ammonium chloride, ammonium carbonate, ammonium hydrogencarbonate, ammonium nitrate, ammonium phosphate, ammonium hydrogenphosphate, ammonium dihydrogenphosphate, ammonium sulfate, ammonium acetate and ammonium hydrogensulfate.
  • Ammonium nitrate is preferably used as the NH 4 -containing component.
  • the treatment of the zeolite with the NH 4 -containing mixture is carried out according to the known, suitable for the ammonium exchange of zeolites methods. These include, for example, soaking, dipping or spraying the zeolite with an ammonium salt solution, the solution generally being used in excess.
  • the solvents used are preferably water or alcohols.
  • the solution usually contains 1 to 20 wt .-% of the NH 4 component used.
  • the treatment with the NH 4 -containing mixture is usually carried out over a period of several hours and at elevated temperatures. After the action of the NH 4 -containing mixture on the zeolite, excess mixture can be removed and the zeolite washed.
  • the duration of the calcination is usually 2 to 24 hours, preferably 3 to 10 hours, and more preferably 4 to 6 hours.
  • step II of the present process after which the catalyst according to the invention is obtainable, the zeolite is treated again with a NH 4 -containing mixture and then dried.
  • the zeolite is calcined following the drying in step II. Calcination takes place at the conditions specified for the calcination in step I.
  • the catalyst according to the invention is obtainable according to this preferred embodiment by the following process comprising the steps
  • step I of the process after which the catalyst according to the invention is obtainable has already been obtained from the manufacturer of the present invention Zeolite performed. Therefore, according to the invention, commercially obtained zeolites in the H form can be used directly in step II of the process according to the invention.
  • the catalysts of the present invention comprise at least one element selected from the group consisting of Mo, W, Re, Ir, Ru, Rh, Pt and Pd, preferably Mo. These elements are referred to below as the active component. According to the invention, this at least one element is applied to the zeolite wet-chemically or dry-chemically in step III of the process.
  • the at least one active component is applied in the form of aqueous, organic or organic-aqueous solutions of its salts or complexes by impregnating the zeolite with the appropriate solution.
  • a solvent can also serve 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 maturing, 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 molybdenum compound are (NH 4 ) GMo 7 O 24 , MoO 2 , MoO 3 , H 2 MoO 4 , Na 2 MoO 4 , (NH 3 ) 3 Mo (CO) 3 and Mo (CO) 6 , as tungsten compounds in particular WCI 4 , WCI 6 , WO 3 , WO 2 CI 2 , W (NCCH 3 ) 3 (CO) 3 , WC, (NH 4 ) 6 W 12 O 39 and W (CO) 6 , in particular ReCl 5 can be used as rhenium compounds , ReCl 3 , Re (CO) 5 Cl, Re (CO) 5 Br, Re 2 (CO) i 0 , Re 2 O 7 , ReO 3 , ReO 2 , NH 4 ReO 4 , K 2 ReCl 6 , Na 2 ReCl 6 are used.
  • the catalyst is dried at about 80 to 130 0 C usually for 4 to 20 hours
  • the at least one active component can also be applied by dry chemical methods, for example by precipitating gaseous metal carbonyls such as Mo (CO) 6 from the gas phase on the zeolite at higher temperatures.
  • the deposition of the metal carbonyl compound is usually carried out before or after the calcination of the zeolite according to step IV.
  • the catalyst contains 0.1 to 20 wt .-%, preferably 0.2 to 15 wt .-%, particularly preferably 0.5 to 10 wt .-%, each based on the total weight of the catalyst, at least one element selected from the group Mo, W, Re, Ir, Ru, Rh, Pt and Pd, preferably 0.1 to 20 wt .-%, preferably 0.2 to 15 wt .-%, particularly preferably 0.5 to 10 wt. % Not a word.
  • binder precursors are, for example, tetraalkoxysilanes or a mixture of two or more different tetraalkoxysilanes.
  • binders which consist either entirely or partially of SiC> 2 and binders which are wholly or partially a precursor to SiO 2 , from which SiO 2 is then formed during the production of the moldings.
  • SiO 2 -containing inorganic binders are colloidal silicon dioxide, so-called “wet process” silicon dioxide and so-called “dry process” silicon dioxide.
