WO2015132200A1 - Procédé de production combinée d'hydrocarbures aromatiques et d'amino-hydrocarbures aromatiques - Google Patents

Procédé de production combinée d'hydrocarbures aromatiques et d'amino-hydrocarbures aromatiques Download PDF

Info

Publication number
WO2015132200A1
WO2015132200A1 PCT/EP2015/054300 EP2015054300W WO2015132200A1 WO 2015132200 A1 WO2015132200 A1 WO 2015132200A1 EP 2015054300 W EP2015054300 W EP 2015054300W WO 2015132200 A1 WO2015132200 A1 WO 2015132200A1
Authority
WO
WIPO (PCT)
Prior art keywords
aromatic
hydrocarbons
process step
hydrogen
butyl
Prior art date
Application number
PCT/EP2015/054300
Other languages
German (de)
English (en)
Inventor
Bernd Bastian SCHAACK
Thomas Heidemann
Philipp Brüggemann
Michael HÜBNER
Michael Reiser
Original Assignee
Basf Se
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Application filed by Basf Se filed Critical Basf Se
Publication of WO2015132200A1 publication Critical patent/WO2015132200A1/fr

Links

Classifications

    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C209/00—Preparation of compounds containing amino groups bound to a carbon skeleton
    • C07C209/30—Preparation of compounds containing amino groups bound to a carbon skeleton by reduction of nitrogen-to-oxygen or nitrogen-to-nitrogen bonds
    • C07C209/32—Preparation of compounds containing amino groups bound to a carbon skeleton by reduction of nitrogen-to-oxygen or nitrogen-to-nitrogen bonds by reduction of nitro groups
    • C07C209/36—Preparation of compounds containing amino groups bound to a carbon skeleton by reduction of nitrogen-to-oxygen or nitrogen-to-nitrogen bonds by reduction of nitro groups by reduction of nitro groups bound to carbon atoms of six-membered aromatic rings in presence of hydrogen-containing gases and a catalyst
    • 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
    • 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

