EP2282835A1 - Procédé de déshydroaromatisation de mélanges contenant du méthane avec régénération des catalyseurs correspondants exempts de métaux précieux - Google Patents

Procédé de déshydroaromatisation de mélanges contenant du méthane avec régénération des catalyseurs correspondants exempts de métaux précieux

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Publication number
EP2282835A1
EP2282835A1 EP09729859A EP09729859A EP2282835A1 EP 2282835 A1 EP2282835 A1 EP 2282835A1 EP 09729859 A EP09729859 A EP 09729859A EP 09729859 A EP09729859 A EP 09729859A EP 2282835 A1 EP2282835 A1 EP 2282835A1
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EP
European Patent Office
Prior art keywords
catalyst
carrier
zeolite
regeneration
active component
Prior art date
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Application number
EP09729859A
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German (de)
English (en)
Inventor
Frank Kiesslich
Joana Coelho Tsou
Alexander Schulz
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BASF SE
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BASF SE
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Publication date
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Priority to EP09729859A priority Critical patent/EP2282835A1/fr
Publication of EP2282835A1 publication Critical patent/EP2282835A1/fr
Withdrawn legal-status Critical Current

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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
    • C07C2/78—Processes with partial combustion
    • 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
    • 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
    • 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
    • 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
    • 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
    • B01J37/00—Processes, in general, for preparing catalysts; Processes, in general, for activation of catalysts
    • B01J37/0009—Use of binding agents; Moulding; Pressing; Powdering; Granulating; Addition of materials ameliorating the mechanical properties of the product catalyst
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J37/00—Processes, in general, for preparing catalysts; Processes, in general, for activation of catalysts
    • B01J37/16—Reducing
    • B01J37/18—Reducing with gases containing free hydrogen
    • 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
    • Y02P20/584—Recycling of catalysts

Definitions

  • the present invention relates to a process for the non-oxidative dehydroaromatization of aliphatic hydrocarbons by reacting a reactant stream comprising aliphatic hydrocarbons in the presence of a catalyst comprising at least one metallosilicate as support, at least one element selected from Mo, W and Re as active component and at least one another transition metal, which is not a noble metal, as doping, wherein the catalyst is regenerated regularly under non-oxidative conditions with hydrogen.
  • a catalyst comprising at least one metallosilicate as support, at least one element selected from Mo, W and Re as active component and at least one another transition metal, which is not a noble metal, as doping, wherein the catalyst is regenerated regularly under non-oxidative conditions with hydrogen.
  • a catalyst comprising at least one metallosilicate as support, at least one element selected from Mo, W and Re as active component and at least one another transition metal, which is not a noble metal, as doping, wherein the catalyst is regenerated regularly under non-oxidative conditions with
  • 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 studies show that global 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 which have been modified with molybdenum and doped with further elements have proven particularly suitable.
  • Y. Xu et al. (Journal of Catalysis 216, (2003), pages 386 to 395) describe in a review the problems that occur when using molybdenum-containing H-ZSM-5 catalysts for the dehydroaromatization of methane. In particular, the deactivation of the catalyst by coke deposits is a major problem.
  • Y. Xu et al. summarize some of the possibilities described in the literature for improving the activity and stability of Mo / H-ZSM-5 catalysts, such as steam dealumination, dealumination by acidic solutions, or silanization.
  • H-ZSM-5 zeolites were prepared by aqueous solutions containing ammonium nitrate and sodium chloride in different concentrations, subjected to a partial or complete ion exchange to obtain zeolites which are completely, only partially or not at all in the H-form.
  • the zeolites were then doped with Ga, Zn or Cr in conjunction with Ru or Pt and Mo, Cu, Zn and Fe. There were found metal conversions of 0.2 to 7.9% at benzene selectivities from 0 to almost 80%.
  • coke deposits called coking 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.