  • Colloidal silica is commercially available as, for example, Ludox®, Syton®, Nalco® or Snowtex®.
  • Weight process silica is commercially available as, for example, Hi-Sil®, Ultrasil®, Vulcasil®, Santocel®, Valron-Estersil®, Tokusil® or Nipsil®.
  • “Dry process” silica is commercially available as, for example, Aerosil®, Reolosil®, Cab-O-Sil®, Fransil® or ArcSilica®.
  • organosilicon binders are particularly suitable. These are in each case monomeric, oligomeric or polymeric silanes, alkoxysilanes, aryloxysilanes, acyloxysilanes, oximinosilanes, halosilanes, aminooxysilanes, aminosilanes, amidosilanes, silazanes or silicones, as described, for example, in Ullman's Encyclopedia of Industrial Chemistry, Vol. A24 on pages 21 to 56 are. Examples of oligomeric and polymeric organosilicon compounds are methyl silicones and ethyl silicones. Particularly preferred organosilicon binders are methyl silicone (commercially available as 70 wt .-% - solution in toluene about under the name Silres ®).
  • the binders are preferably used in an amount which leads to ultimately resulting moldings whose binder content is in the range from 5 to 80% by weight, preferably in the range from 10 to 50% by weight and more preferably in the range from 10 to 30 % By weight, in each case based on the total weight of the resulting final molding.
  • the mixture F comprising at least one binder or precursor to form a binder and at least one zeolite can be mixed with at least one further compound for further processing and for the formation of a plastic mass.
  • the mixture F contains at least one pasting agent.
  • Pasting agents are compounds that improve the mixing, kneading and flow properties of the molding compound.
  • Suitable compounds can be used. These are preferably organic, in particular hydrophilic polymers such as cellulose, cellulose derivatives such as methylcellulose, starch such as potato starch, wallpaper patches, wallpaper pastes, polyacrylates, polymethacrylates, polyvinyl alcohol, polyvinylpyrrolidone, polyisobutene, polytetrahydrofuran, polyglycol ethers, fatty acid compounds, wax emulsions, water or mixtures two or more of these compounds.
  • hydrophilic polymers such as cellulose, cellulose derivatives such as methylcellulose, starch such as potato starch, wallpaper patches, wallpaper pastes, polyacrylates, polymethacrylates, polyvinyl alcohol, polyvinylpyrrolidone, polyisobutene, polytetrahydrofuran, polyglycol ethers, fatty acid compounds, wax emulsions, water or mixtures two or more of these compounds.
  • the mixture F contains at least one pore-forming agent.
  • all compounds which provide a specific pore size, a specific pore size distribution and / or specific pore volumes with respect to the finished shaped article can be used as pore formers.
  • Polymers which are dispersible, suspendable or emulsifiable in water or in aqueous solvent mixtures are preferably used as pore formers in the process according to the invention.
  • Preferred polymers here are polymeric vinyl compounds such as, for example, polyalkylene oxides, such as polyethylene oxides, polystyrene, polyacrylates, polymethacrylates, polyolefins, polyamides and polyesters, carbohydrates, such as cellulose or cellulose derivatives, for example methylcellulose, or sugars or natural fibers.
  • Other suitable pore formers are for example PuIp or graphite.
  • two or more pore-forming agents can also be used, in particular if this is desired for the pore size distribution to be achieved.
  • the order of addition of the components of the mixture F containing the at least one zeolite is not critical. It is both possible first to add the at least one binder, then to interchange the at least one pore former and finally the at least one pasting agent, as well as the order with respect to the at least one binder, the at least one pore former and the at least one pasting agent.
  • the mixture F is homogenized according to (ii). This usually takes 10 to 180 minutes. Kneaders, rollers or extruders are particularly preferably used for homogenization. Preferably, the mixture is kneaded. On an industrial scale is preferably gekollert for homogenization.
  • the homogenization is usually carried out at temperatures in the range of about 10 0 C to the boiling point of the pasting agent and normal pressure or slightly superatmospheric pressure.
  • the mixture thus obtained is usually homogenized, preferably kneaded, until a distensible plastic mass has formed.
  • a shaping step (iii) takes place, in which the mixture F is shaped according to the processes known to the person skilled in the art to obtain at least one shaped article.