Definitions

  • the present invention relates to a process for combined production of aromatic hydrocarbons and aromatic aminocarbons.
  • Aromatic hydrocarbons such as benzene, toluene, ethylbenzene, styrene, xylenes, and naphthalene are important intermediates in the chemical industry.
  • aromatic hydrocarbons are obtained by catalytic reforming of naphtha, which in turn is derived from petroleum.
  • Recent research has shown that global oil reserves are more limited compared to global natural gas reserves. For this reason, recently developed methods that allow the production of aromatic hydrocarbons from educts that can be obtained from natural gas.
  • the main component of natural gas is usually methane.
  • a possible reaction route for the preparation of aromatic hydrocarbons is the reaction of aliphatic hydrocarbons having 1 to 4 carbon atoms in the presence of a catalyst under non-oxidative conditions, preferably in the absence of oxygen. This reaction is also called “dehydroaromatization” or “non-oxidative dehydroaromatization " designated.
  • dehydroaromatization the aliphatic hydrocarbons having 1 to 4 carbon atoms cycle to form the corresponding aromatic hydrocarbons to release hydrogen.
  • methane to benzene for example, 6 moles of methane gives 1 mole of benzene and 9 moles of hydrogen.
  • Thermodynamic considerations show that the reaction of the aliphatic hydrocarbons having 1 to 4 carbon atoms with the aromatic hydrocarbons is limited by the position of the equilibrium.
  • Thermodynamic calculations with consideration of the components methane, benzene, naphthalene and hydrogen have shown that the equilibrium conversions for the isothermal conversion of methane to benzene and naphthalene decrease with increasing pressure and falling temperature.
  • the equilibrium conversion at 1 bar and 750 ° C is about 17%.
  • the methane (or the aliphatic hydrocarbons having 1 to 4 carbon atoms) must be recycled to the dehydroaromatization.
  • 7,019,184 B2 describes a process for the dehydroaromatization of hydrocarbons, in which natural gas is used. From the product-gas mixture obtained in the dehydroaromatization hydrogen and aromatic hydrocarbons are separated. After separation, the aliphatic hydrocarbons are recycled to the dehydroaromatization reactor for re-conversion. As methods for the separation of the hydrogen hydrogen-selective membranes as well as a pressure swing adsorption are described.
  • the diffusion rate of the hydrogen molecules through the membrane depends on the partial pressure difference of the hydrogen between the retentate and permeate sides of the membrane.
  • the partial pressure can in principle be influenced by three different methods: 1) compression of the feed gas on the retentate side, whereby the partial pressure of the hydrogen is increased, 2) generation of a vacuum on the permeate side, or 3) use of a permeate side sweep gas, the partial pressure of the Hydrogen lowers.
  • the methods 1) and 2) are mechanically demanding, whereby the life of the selectively hydrogen-permeable membrane is shortened.
  • a sweep gas (method 3))
  • the sweep gas must subsequently be separated from the hydrogen.
  • appropriate devices for compacting and expanding the gas mixtures must be maintained.
  • an adsorbent In pressure swing adsorption, an adsorbent is cyclically charged in a first phase with the hydrogen-containing stream, whereby all components except hydrogen are retained by adsorption. In a second phase, these components are desorbed by lowering the pressure.
  • Cold ßox is a common process for the separation of hydrogen from gas mixtures, whereby the gas mixture is cooled to temperatures ranging from -150 ° C to -190 ° C for hydrogen separation at a pressure in the range from 30 to 50 bar
  • the hydrogen-liberated gas mixture which is to be reused in the reaction, must subsequently be reheated to the appropriate reaction temperature in the range of 600 to 1000 ° C.
  • the separation of the hydrogen from the product stream obtained in the dehydroaromatization is carried out electrochemically by means of a gas-tight membrane-electrode assembly which has at least one selectively proton-conducting membrane and at least one electrode catalyst on each side of the membrane.
  • a gas-tight membrane-electrode assembly which has at least one selectively proton-conducting membrane and at least one electrode catalyst on each side of the membrane.
  • the hydrogen on the anode catalyst is oxidized to protons that traverse the membrane.
  • the protons on a cathode catalyst are reduced to hydrogen and / or react with oxygen to form water.
  • the object of the present invention is therefore to provide a process for the production of aromatic hydrocarbons from aliphatic hydrocarbons having 1 to 4 carbon atoms, which works without the removal of hydrogen from the reaction mixture of the dehydroaromatization by means of membranes.
  • the aliphatic hydrocarbons used with 1 to 4 carbon atoms, as well as the by-products obtained in the reaction, in particular hydrogen, should be used efficiently.
  • the method should have the best possible energy balance and the lowest possible expenditure on equipment.
  • the object is achieved by a process for the combined production of aromatic hydrocarbons (A) and aromatic amino hydrocarbons (AA) comprising the steps a) reacting aliphatic hydrocarbons having 1 to 4 carbon atoms in the presence of a first catalyst (K1) under non-oxidative conditions to obtain a first product mixture (P1) containing the aromatic hydrocarbons (A), hydrogen and the unreacted aliphatic hydrocarbons having from 1 to 4 carbon atoms, b) separating the aromatic hydrocarbons (A) from the first product mixture (P1) to obtain a first mixture (E1) containing hydrogen and the unreacted aliphatic hydrocarbons having 1 to 4 carbon atoms, c) reacting aromatic nitrohydrocarbons with the first mixture (E1) in the presence of a second catalyst (K2) to obtain a second product mixture (P2) that the d) separating the aromatic amino hydrocarbons (AA) and the water from the second product mixture (P2) to obtain a second mixture (E2) containing the aromatic hydrocarbons (AA), water