  • Coking also poses a major problem for the industrial use of dehydroaromatization under non-oxidative conditions because it lowers the activity of the catalyst in a relatively short time, resulting in short production cycles and a high regeneration requirement. Frequently, the coking is accompanied by a shortened life of the catalyst. Also, the regeneration of the catalysts is not without problems, since for an economic process on the one hand regularly the output activities must be restored and on the other hand this must be possible over a large number of cycles.
  • H. Ma et al. (Applied Catalysis, A: General 275 (2004), pages 183 to 187) describe the oxidative regeneration of a Mo / H-ZMS-5 used as a DHAM catalyst by means of air to which NO has been added.
  • a principal disadvantage of the oxidative regeneration in the DHAM is that inadequate flushing with inert gas between the reaction phase in which the catalyst is loaded with methane or other aliphatic hydrocarbons, and the regeneration phase, in the oxidizing agent such as O 2 and NO by the catalyst can form explosive mixtures of methane and oxidizing agents.
  • a purging step with inert gas between the two reaction phases is therefore always necessary and increases the effort.
  • the metallic elements present in oxidized form after the oxidative regeneration in the catalyst must again be converted into the active form for reuse. be led.
  • the disadvantage here can be that many metal oxides are volatile at high temperatures.
  • WO 2006/01 1568 a process for the preparation of aromatics and hydrogen by means of DHAM in the presence of Mo / H-ZSM-5 and Rh-doped Mo / H-ZSM-5 is described.
  • the methane 2 to 10 wt .-% H 2 is added and in each case after a few hours, the supply of methane for some time completely interrupted to regenerate the catalyst in a hydrogen atmosphere.
  • the Rh-doped Mo / H-ZSM-5 catalyst approaches the initial activity after regeneration much more than the non-doped catalyst.
  • a disadvantage of this method is the use of relatively expensive Rh as a doping material.
  • the object of the present invention is an economical process for the dehydroaromatization of aliphatic hydrocarbons, in particular methane, for the preparation of aromatics such as benzene.
  • aliphatic hydrocarbons in particular methane
  • aromatics such as benzene.
  • These include, in particular, low costs for the catalyst, high activity and stability of the catalyst and a long service life.
  • a process is to be found in which the catalyst can be regenerated easily and without great expense and is raised to the level of its initial activity by regular regeneration or comes at least very close to this level.
  • the object is achieved according to the invention by a process for the nonoxidative dehydroaromatization of a starting material E comprising C 1 -C 4 -aliphatic compounds comprising the steps
  • a catalyst comprising a) at least one metallosilicate as carrier, b) at least one element selected from the group consisting of Mo, W and Re as active component and c) at least one further transition metal which does not Is precious metal, containing as doping, and II. Regeneration of the catalyst under non-oxidative conditions with a hydrogen-containing mixture H.
  • the regeneration of a Mo, W and / or Re contained the catalyst based on a metallosilicate whose activity is reduced after its use in the DHAM due to coke deposits, with complete or almost complete achievement of the original catalyst activity by means of hydrogen, if the Catalyst with at least one further element which is not a noble metal is doped.
  • the regeneration can be carried out repeatedly with a constant or almost constant recovery of the initial catalyst activity. With the process according to the invention, long catalyst lifetimes can be achieved while maintaining the high activity of the catalyst.
  • the regeneration can be carried out easily and without additional rinsing steps with inert gas. In this case, further activation steps are not necessary.
  • Non-oxidative according to the present invention means with respect to the DHAM, that the concentration of oxidizing agents such as oxygen or nitrogen oxides in the reactant stream E below 5 wt .-%, preferably below 1 wt .-%, more preferably below 0.1 % By weight. Most preferably, the mixture is free of oxygen. Also particularly preferred is a concentration of oxidizing agent in the mixture E which is equal to or less than the concentration of oxidizing agents in the source of the dC 4 -aliphatic.
  • non-oxidative in the context of the present invention means that the coke deposits originating from the DHAM on the catalyst for its regeneration are not converted into CO and / or CO 2 by means of oxidants.