  • spray-drying of a suspension containing the mixture F, tabletting, pelleting, compression in the moist or dry state and, for example, as shaping processes are To call extruding. Two or more of these methods can also be combined.
  • compaction of the mixture F is part of the shaping.
  • those processes are preferred for the shaping processes in which the deformation takes place by extrusion in conventional extruders, for example into strands having a diameter of preferably 1 to 10 mm and more preferably 2 to 5 mm.
  • extrusion devices are described, for example, in Ullmann's Enzyklopadie der Technischen Chemie, 4th Edition, Vol. 2, p. 295 et seq., 1972.
  • extrusion press it is also preferable to use an extrusion press for deformation.
  • Step (iii) in the context of the present invention is followed by at least one drying step (iv).
  • This at least one drying step (iv) is carried out at temperatures in the range of generally 80 to 160 0 C, preferably from 90 to 145 0 C and particularly preferably from 100 to 130 0 C, wherein the drying time is generally 6 hours or more, for example in the range of 6 to 24 hours.
  • shorter drying times for example 1, 2, 3, 4 or 5 hours, are also possible.
  • the geometry of the catalysts obtainable according to the invention can be, for example, spherical (hollow or full), cylindrical (hollow or full), ring, saddle, star, honeycomb or tablet shape.
  • extrudates are for example in strand, trilobium, Quatrolob-, star or hollow cylindrical shape in question.
  • the extrudates preferably obtained may be broken before and after the drying step (iv) and optionally after a successful calcination 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.
  • the catalyst is used as a shaped body or grit.
  • the steps (i) to (iv) for the preparation of shaped catalyst bodies can be carried out between step I and step II or step II and step III of the process after which the catalyst according to the invention is obtainable.
  • the preparation of the shaped catalyst bodies (steps (i) to (iv)) between step I and step II or between step II and step III is followed in a preferred embodiment by drying (iv) by a calcining step (v).
  • the catalyst is obtainable by the following process comprising the steps
  • the calcining step (v) is carried out when the preparation of the shaped catalyst bodies is carried out between step I and step II.
  • the temperatures remaining the same during a calcining step or continuously or discontinuously can be changed. If calcination is performed twice or more times, the calcination temperatures in the individual steps may differ or be the same.
  • the catalyst is calcined both following the drying in step II and the calcination according to step (v) is carried out in the preparation of the shaped catalyst bodies.
  • the catalyst according to this embodiment is obtainable through the steps
  • the catalyst contains as doping at least one further element selected from the group Mn, Cr, Zr, V, Zn,
  • the catalyst which, in addition to molybdenum, contain Cu as doping.
  • the catalyst contains, in addition to molybdenum as doping, Ni.
  • the catalyst according to the invention contains more than one further element selected from the group Mn, Cr, Zr, V, Zn, Ga, Cu, Ni, Fe and Co as doping in addition to at least one active component.
  • the doping is present in the catalyst according to the invention in a concentration of at least 0.1 wt .-%, based on the total weight of the catalyst before.
  • the catalysts according to the invention particularly preferably contain at least 0.2% by weight, very particularly preferably at least 0.5% by weight of at least one further element selected from among Mn, Cr, Zr, V, Zn, Ga, Cu, Ni, Fe and Co as a doping, based on the total weight of the catalyst.
  • catalysts which contain from 0.1 to 20% by weight of molybdenum and at least 0.1% by weight of Cu, based on the total weight of the catalyst.
  • Mo- and Cu-containing catalysts contain MCM-22 as zeolite.
  • catalysts which contain 0.1 to 20% by weight of Mo and at least 0.1% by weight of Ni, particularly preferably 0.1 to 20% by weight of Mo and 0.5 to 2% by weight. % Ni, in each case based on the total weight of the catalyst.
  • the Ni and Cu containing catalysts contain ZSM-5 as zeolite.
  • halides especially chloride, acetate, alkaline carbonates, formate, tartrate, acetate, complexes with ligands such as acetylacetonate, amino alcohols, EDTA, carboxylates such as oxalate, citrate, etc., and Hydroxycarbonklaresalze.
  • step III If the active component is applied in step III by dry-chemical means, the impregnation with the doping is usually carried out before step III. Between the impregnation and the dry chemical application of the active component is then usually calcined again. If more than one further element is applied as doping, these can be applied together or in succession, with drying taking place between the individual impregnation stages. It may be advantageous to apply the individual elements in a certain order.