  • Aromatic hydrocarbons (A) such as benzene, toluene, ethylbenzene, styrene, xylenes and naphthalene are important intermediates in the chemical industry.
  • aromatic aminocarbons (AA) such as aniline, which is used as an intermediate for the production of dyes, polyurethanes and crop protection products can be.
  • the production of aromatic amino hydrocarbons (AA) is carried out industrially generally by hydrogenation of the corresponding aromatic nitrohydrocarbons.
  • the hydrogenation of aromatic nitrohydrocarbons to the corresponding aromatic aminocarbons (AA) is highly exothermic. For example, at the Hydrogenation of 1 mol of nitrobenzene with 3 mol of hydrogen to give 1 mol of aniline and 2 moles of water an amount of energy of about -544 kJ / mol free.
  • a first product mixture (P1) is obtained. It has surprisingly been found that after the removal of the aromatic hydrocarbons (A) from the first product mixture (P1) to obtain the first mixture (EI), this first mixture (E1) can be used for the hydrogenation of aromatic nitrocarboxylic hydrocarbons according to process step c) , Here, the hydrogen contained in the first mixture (E1) in process step c) is at least partially consumed.
  • a second product mixture (P2) is obtained, which contains the economically interesting aromatic amino hydrocarbons (AA) and the unreacted aliphatic hydrocarbons having 1 to 4 carbon atoms.
  • the second product mixture (P2) after hydrogenation in step c) contains significantly less hydrogen than the first mixture (E1).
  • the aromatic amino hydrocarbons (AA) can be separated from the second product mixture (P2) to obtain a second mixture (E2) containing the unreacted aliphatic hydrocarbons having 1 to 4 carbon atoms. These can be recycled to the dehydroaromatization reaction according to process step a) and converted there again to the aromatic hydrocarbons (A).
  • the process according to the invention thus enables an efficient separation of the hydrogen obtained from the first product mixture (P1) in the dehydroaromatization according to process step a).
  • the process of the present invention enables efficient recycling of the unreacted aliphatic hydrocarbons having 1 to 4 carbon atoms.
  • the inventive method allows the combined production of two economically extremely interesting target products, that is, aromatic hydrocarbons (A) and aromatic amino hydrocarbons (AA).
  • reaction of the aliphatic hydrocarbons having 1 to 4 carbon atoms to aromatic hydrocarbons (A) according to process step a) proceeds strongly endothermic. For example, to convert 6 moles of methane to 1 mole of benzene and 9 moles of hydrogen, an energy amount of 532 kJ is necessary.
  • aliphatic hydrocarbons having 1 to 4 carbon atoms in the presence of a first catalyst (K1) are reacted under non-oxidative conditions to give a first product mixture (P1) containing the aromatic hydrocarbons (A), hydrogen and unreacted aliphatic Hydrocarbons containing 1 to 4 carbon atoms.
  • the reaction according to process step a) is also referred to below as dehydroaromatization or as non-oxidative dehydroaromatization.
  • the aliphatic hydrocarbons having 1 to 4 carbon atoms are the reaction according to process step a) generally supplied in the form of a reactant stream (E) containing the aliphatic hydrocarbons having 1 to 4 carbon atoms.
  • non-oxidative dehydroaromatization according to process step a) is known in principle and described, for example, in the publications WO 2010/1 15747 A1, WO 2010/1 15768 A1, WO 2010/1 15761 A1 and WO 2010/1 15765 A1.
  • non-oxidative conditions with reference to process step a) is understood to mean that the concentration of oxidizing agents such as oxygen or nitrogen oxides in the reaction according to process step a) is below 5% by weight, preferably below 1 wt .-%, more preferably below 0, 1 wt .-%, in each case based on the total weight of the reactants used in the reaction according to process step a).
  • the oxygen content in the reactant stream (E) is less than 5% by weight, preferably less than 1% by weight and more preferably less than 0.1% by weight, in each case based on the total weight of the reactant stream (E).
  • the reactant stream (E) is free of oxygen.
  • the reaction according to process step a) takes place with the exclusion of oxygen.
  • the dehydroaromatization of aliphatic hydrocarbons having 1 to 4 carbon atoms according to process step a) can in principle be carried out in all reactor forms known from the prior art. Suitable reactor forms are, for example, fixed-bed, radial-flow, tubular or Tube reactors. In these reactor forms, the first catalyst (K1) is a fixed bed in a reaction tube or a bundle of reaction tubes. Moreover, it is possible and preferred according to the invention to use the first catalyst (K1) as a fluidized bed, moving bed or fluidized bed in a corresponding 5 fluidized bed, moving bed or fluidized bed reactor.
  • the dehydroaromatization according to process step a) is particularly preferably carried out in a fluidized-bed reactor in which the first catalyst (K1) is present as a fluidized bed.
  • the educt stream (E) preferably contains at least one aliphatic hydrocarbon having 1 to 4 carbon atoms.
  • These aliphatic compounds include, for example, methane, ethane, propane, n-butane, isobutane, ethene, propene, 1-butene, 2-butene and isobutene.
  • the 15 invention contains the educt stream (E) at least 50 mol%, preferably at least 60 mol%, more preferably at least 70 mol%, more preferably at least 80 mol% and most preferably at least 90 mol% of the aliphatic hydrocarbons described above with 1 to 4 carbon atoms, in each case based on the total amount of material contained in the reactant stream (E)
  • the saturated alkanes are particularly preferred.