  • concentration of oxidizing agents such as oxygen or nitrogen oxides in the mixture H to be used for regeneration in step II is below 5% by weight, preferably below 1% by weight, particularly preferably below 0.1% by weight.
  • the catalyst according to the invention contains at least one metallosilicate.
  • carrier a) aluminum silicates are preferably used.
  • the carrier a) zeolites are used. From the group of zeolites zeolites of the pentasil type are preferably used according to the invention. Very particular preference is given to using zeolites with MFI structure and particularly preferably ZSM-5 zeolites, likewise preferably zeolites of the structure type MEL and preferably ZSM-1 1 and zeolites of the structure type MWW, in which case the MCM-22 zeolite is particularly preferably used. It is also possible to use mixtures of the different zeolites.
  • the zeolites may contain, in addition to AI, further elements of the third main group such as Ga, B or In.
  • the aforementioned zeolites are prepared by direct synthesis from alkali aluminate, alkali silicate and amorphous SiO 2 under hydrothermal conditions.
  • the type of channel systems formed in the zeolite can be controlled via organic template molecules, the temperature and other experimental parameters.
  • the zeolites usually fall in the synthesis in the Na form. 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 zeolites preferably used as the carrier a) in the H-form, in which the zeolites are also commercially available, are used.
  • Very particularly preferred as carrier a) is an H-ZSM-5 zeolite having a SiO 2 : Al 2 O 3 ratio of 10 to 100.
  • a common and preferred process according to the present invention for converting the catalysts into the H form is a two-stage process in which the alkali metal and / or alkaline earth metal ions are first exchanged for ammonium ions.
  • the ammonium ion decomposes into volatile ammonia and the proton remaining in the zeolite.
  • the zeolite is treated with a 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 halides, ammonium acetate, ammonium carbonate, ammonium hydrogencarbonate, ammonium nitrate, ammonium phosphate, ammonium hydrogenphosphate, ammonium dihydrogenphosphate, ammonium sulfate 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 methods suitable for the ammonium exchange of zeolites. 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 mixture 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 zeolite at 40 to 150 0 C for several hours, usually dried for 4 to 20 hours.
  • the duration of the calcination is usually 2 to 24 hours, preferably 3 to 10 hours, more preferably 4 to 6 hours.
  • zeolites are used which have been treated at least twice with an NH 4 -containing mixture and the support a) has been dried and calcined between the first and second treatment.
  • the at least two treatment with NH 4 -containing mixtures and the drying and calcining carried out as described above.
  • H-form zeolites have usually undergone a first ammonium exchange by treatment with an NH 4 -containing mixture followed by drying and calcining. Therefore, in accordance with the invention, commercially available zeolites in the H form can be used as the carrier a), but they are preferably subjected to a renewed treatment with an NH 4 -containing mixture and optionally calcined before the components b) and c) are applied.
  • the catalysts to be used for the process according to the invention contain at least one element selected from Mo, W and Re as active component b). This is applied wet-chemically or dry-chemically to the support a) according to the invention.
  • Mo, W or Re compounds are particularly suitable (NhU) 6 Mo 7 O 24 , MoO 2 , MoO 3 , H 2 MoO 4 , Na 2 MoO 4 , (NH 3 ) 3 Mo (CO) 3 , Mo (CO) 6 .
  • W compounds are particularly suitable (NhU) 6 W 12 O 39 , WO 2 , WO 3 , W (CO) 6 .
  • Re compounds particularly suitable as Re compounds are NH 4 ReO 4 , ReO 2 , ReO 3 , Re 2 (CO) io.
  • the catalyst is dried at about 80 to 130 ° C., usually for 4 to 20 hours, in vacuo or in air.
  • the active component b) can also be applied by dry chemical methods, for example by precipitating the metal carbonyls which are gaseous at elevated temperatures, such as Mo (CO) 6 , W (CO) 6 and Re 2 (CO) i 0, from the gas phase on the carrier.