  • the catalyst After applying at least one active component according to step III of the process, after which the catalyst according to the invention is obtainable, the catalyst is re-calcined in step IV.
  • the calcination is carried out according to the conditions given above for the calcination.
  • Another object of the present invention is a process for the preparation of a catalyst for the dehydroaromatization of CrC 4 -Aliphaten, containing at least one silicon-containing binder and at least one element selected from the group Mo, W, Re, Ir, Ru, Rh, Pt and Pd as above described comprising the steps
  • the present invention is the use of the above-described catalyst according to the invention for the dehydroaromatization of a starting material E containing C 1 -C 4 -aliphatic compounds, in particular the use for non-oxidative dehydroaromatization is preferred according to the invention.
  • This activation can be carried out with a CrC 4 -alkane, such as, for example, methane, ethane, propane, butane, or a mixture thereof, preferably butane.
  • the activation is carried out at a temperature of 250 to 850 0 C, preferably at 350 to 650 0 C, and a pressure of 0.5 to 5 bar, preferably at 0.5 to 2 bar performed.
  • the GHSV (gas hourly space velocity) at activation is 100 to 4000 h -1 , preferably 500 to 2000 h -1 .
  • the activation is carried out at a temperature of 250 to 650 ° C., preferably at 350 to 550 ° C., and at a pressure of 0.5 to 5 bar, preferably at 0.5 to 2 bar.
  • the GHSV (gas hourly space velocity) at activation is 100 to 4000 h -1 , preferably 500 to 2000 h -1 .
  • the catalyst is activated with a gas stream containing H 2 and / or CH 4 , which may additionally contain inert gases such as N 2 , He, Ne and Ar.
  • the present invention further provides a process for the dehydroaromatization of a feed stream E comprising C 1 -C 4 -aliphates by reacting the feed stream E in the presence of a catalyst as described above, which is obtainable by the following steps: I. treating at least one zeolite with an NH 4 -containing mixture, followed by drying and calcination of the zeolite,
  • step I the steps or between step II and step III
  • the reactant stream E contains at least one aliphatic having 1 to 4 carbon atoms.
  • these aliphatics include, for example, methane, ethane, propane, n-butane, i-butane, ethene, propene, 1- and 2-butene, isobutene, etc., more preferably the starting material stream E contains aliphatic compounds having 1 to 4 carbon atoms.
  • the reactant stream E contains at least 50 mol%, preferably at least 60 mol%, particularly preferably at least 70 mol%, even more preferably at least 80 mol%, in particular at least 90 mol%, of CrC 4 aliphatics ,
  • the reactant stream E preferably contains at least 50 mol%, preferably at least 60 mol%, particularly preferably at least 70 mol%, most preferably at least 80 mol%, in particular at least 90 mol%, of methane.
  • natural gas is used as the source of the Ci-C 4 -Aliphaten.
  • the typical composition of natural gas is as follows: 75 to 99 mol% methane, 0.01 to 15 mol% ethane, 0.01 to 10 mol% propane, up to 6 mol% butane and higher hydrocarbons, up to 30 mol% of carbon dioxide, up to 30 mol% of hydrogen sulfide, up to 15 mol% of nitrogen and up to 5 mol% of helium.
  • the natural gas can be purified and enriched prior to use in the process according to the invention by methods known to those skilled in the art. Purification includes, for example, the removal of any hydrogen sulfide or carbon dioxide present in natural gas and other undesirable compounds in the subsequent process.
  • the feed stream E may additionally contain ammonia, traces of lower alcohols and further admixtures typical of biogas.
  • hydrogen, steam, carbon monoxide, carbon dioxide, nitrogen and one or more noble gases can be admixed with the reactant stream E.
  • the reaction is carried out at a GHSV (Gas Hourly Space Velocity) of 100 to 10,000 h -1 , preferably 200 to 3000 h -1 .
  • the catalysts according to the invention which contain at least one further element selected from the group Cu, Ni, Fe and Co, can be easily regenerated by means of hydrogen.
  • the dehydroaromatization of Ci-C 4 -Aliphaten can in principle be carried out in all known from the prior art reactor types.