  • the educt stream (E) then contains at least 50 mol%, preferably at least 60 mol%, more preferably at least 25 70 mol%, particularly preferably at least 80 mol% and most preferably at least 90 mol% of saturated alkanes having 1 to 4 carbon atoms, in each case based on the total amount of substance in the reactant stream (E) compounds.
  • the reactant stream (E) contains at least 50 mol%, preferably at least 60 mol%, particularly preferably at least 70 mol%, particularly preferably at least 80 mol% and most preferably at least 90 mol% methane , in each case based on the total amount of substance in the educt stream (E) compounds.
  • the reactant stream (E) contains 50 to 100 mol%, preferably 60 to 100 mol%, most preferably 90 to 100 mol% of methane, in each case based on the total amount of the compounds contained in the educt stream (E).
  • the present invention therefore also encompasses a process in which the proportion of methane in the aliphatic hydrocarbons having 1 to 4 carbon atoms is at least 50 mol%, based on the total amount of the aliphatic hydrocarbons having 1 to 4 carbon atoms.
  • Natural gas As source for the aliphatic hydrocarbons having 1 to 4 carbon atoms. Natural gas generally has the following composition:
  • the natural gas Before being used in process step a) of the process according to the invention, the natural gas can be purified and possibly enriched by methods known to the person skilled in the art. Purification includes, for example, the removal of hydrogen sulfide or carbon dioxide optionally contained in natural gas and further undesirable compounds in the dehydroaromatization according to process step a).
  • hydrogen, steam, carbon monoxide, carbon dioxide, nitrogen and one or more noble gases can be added to the reactant stream (E).
  • the dehydroaromatization according to process step a) of the process according to the invention in the presence of the first catalyst (K1) is generally at temperatures in the range from 400 to 1000 ° C, preferably from 500 to 900 ° C, more preferably from 600 to 800 ° C and particularly preferred performed from 700 to 750 ° C.
  • the pressure in process step a) is generally in the range from 0.5 to 100 bar, preferably in the range from 1 to 50 bar, more preferably in the range from 1 to 30 bar and particularly preferably in the range from 1 to 10 bar.
  • the dehydroaromatization according to process step a) of the process according to the invention is generally carried out at a GHSV (gas hourly space velocity) of 100 to 10000 h -1 , preferably 200 to 3000 r -1 .
  • Suitable catalysts which can be used as the first catalyst (K1) in process step a) are, for example, in the publications WO 2010/1 15747 A1, WO 2010/1 15768 A1, WO 2010/1 15761 A1, WO 2010/1 15765 A1 and WO 201 1/042451 A1, to which reference is hereby made.
  • the catalysts contain a porous support and at least one metal deposited thereon.
  • the carrier usually contains a crystalline or amorphous inorganic compound.
  • the first catalyst (K1) preferably contains at least one metallosilicate as a carrier.
  • H-ZSM-5 is used as the zeolite.
  • the first catalyst (K1) contains at least one active metal.
  • the active metal is selected from Groups 3 to 12 of the Periodic Table of the Elements.
  • the first catalyst (K1) contains an active metal selected from the group consisting of Mo, W, Re, Ir, Ru, Rh, Pt, Pd and mixtures thereof. It particularly preferably contains an active metal from the group consisting of Mo, W, Re and mixtures thereof.
  • the first catalyst (K1) contains Mo as active metal.
  • the first catalyst (K1) contains 0, 1 to 20 wt .-% of active metal, preferably 0.2 to 15 wt .-%, particularly preferably 0.5 to 10 wt .-%, each based on the total weight of the first catalyst (K1).
  • the first catalyst (K1) contains, in addition to at least one active metal, at least one further metal selected from the group consisting of W, Cu, Ni, Fe, Co, Mn, Cr, Nb, Ta, Zr, V, Zn, Ga and mixtures thereof, more preferably selected from the group consisting of W, Cu, Ni, Fe and mixtures thereof.
  • the average particle size of the first catalyst (K1) is in the range from 10 to 250 ⁇ m, preferably in the range from 20 to 220 ⁇ m, and particularly preferably in the range from 45 to 200 ⁇ m, determined with a Malvern device (Malvern Mastersizer 2000).
  • the first catalyst (K1) can be used undiluted or mixed with inert material.
  • Preferred according to the present invention is the first catalyst (K1) undiluted or mixed with inert material as a fixed, moving or fluidized bed.
  • the first catalyst (K1) or the mixture of the first catalyst (K1) and inert material is present as a fluidized bed.
  • the first catalyst (K1) is regularly regenerated according to an embodiment of the invention.
  • the regeneration can be carried out according to the usual methods known to the person skilled in the art. According to the invention, the regeneration is preferably carried out under reducing conditions by means of a hydrogen-containing gas stream.
  • the regeneration is carried out at temperatures of 600 ° C to 1000 ° C and more preferably from 700 ° C to 900 ° C and pressures of 1 bar to 30 bar, preferably from 1 bar to 15 bar and more preferably from 1 bar to 10 bar ,
  • the first catalyst (K1) can be activated before use in process step a).
  • the activation may take place in the reactor used for dehydroaromatization or in a separate reactor. According to the invention, the activation of the first catalyst (K1) is preferred in the reactor used for dehydroaromatization.
  • the activation can be carried out with an aliphatic hydrocarbon having 1 to 4 carbon atoms, preferably the activation takes place with methane.
  • the activation is carried out at a temperature of 250 to 850 ° C, preferably at 350 to 650 ° C, and a pressure of 0.5 to 5 bar, preferably from 0.5 to 2 bar performed. This process is also known as carbidation.
  • the aliphatic hydrocarbons having 1 to 4 carbon atoms are reacted according to the invention with the release of hydrogen to form aromatic hydrocarbons (A).