  • the deposition of the metal carbonyl compound is carried out following calcination of the carrier.
  • 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, the active component b).
  • the catalyst may contain only one element selected from Mo, W and Re, it may also contain a mixture of two or even all three elements.
  • the elements can be wet-chemically applied together in a solution or in successive different solutions with drying steps between the individual applications.
  • the elements can also be applied mixed, i. one part wet-chemical and another part dry-chemical.
  • Mo is used as active component b).
  • the catalyst contains at least one further transition metal, which is not a noble metal, as doping c).
  • noble metals are understood as meaning the group consisting of Rh, Pd, Ag, Ir, Pt and Au.
  • preference is given to using as doping c) Fe, Ni, Co and Cu and mixtures thereof.
  • the methods described above for the wet-chemical impregnation of the carrier with the active component b) are used. It is possible to use the customary metal compounds known to the person skilled in the art. Particular preference is given to the nitrates, but also other salts known to the person skilled in the art for wet-chemical application can be used. Suitable are, for example, halides, in particular chloride, acetate, alkaline carbonates, formate, tartrate, acetate, complexes with ligands such as acetylacetate. tantate, aminoalkanols, EDTA, carboxylates such as oxalate and citrate, and hydroxycarboxylic acid salts.
  • the doping c) can be applied together with it. However, it is also possible to apply the doping c) and the active component b) in succession, drying being carried out after each application. It may also be advantageous to follow a certain sequence when applying. If the catalyst contains more than one element as doping c), the active component b) as well as the elements used as doping can likewise be applied together or in succession, the support being dried in each case between the different applications. Again, it may be advantageous to apply the individual elements of the doping c) and the active component b) in a certain order.
  • the solution with which the active component b) and the doping c) are applied to the zeolite 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 component b) is applied by dry chemical means, it is usually further calcined between the impregnation with the doping c) and the dry chemical application of the active component b). If more than one further element is applied, 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 doping c) is present in the catalyst according to the invention in a concentration of at least 0.1% by weight, based on the total weight of the catalyst.
  • 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 transition metal which is not a noble metal, 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.
  • catalysts which contain 6% by weight of Mo and 1% by weight of Cu.
  • catalysts which contain from 0.1 to 20% by weight of Mo and at least 0.1% by weight of Ni.
  • catalysts which contain 6% by weight of Mo and 1% by weight of Ni.
  • the catalyst is mixed with a Si-containing binder.
  • Si-containing binders are tetraalkoxysilanes, polysiloxanes and colloidal SiO 2 sols.
  • a shaping step takes place in which the catalyst composition is processed into shaped bodies according to the processes known to the person skilled in the art.
  • the shaping processes to be mentioned are, for example, spraying of a suspension containing the carrier a) or the catalyst mass, 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, for example, cellulose, cellulose derivatives such as methylcellulose, starch such as potato starch, wallpaper pastes, acrylates, polyacrylates, polymethacrylates, polyvinyl alcohols, polyvinylpyrrolidone, polyisobutylene, polytetrahydrofuran, polyglycol ethers, fatty acid compounds, wax emulsions, water or mixtures of two or more of these compounds.
  • hydrophilic polymers such as, for example, cellulose, cellulose derivatives such as methylcellulose, starch such as potato starch, wallpaper pastes, acrylates, polyacrylates, polymethacrylates, polyvinyl alcohols, polyvinylpyrrolidone, 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, for example, methylcellulose, sugar natural fibers, To call PuIp, graphite or mixtures of two or more of these compounds.
  • Pore formers and / or pasting agents are preferably removed after deformation from the resulting shaped body by at least one suitable drying and / or calcination step. The conditions required for this can be selected analogously to the parameters described above for calcination and are known to the person skilled in the art.
  • 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, Trilob, Quatrolob, star or hollow cylindrical shape in question.
  • the catalyst mass to be molded can be extruded, calcined and the resulting extrudates can be broken. and processed into SpNt.
  • the SpNt can be separated into different sieve fractions.