  • a suitable reactor form is the fixed bed, tube or shell and tube reactor.
  • the catalyst is as a fixed bed in a reaction tube or in a bundle of reaction tubes.
  • the catalysts according to the invention can be used as fluidized bed, moving bed or fluidized bed in the appropriate, suitable reactor types and the process according to the invention for dehydroaromatization can be carried out with the catalysts present in this way.
  • 100 g of a commercially available ZSM-5 zeolite in H form are mixed with 100 g of ammonium nitrate and 900 g of water and heated for 2 hours in a stirred apparatus at 80 0 C. After cooling, the suspension is filtered and washed with water. The filter cake is dried at 120 0 C overnight.
  • the microstructure of the untreated and treated with NH 4 NOs H-PZ2-25 zeolites was determined by nitrogen adsorption (Quantachrom Autosorb). The nitrogen was adsorbed at -196 0 C, the Ausgastemperatur was 200 0 C, the Ausgaszeit 14 hours.
  • the pore volume (total) indicates the pore volume of all pores with a diameter below 335.47 nm. Pores with a diameter of 0 to 2 nm are regarded as micropores, pores with a diameter of 2 to 50 nm as mesopores and pores with a pore diameter> 50 nm (IUPAC) as macroporous.
  • Table 3 shows the results of the characterization of the zeolite microstructure.
  • a zeolite 100 g are impregnated according to C with molybdenum, but finally only dried and not calcined.
  • the corresponding Mo-loaded zeolite is placed in a dish.
  • Approximately 4.1 g of copper (II) nitrate 2.5 hydrate (> 99%, Ried-de-Haen) are made up with water to the corresponding volume of the water uptake (about 100 ml) of the zeolite and to the stirred to complete dissolution.
  • the solution is then added with stirring to the zeolite and the mass further mixed for 15 min at room temperature.
  • the mass is then dried in the dry Cabinet heated to 120 0 C, dried overnight and then calcined at 500 0 C for 5 h.
  • zeolite 100 g of a (optionally pretreated with NH 4 NO 3 according to A) zeolite are placed in a shell. Approximately 4.1 g of copper (II) nitrate 2.5 hydrate (> 99%, Riedel-de- Haen) are made up with water to the appropriate volume of water absorption (about 100 ml) of the zeolite and until complete dissolution touched. The solution is then added with stirring to the zeolite and the mass further mixed for 15 min at room temperature. The mass is then heated in a drying oven to 120 0 C and dried overnight, but not calcined. Subsequently, the already Cu-loaded catalyst is impregnated according to C with Mo.
  • the catalyst was prepared from the thus obtained carrier according to C and tested according to G.
  • Example 6 6% by weight Mo / 1% by weight Cu on H-ZSM-5 (powder) (not according to the invention)
  • Example 7 6% by weight of Mo on H-ZSM-5 (chippings) (not according to the invention)
  • the catalyst was prepared from the resulting grit according to C and tested according to G.
  • Example 8 6% by weight Mo / 1% by weight Cu on H-ZSM-5 (powder) (not according to the invention)
  • Example 9 6% by weight of Mo on H-ZSM-5 (chippings) (according to the invention)
  • the catalyst was prepared from the resulting grit according to C and tested according to G.
  • Example 10 6% by weight Mo / 1% by weight Cu on H-ZSM-5 (chippings) (according to the invention)
  • Example 11 6% by weight Mo / 1% by weight Cu on H-ZSM-5 (chippings) (according to the invention)
  • the catalyst was prepared from the resulting grit according to F and tested according to G.
  • the catalyst was prepared from the grit thus obtained according to E and tested according to G.
  • Example 13 6% by weight Mo / 1% by weight Ni on H-ZSM-5 (chippings) (according to the invention)
  • the catalyst was prepared from the resulting grit according to F, with 20 g of zeolite, about 2.4 g of the molybdate compound and about 1.06 g of nickel (II) nitrate hexahydrate (> 99%, Riedel). de-Haen) were used with about 20 ml of water.
  • the catalyst was tested according to G.
  • Example 14 6% by weight Mo / 1% by weight Cu on H-MCM-22 (chippings) (according to the invention)
  • the catalysts of the invention show high benzene selectivities with low coke selectivities and high methane conversions.