  • the first product mixture (P1) therefore contains in a preferred embodiment at least one aromatic hydrocarbon (A) selected from the group consisting of benzene, toluene, ethylbenzene, styrene, xylenes and naphthalene.
  • Xylenes include 1, 2-dimethylbenzene, 1, 3-dimethylbenzene and 1, 4-dimethylbenzene.
  • the first product mixture (P1) contains benzene and toluene, more preferably the first product mixture (P1) contains benzene.
  • the first product mixture (P1) may also contain gases contained in the reactant stream (E), such as carbon dioxide, nitrogen and one or more noble gases.
  • the first product mixture (P1) obtained in the reaction of aliphatic hydrocarbons having 1 to 4 carbon atoms according to process step a) contains at least one aromatic Hydrocarbon (A) selected from the group of benzene, toluene, ethylbenzene, styrene, xylenes and naphthalene, wherein xylenes 1, 2-dimethylbenzene, 1, 3-dimethylbenzene and 1, 4-dimethylbenzene comprises.
  • the first product mixture (P1) obtained in the reaction of aliphatic hydrocarbons having 1 to 4 carbon atoms according to process step a) preferably contains benzene and / or toluene as the aromatic hydrocarbon (A).
  • the first product mixture (P1) obtained in the reaction of aliphatic hydrocarbons having 1 to 4 carbon atoms according to process step a) preferably contains benzene as the aromatic hydrocarbon (A).
  • the aromatic hydrocarbons (A) obtained in process step a) are different from the aromatic nitrohydrocarbons used in process step c) and from the aromatic amino hydrocarbons (AA) obtained in process step c).
  • the aromatic hydrocarbons (A) contain no amino group and no nitro group.
  • the present invention thus also encompasses a process in which the aromatic hydrocarbon (A) obtained in the reaction according to process step a) is at least one aromatic hydrocarbon (A) selected from the group consisting of benzene, toluene, styrene, xylenes and naphthalene.
  • the present invention thus also encompasses a process in which the aromatic hydrocarbon (A) obtained in the reaction according to process step a) is benzene.
  • Process step b) the aromatic hydrocarbon (A) obtained in the reaction according to process step a) is benzene.
  • the aromatic hydrocarbons (A) are separated from the first product mixture (P1) to obtain a first mixture (E1) containing hydrogen and the unreacted aliphatic hydrocarbons having 1 to 4 carbon atoms.
  • the separation of the aromatic hydrocarbons (A) is carried out according to methods known to those skilled in the art.
  • the separation of the aromatic hydrocarbons (A) from the first product mixture (P1) can be carried out, for example, by fractional condensation, by rectification or by gas scrubbing.
  • the high-boiling aromatic hydrocarbons (A) are condensed by condensation in the first product mixture (P1). contained unreacted aliphatic hydrocarbons having 1 to 4 carbon atoms and the hydrogen, and optionally other gases contained, separated.
  • the separation of the aromatic hydrocarbons (A) from the first product mixture (P1) by gas scrubbing is preferred.
  • the washing liquid contains in one embodiment a high-boiling hydrocarbon, in another embodiment, the washing liquid contains a liquid selected from the group consisting of N-methylpyrrolidone (NMP), N-ethylpyrrolidone and sulfolane.
  • NMP N-methylpyrrolidone
  • the washing liquid dissolves the aromatic hydrocarbons (A) from the first product mixture (P1) and thus separates them from the first product mixture (P1). The separation of the aromatic hydrocarbons (A) by gas scrubbing is preferred.
  • nonane, decane, undecane, dodecane, tridecane, tetradecane, pentadecane, hexadecane, heptadecane, octadecane, nonadecane, eicosane, heneicosane, docosane, tricosane, tetracosane, pentacosane, hexacosane, heptacosane, octacosane, nonacosane or triacontane are used as high-boiling hydrocarbons and mixtures thereof used.
  • the high-boiling hydrocarbons can be present both branched and straight-chain.
  • the separation of the aromatic hydrocarbons (A) by gas scrubbing, which is preferred in process step b), can be carried out, for example, by means of a bubble column.
  • the aromatic hydrocarbons (A) are preferably removed from the first product mixture (P1) in a process under the same pressure as in process step a).
  • equal pressure means a pressure difference of + / - 2 bar, preferably + / - 1 bar, and more preferably + / - 0.5 bar.
  • the performance of process step b) at the same pressure as process step a) is advantageous, since This makes the present method extremely economical due to the cost savings
  • the present invention thus also encompasses a method in which method step b) is carried out under the same pressure as method step a).
  • the aromatic hydrocarbons (A) are separated from the first product mixture (P1) by gas scrubbing.
  • the aromatic hydrocarbons (A) are separated off from the first product mixture (P1) by means of gas scrubbing, a straight-chain high-boiling hydrocarbon being used as the scrubbing liquid.
  • the aromatic hydrocarbons (A) are separated off from the first product mixture (P1) by gas scrubbing, the scrubbing liquid comprising at least one high-boiling hydrocarbon selected from the group consisting of decane, undecane, dodecane, tridecane, tetradecane, pentadecane, hexadecane, Contains heptadecane and octadecane.
  • the present invention thus also encompasses a process in which the aromatic hydrocarbons (A) are separated off from the first product mixture (P1) in process step b) by means of gas scrubbing.
  • the further separation of the aromatic hydrocarbons (A) from the washing liquid and the purification of the aromatic hydrocarbons (A) can be carried out by known processes, for example by distillation.
  • the distillation can be carried out at the same pressure as process step b). In a further preferred embodiment, the distillation is carried out at a pressure between 0 and 1.5 bar.