  • a preferred sieve fraction has a particle size of 0.25 to 0.5 mm.
  • the catalyst is used as a shaped body or SpNt.
  • the catalyst is used as a powder.
  • the catalyst powder may contain Si-containing binder, but also be present free of Si-containing binder.
  • the catalyst according to the invention contains an Si-containing binder, this is present in a concentration of 5 to 60 wt .-%, based on the total weight of the catalyst, preferably from 10 to 40 wt .-%, particularly preferably from 15 to 30 wt .-%.
  • This activation can be carried out with a C 1 -C 4 alkane, such as, for example, ethane, propane, butane or a mixture thereof, preferably butane.
  • 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 feedstock stream E contains the C 1 -C 4 -alkane, or a mixture thereof, per se, or the CrC 4 -alkane, or a mixture thereof, is added to the feedstock stream E.
  • the activation is carried out at a temperature of 250 to 650 ° C, preferably at 350 to 550 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
  • the GHSV gas hourly space velocity
  • the catalyst is activated with a H 2 -containing gas stream, a CH 4 -containing gas stream or a CH 4 and H 2 -containing gas stream, the gas stream used for activation additionally comprising inert gases such as N 2 , He, Ne and / or Ar.
  • the reactant stream E contains at least one aliphatic having 1 to 4 carbon atoms.
  • the aliphatics include methane, ethane, propane, n-butane, i-butane, ethene, propene, 1- and 2-butene and isobutene.
  • the reactant stream E comprises 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 Ci-C 4 -aliphatic ,
  • Educt stream E then preferably contains at least 50 mol%, preferably at least 60 mol%, more preferably at least 70 mol%, even more preferably at least 80 mol%, in particular at least 90 mol%.
  • the reactant stream E preferably contains at least 50 mol%, preferably at least 60 mol%, particularly preferably at least 70 mol%, very 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 dC 4 -aliphates contained in the educt current E can also originate from other sources, for example, incurred during petroleum refining.
  • the CrC 4 aliphatics may also have been produced regeneratively (eg biogas) or synthetically (eg Fischer-Tropsch synthesis).
  • the feedstock stream E may additionally contain ammonia, traces of lower alcohols and further admixtures typical of biogas.
  • LPG liquid petroleum gas
  • LNG Liquified Natural Gas
  • hydrogen, steam, carbon monoxide, carbon dioxide, nitrogen and one or more noble gases can be added to 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 3,000 h -1 .
  • 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 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.
  • the C 1 -C 4 -aliphatic compounds are converted according to the invention into aromatics with liberation of H 2 .
  • the product stream P therefore contains at least one aromatic hydrocarbon selected from the group consisting of benzene, toluene, ethylbenzene, styrene, xylene and naphthalene. Most preferably, it contains benzene and toluene.
  • the product stream contains unconverted CrC 4 -aliphatics, resulting hydrogen and the inert gases contained in the reactant stream E, such as N 2 , He, Ne, Ar, the reactant stream E added substances such as H 2 and already present in E impurities.
  • the catalyst is regenerated under non-oxidative conditions with a hydrogen-containing mixture H.
  • the mixture H contains at least 50% by volume of H 2 , preferably at least 80% by volume of H 2 , particularly preferably at least 98% by volume of H 2 .
  • the mixture H may contain inert gases such as noble gases He, Ne and Ar and N 2 .
  • the regeneration in stage II is carried out for at least 30 minutes, preferably for at least 3 hours, more preferably for at least 5 hours.
  • the regeneration in stage II is carried out at least every 50 hours, preferably at least every 20 hours, more preferably at least every 6 hours runtime of stage I, ie after a reaction time of at most 50 hours, preferably at most 20 hours, particularly preferably At the most 6 hours, the regeneration is carried out according to the stage II.
  • the temperature in the regeneration according to the stage II is at least 600 0 C, preferably at 700 to 850 0 C.