  • the two catalysts of the invention differ in the zeolite used; in Example 11, a ZSM-5 zeolite, in Example 14, an MCM-22 zeolite was used. Both catalysts show extremely low coke selectivities compared to the catalysts not according to the invention shown in Table 4, wherein, when comparing with the values in Table 4, it should be taken into account that the data shown there after 7 h reaction time, those from Table 5 after 5 h Response time were recorded.
  • the MCM-22 containing catalyst has a significantly higher selectivity for benzene and a slightly reduced selectivity to coke compared to the ZSM-5-containing catalyst.

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Abstract

L'invention concerne un catalyseur de déhydroaromatisation de composés acycliques C1-C4, obtenu par double traitement d'une zéolithe avec des mélanges contenant NH4. Ce catalyseur contient au moins un liant à teneur en silicium et au moins un métal sélectionné dans le groupe comprenant Mo, W, Re, Ir, Ru, Rh, Pt et Pd. L'invention porte également sur un procédé de production d'un catalyseur et sur un procédé de déhydroaromatisation de composés acycliques C1-C4 par mise en réaction d'un mélange contenant des composés acycliques C1-C4 en présence d'un catalyseur.
PCT/EP2009/054078 2008-04-08 2009-04-06 Catalyseur de déhydroaromatisation d'hydrocarbures aliphatiques, contenant un liant à teneur en silicium WO2009124902A1 (fr)

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DE112009000581T DE112009000581A5 (de) 2008-04-08 2009-04-06 Katalysator zur Dehydroaromatisierung von aliphatischen Kohlenwasserstoffen mit siliziumhaltigem Bindemittel

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Cited By (15)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US8742189B2 (en) 2008-04-08 2014-06-03 Basf Se Catalyst for the dehydroaromatisation of methane and mixtures containing methane
US8785704B2 (en) 2008-05-21 2014-07-22 Basf Se Process for obtaining benzene, toluene (and naphthalene) from C1-C4-alkanes with co-dosage of hydrogen at a separate location
US9260313B2 (en) 2009-03-03 2016-02-16 Basf Se Process for the preparation of pillared silicates
US8487152B2 (en) 2009-04-06 2013-07-16 Basf Se Process for converting natural gas to aromatics with electrochemical removal of hydrogen to generate electrical power and obtain hydrogen
US8609914B2 (en) 2009-04-06 2013-12-17 Basf Se Process for converting natural gas to aromatics with electrochemical removal of hydrogen
US8729331B2 (en) 2009-04-06 2014-05-20 Basf Se Method for electrochemically removing hydrogen from a reaction mixture
US8796496B2 (en) 2009-09-03 2014-08-05 Basf Se Process for preparing benzene from methane
WO2011042451A1 (fr) * 2009-10-08 2011-04-14 Basf Se Procédé de fabrication d'un catalyseur en lit fluidisé relié à si
EA024080B1 (ru) * 2009-10-08 2016-08-31 Басф Се Способ получения связанного с кремнием псевдоожиженного катализатора, получаемый им гранулированный псевдоожиженный катализатор, его применение для неокислительной дегидроароматизации c-c-алифатических соединений и способ неокислительной дегидроароматизации c-c-алифатических соединений
US9486796B2 (en) 2009-10-08 2016-11-08 Basf Se Process for producing an si-bonded fluidized-bed catalyst
US9821300B2 (en) 2009-10-08 2017-11-21 Basf Se Process for producing an Si-bonded fluidized-bed catalyst
US9517461B2 (en) 2009-12-18 2016-12-13 Basf Se Ferrous zeolite, method for producing ferrous zeolites, and method for catalytically reducing nitrous oxides
CN110882721A (zh) * 2018-09-10 2020-03-17 国家能源投资集团有限责任公司 芳构化催化剂及其制备方法和应用
US20210275995A1 (en) * 2020-03-06 2021-09-09 Korea University Research And Business Foundation Dissimilar metal-supported catalyst for the production of aromatics by methane dehydroaromatization and method for producing aromatics using the same
US11919832B2 (en) * 2020-03-06 2024-03-05 Korea University Research And Business Foundation Dissimilar metal-supported catalyst for the production of aromatics by methane dehydroaromatization and method for producing aromatics using the same

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