  • the first mixture (E1) after separation of the aromatic hydrocarbons (A) from the first product mixture (P1) contains hydrogen and the unreacted aliphatic hydrocarbons having 1 to 4 carbon atoms in a ratio of 1: 2 to 1: 20, preferably 1: 5 to 1: 10 and optionally further already in the reactant stream (E) contained gases such as carbon dioxide, nitrogen and one or more noble gases.
  • the first mixture (E1) obtained in process step b) contains, after the removal of the aromatic hydrocarbons (A) 0 to 5 wt .-%, preferably 0 to 2 wt .-%, particularly preferably 0 to 1 wt .-% of aromatic hydrocarbons (A), based on the total weight of the first mixture (E1). Most preferably, the first mixture (E1) is substantially free of aromatic hydrocarbons (A). "Substantially free of aromatic hydrocarbons (A)" is understood according to the invention as 0 to 0, 1 wt .-% aromatic hydrocarbons (A) based on the total weight of the first mixture (E1).
  • process step c) aromatic nitrocarboxides are reacted with the first mixture (E1) obtained in process step b) in the presence of a second catalyst (K2) to give a second product mixture (P2), the aromatic amino hydrocarbons (AA), water and the unreacted contains aliphatic hydrocarbons having 1 to 4 carbon atoms reacted.
  • the reaction according to process step c) is also referred to below as hydrogenation.
  • the reaction according to process step c) takes place in a reactor, which is also referred to below as the hydrogenation reactor.
  • the aromatic nitrohydrocarbon and the first mixture (E1) on entering the hydrogenation reactor at a temperature in the range of 200 to 400 ° C, preferably the temperature between 230 and 370 ° C, more preferably between 250 and 350 ° C.
  • the aromatic nitrohydrocarbon is fed to the hydrogenation reactor in liquid form.
  • suitable aromatic nitrohydrocarbons are, for example, aromatic nitrohydrocarbons of the formula (I)
  • R 1 is hydrogen, methyl, ethyl, propyl, iso-propyl, butyl, iso-butyl or tert-butyl, and
  • R 2 is hydrogen, methyl, ethyl, propyl, iso-propyl, butyl, iso-butyl, tert-butyl or nitro.
  • nitro is meant herein the functional group -NO 2 .
  • Nitrobenzene and the isomeric nitrotoluenes are preferred according to the invention as aromatic nitrohydrocarbons.
  • Isomeric nitrotoluenes are 2-nitrotoluene, 3-nitrotoluene and 4-nitrotoluene.
  • Nitrobenzene is particularly preferred according to the invention as the aromatic nitrohydrocarbyl.
  • the present invention thus also includes a process in which the process step c) used aromatic nitrohydrocarbon is at least aromatic nitrohydrocarbyl of the formula (I)
  • R is hydrogen, methyl, ethyl, propyl, iso-propyl, butyl, iso-butyl or tert-butyl, and
  • R 2 is hydrogen, methyl, ethyl, propyl, iso-propyl, butyl, iso-butyl, tert-butyl or
  • the present invention thus also provides a process in which the aromatic nitrohydrocarbyl used in process step c) is nitrobenzene.
  • the aromatic nitrohydrocarbons are reacted in the presence of a catalyst with hydrogen gas which may still contain steam and inert gas. It has surprisingly been found in the present invention that the process for the hydrogenation of aromatic nitrohydrocarbons can also be carried out in the presence of aliphatic hydrocarbons having 1 to 4 carbon atoms. Neither the reactivity of the aromatic nitrohydrocarbons nor that of the hydrogen contained in the first mixture (E1) nor that of the second catalyst (K2) is reduced by the aliphatic hydrocarbons having 1 to 4 carbon atoms.
  • the present invention it is thus possible to react the aromatic nitrohydrocarbons with the first mixture (E1) in the presence of a second catalyst (K2), the first mixture (E1) containing, in addition to hydrogen, the unreacted aliphatic hydrocarbons having 1 to 4 carbon atoms ,
  • the reaction of aromatic nitrohydrocarbons with the first mixture (E1) in the presence of a second catalyst (K2) takes place according to the invention at catalyst temperatures of not more than 600 ° C., preferably not more than 550 ° C., more preferably not more than 500 ° C.
  • the pressures in the reaction in process step c) are between 1 and 30 bar, preferably between 1 and 10 bar, more preferably between 3 and 8 bar.
  • process step c) is carried out at the same pressure as process step a).
  • "Equal pressure” according to the invention means a pressure difference of + / - 2 bar, preferably + / - 1 bar, more preferably + / - 0.5 bar.
  • process step c) is carried out under the same pressure as process step a).
  • the aromatic nitrohydrocarbons can be used both liquid and gaseous.
  • process step c the use of the aromatic nitrohydrocarbons in gaseous form is preferred.
  • the conversion of the aromatic nitrohydrocarbons to aromatic amino hydrocarbons (AA) according to process step c) can take place as a liquid-phase reaction or as a gas-phase reaction. According to the invention, the reaction is preferred as a gas phase reaction.
  • both the aromatic nitrohydrocarbons and the first mixture (E1) are in the gas phase.
  • the aromatic nitrohydrocarbyl is introduced in liquid form into the hydrogenation reactor and passes into the gas phase on contact with the catalyst.
  • the molar ratio between the aromatic nitrocarbons and the first mixture (E1) according to the invention is between 1:10 and 1: 120.
  • the molar ratio is preferably between 1: 30 and 1: 120, more preferably between 1:30 and 1:60.
  • the present invention thus also provides a process in which the molar ratio of aromatic nitrohydrocarbon to the first mixture (E1) in process step c) is between 1: 3 and 1: 120.
  • the hydrogenation of the aromatic nitrohydrocarbons according to process step c) can be carried out according to the invention in all known from the prior art for the hydrogenation reactor forms. Suitable reactor forms are For example, fixed-bed, radial flow, tube or tube bundle reactors.
  • the second catalyst (K2) is present as a fixed bed, for example as a catalyst bed.