  • the regeneration according to the stage II at pressures of 1 to 10 bar, preferably from 2 to 7 bar performed.
  • the catalyst can be flushed with an inert gas, for example He, Ar or N 2 .
  • a to D reflect the general rules.
  • 100 g of a commercially available zeolite in H form are mixed with 100 g of ammonium nitrate and 900 g of water and heated for 2 hours in a stirring apparatus at 80 0 C. After cooling, the suspension is filtered and washed with water. The filter cake is dried at 120 ° C overnight.
  • a zeolite 100 g of a zeolite are mixed with 10 g of sodium carboxymethylcellulose and, after addition of 30 g of an Si-containing binder (Silres® MSE 100, Wacker Silicons), kneaded with portionwise addition of about 100 ml of water for 60 minutes.
  • the mass thus obtained is extruded through a die of round cross-section (2 mm diameter) and the extrudates obtained are dried at 120 ° C and 5 hours at
  • the thus pretreated zeolite support was then impregnated according to C with about 6 wt .-% Mo.
  • the Zeolilth support pretreated in this way is then impregnated in accordance with C with about 6% by weight of Mo.
  • the mass is then heated in a drying oven to 120 ° C, dried overnight and then calcined at 500 0 C for 5 h.
  • the Zeolilth support pretreated in this way is then impregnated in accordance with C with about 3% by weight of Mo.
  • the catalyst is tested according to D.

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  • Chemical Kinetics & Catalysis (AREA)
  • Crystallography & Structural Chemistry (AREA)
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  • Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
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Abstract

L'invention concerne un procédé de déshydroaromatisation non-oxydative d'hydrocarbures aliphatiques par mise en réaction d'un flux d'éduit contenant des hydrocarbures aliphatiques, en présence d'un catalyseur contenant au moins un métallosilicate en tant que support, au moins un élément du groupe Mo, W et Re en tant que composant actif, et au moins un autre métal de transition, n'étant pas un métal précieux, en tant que dopant, le catalyseur étant régulièrement régénéré dans des conditions non-oxydatives avec de l'hydrogène. Fe, Ni, Cu et Co sont de préférence employés en tant qu'autre métal de transition.
EP09729859A 2008-04-08 2009-04-01 Procédé de déshydroaromatisation de mélanges contenant du méthane avec régénération des catalyseurs correspondants exempts de métaux précieux Withdrawn EP2282835A1 (fr)

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EP08154196 2008-04-08
PCT/EP2009/053887 WO2009124870A1 (fr) 2008-04-08 2009-04-01 Procédé de déshydroaromatisation de mélanges contenant du méthane avec régénération des catalyseurs correspondants exempts de métaux précieux
EP09729859A EP2282835A1 (fr) 2008-04-08 2009-04-01 Procédé de déshydroaromatisation de mélanges contenant du méthane avec régénération des catalyseurs correspondants exempts de métaux précieux

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EA020383B1 (ru) 2009-04-06 2014-10-30 Басф Се Способ превращения природного газа в ароматические углеводороды с электрохимическим отделением водорода и с получением электрического тока и водорода
PL2417083T3 (pl) 2009-04-06 2015-05-29 Basf Se Sposób przeprowadzania gazu ziemnego w węglowodory aromatyczne z elektrochemicznym wydzielaniem wodoru i elektrochemicznym przeprowadzaniem wodoru w wodę
CN102596861B (zh) 2009-09-03 2015-04-08 巴斯夫欧洲公司 从甲烷制备苯的方法
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
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AU2009235497B2 (en) 2013-11-14
AU2009235497A1 (en) 2009-10-15
JP2011516518A (ja) 2011-05-26
CN102056666A (zh) 2011-05-11
KR20100134726A (ko) 2010-12-23
EA201001607A1 (ru) 2011-06-30
US8530713B2 (en) 2013-09-10
JP5535192B2 (ja) 2014-07-02
US20110060176A1 (en) 2011-03-10
WO2009124870A1 (fr) 2009-10-15

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