  • the catalyst grains may in principle have any shape. Fluidized bed, moving bed or fluid bed reactors are preferred according to the invention.
  • the second catalyst (K2) is present as a fluidized bed, moving bed or fluidized bed.
  • the hydrogenation according to process step c) is particularly preferably carried out in a fluidized-bed reactor in which the second catalyst (K2) is present as a fluidized bed.
  • a fluidized-bed reactor as described in WO 2008/034770 A1.
  • the heat released in the exothermic hydrogenation of the aromatic nitrocarboxides according to process step c) can be fed to process step a).
  • all methods known to the person skilled in the art are suitable for feeding the heat released into process step a).
  • the reactors used in process step c) can be equipped with heat exchangers through which the heat is supplied to process step a).
  • Suitable heat exchangers are, for example, plate heat exchangers, spiral heat exchangers or tube bundle heat exchangers.
  • the present invention thus also encompasses a process in which, in process step c), heat of reaction is liberated which is fed to process step a).
  • the reactor used in process step c) has at least one solids separator above the reactor zone. Suitable solids are z. B. cyclones or filters. There, entrained catalyst particles are separated from the second product mixture (P2).
  • any known catalyst which catalyzes the hydrogenation of aromatic nitrohydrocarbons is suitable as second catalyst (K2).
  • the second catalyst (K2) contains at least one metal selected from the group Pd, Pt, Ru, Fe, Co, Ni, Mn, Re, Cr, Mo, V, Pb, Ti, Sn, Dy, Zn, Cd, Br, Cu, Ag, Au and their compounds or mixtures of metals.
  • the second catalyst (K2) may also contain oxides, sulfides, selenides or halides of the aforementioned metals.
  • the metals can be applied to supports such as Al 2 O 3 , Fe 2 O 3 / Al 2 O 3 , SiO 2 , silicates, carbon, TiO 2 and Cr 2 O 3 .
  • Metal component in the second catalyst (K2) in process step c) is at least one of the elements Cu, Pd, Mo, W, Ni or Co.
  • the average particle size of the second catalyst (K2) is 10 to 500 ⁇ m, 5 preferably 10 to 400 ⁇ m, particularly preferably 30 to 300 ⁇ m.
  • the second catalyst (K2) can be activated by hydrogen treatment at elevated temperature before hydrogenation of the aromatic nitrocarboxylic acid is started.
  • the temperature of the activation is in the range of 200 10 to 400 ° C, preferably in the range of 200 to 380 ° C.
  • the second catalyst (K2) is regularly regenerated.
  • the second catalyst (K2) can be regenerated in situ, that is in the reactor itself, with air or oxygen-containing gas mixtures.
  • the catalyst is subsequently activated again by treatment with hydrogen at elevated temperature.
  • the second product mixture (P2) obtained in the reaction according to process step c) contains at least the aromatic amino hydrocarbons (AA), water and the unreacted aliphatic hydrocarbons having 1 to 4 carbon atoms. It may also contain unreacted hydrogen as well as unconverted aromatic nitrocarboxylic hydrocarbons as well as other gases contained in the first mixture (E1).
  • the second product mixture (P2) contains 0 to 5 wt .-% hydrogen, more preferably 0 to 2 wt .-% hydrogen, particularly preferably 0 to 1 wt .-% hydrogen, based on the total weight of the second product mixture (P2). Most preferably, according to the invention, the second product mixture (P2) contains substantially no hydrogen.
  • Substantially no hydrogen "in the present invention means between 0 and 0.5% by weight of hydrogen.
  • the second product mixture (P2) contains 0.5 to 20 wt .-% hydrogen, particularly preferably 0.5 to 35 15 wt .-% hydrogen, particularly preferably 0.5 to 10 wt .-% hydrogen, based on the total weight of the second product mixture (P2).
  • the second product mixture (P2) preferably contains from 0 to 5% by weight of aromatic nitrocarbons, more preferably 0 to 2% by weight, 40 particularly preferably 0 to 1% by weight of aromatic nitrocarbons. Most preferably, the second product mixture (P2) contains substantially no aromatic nitrocarbohydrocarbons. "Essentially no aromatic In the context of the present invention, "nitrohydrocarbons” means between 0 and 0.1% by weight of aromatic nitrohydrocarbons, based on the total weight of the second product mixture (P2) . In process step c), for example, aromatic aminohydrocarbons (AA) of the formula (II) are obtained ,
  • R 1 is hydrogen, methyl, ethyl, propyl, iso-propyl, butyl, iso-butyl or tert-butyl, and
  • R 2 is hydrogen, methyl, ethyl, propyl, iso-propyl, butyl, iso-butyl, tert-butyl or amino.
  • amino is meant herein the functional group -NH 2 .
  • aminobenzene is produced as aromatic aminocarbon-hydrogen (AA).
  • 2-nitrotoluene as the aromatic nitrohydrocarbyl according to process step c) 2-methylaniline is obtained as the aromatic amino hydrocarbon (AA).
  • 3-nitrotoluene as the aromatic nitrohydrocarbyl according to process step c) 3-methylaniline is obtained as the aromatic amino hydrocarbon (AA).
  • 4-nitrotoluene as the aromatic nitrohydrocarbyl according to process step c) 4-methylaniline is obtained as the aromatic amino hydrocarbon (AA).
  • Preferred aromatic amino hydrocarbons (AA) according to the invention are aminobenzene (aniline) and the isomeric methylanilines as aromatic amino hydrocarbons (AA).
  • Isomeric methylanilines are 2-methylaniline, 3-methylaniline and 4-methylaniline.
  • Particularly preferred as the aromatic amino hydrocarbon (AA) according to the invention is aminobenzene (aniline).
  • the present invention thus also encompasses a process in which the aromatic aminohydrocarbyl (AA) obtained in process step c) is at least one aromatic aminohydrocarbyl (AA) of the formula (II). in the
  • R 1 is hydrogen, methyl, ethyl, propyl, iso-propyl, butyl, iso-butyl or tert-butyl, and
  • R 2 is hydrogen, methyl, ethyl, propyl, iso-propyl, butyl, iso-butyl, tert-butyl or amino.
  • the invention thus also provides a process in which the aromatic aminohydrocarbyl (AA) obtained in process step c) is aminobenzene.
  • Process Step d) the aromatic amino hydrocarbons (AA) and the water from the second product mixture (P2) are separated off in process step d) to obtain a second mixture (E2).
  • the separation of the high-boiling aromatic amino hydrocarbons (AA) and the water can be carried out by known methods.
  • the separation according to the invention is preferred by means of one-stage or multistage condensation.
  • In the second product mixture (P2) optionally still contained aromatic nitrocarboxylic hydrocarbons are also separated.
  • the aromatic amino hydrocarbons (AA) are obtained as a mixture with water.
  • the further purification of the separated aromatic amino hydrocarbons (AA) is carried out by known methods.
  • the aromatic amino hydrocarbons (AA) can first be separated from the water by phase separation and then purified by distillation.
  • the distillation can be carried out at the same pressure as process step d).
  • the distillation is carried out at a pressure between 0 and 1, 5 bar.
  • a second mixture (E2) is obtained in process step d).
  • the second mixture (E2) contains the unreacted aliphatic hydrocarbons having 1 to 4 carbon atoms. It may also contain unreacted hydrogen and other inert gases contained in the product mixture (P2).
  • the second mixture (E2) contains 0 to 5 wt .-% hydrogen, more preferably 0 to 2 wt .-% hydrogen, particularly preferably 0 to 1 wt .-% hydrogen, based on the total weight of the second mixture (E2). Most preferably, the second mixture (E2) contains substantially no hydrogen. "Substantially no hydrogen” is understood according to the invention as 0 to 0.5 wt .-% hydrogen, based on the total weight of the second mixture (E2).
  • the second mixture (E2) contains 0.5 to 20 wt .-% hydrogen, more preferably 0.5 to 15 wt .-% hydrogen, particularly preferably 0.5 to 10 wt .-% hydrogen, based on the total weight of the second mixture (E2).
  • the second mixture (E2) obtained in process step d) can be recycled in process step a).
  • the present invention thus also encompasses a process in which the second mixture (E2) obtained in process step d) is recycled in process step a).
  • process step d) is carried out at the same pressure as the preceding process steps a), b) and c).
  • "Equal pressure" in the context of the present invention means a pressure difference of + / - 2 bar, preferably + / - 1 bar, more preferably + / - 0.5 bar
  • An advantage of the present inventive method is that the reaction at the same pressures a costly and sophisticated apparatus compression and expansion of the gases is avoided.
  • a portion of the heat required for the dehydroaromatization can also be generated in the system itself, which also makes the process more economical than the previously known.
  • the present process provides an easy way to separate the hydrogen released in the dehydroaromatization of aliphatic hydrocarbons of 1 to 4 carbon atoms by the production of economically important aromatic amino hydrocarbons (AA). Since the aliphatic hydrocarbons having 1 to 4 carbon atoms after separation of the hydrogen again dehydroaromatization according to Process step a) are recycled, the present method additionally allows optimal utilization of the product streams.
  • the catalyst used for the non-oxidative dehydroaromatization of methane was prepared as described in WO 201 1/042451.
  • the catalyst contains as carrier ZSM-5, as active metal 5.97% Mo and 0.98% Ni.
  • the dehydroaromatization of methane was carried out in a fluidized bed reactor with 100 g of catalyst. Prior to the reaction, the catalyst was carbidized by passing a stream of methane through the reactor at a flow rate of 100 NL / h until the reaction temperature was reached.
  • the reaction then started immediately thereafter at a temperature of 730 ° C and 2.5 bar and was carried out with a mixture of CH 4 / He (90:10) at a flow of 20 NL / h.
  • the catalyst was regenerated at regular intervals by passing hydrogen at 4 bar and 800 ° C for 5 h.
  • One reaction cycle lasted 10 h.
  • Methane conversion was 7.4%, with a benzene selectivity of 88.9%.
  • the hydrogenation of nitrobenzene was carried out in a continuously operated 5 L fluidized bed reactor on a copper catalyst. Nitrobenzene was reacted at 290 ° C and 6 bar with a mixture of H 2 and CH 4 (2 Nm 3 / h H2, 8 Nm 3 / h CH 4 ) to aniline.
  • the composition of the H 2 / CH 4 mixture used corresponds to the composition of the first mixture (E1) according to the invention.
  • the preheated nitrobenzene was fed into the reactor by means of a two-fluid nozzle and there nebulized with a portion of the H 2 / CH 4 stream at the nozzle opening. Over a period of 250 h, a nitrobenzene conversion of 100% was achieved

Landscapes

  • Chemical & Material Sciences (AREA)
  • Organic Chemistry (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)

Abstract

La présente invention concerne un procédé de production combinée d'hydrocarbures aromatiques et d'amino-hydrocarbures aromatiques.
PCT/EP2015/054300 2014-03-05 2015-03-02 Procédé de production combinée d'hydrocarbures aromatiques et d'amino-hydrocarbures aromatiques WO2015132200A1 (fr)

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
EP14157901.1 2014-03-05
EP14157901 2014-03-05

Publications (1)

Publication Number Publication Date
WO2015132200A1 true WO2015132200A1 (fr) 2015-09-11

Family

ID=50230968

Family Applications (1)

Application Number Title Priority Date Filing Date
PCT/EP2015/054300 WO2015132200A1 (fr) 2014-03-05 2015-03-02 Procédé de production combinée d'hydrocarbures aromatiques et d'amino-hydrocarbures aromatiques

Country Status (1)

Country Link
WO (1) WO2015132200A1 (fr)

Citations (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO2008034770A1 (fr) * 2006-09-19 2008-03-27 Basf Se Procédé pour produire des amines aromatiques dans un réacteur à lit fluidisé
WO2010115747A1 (fr) * 2009-04-06 2010-10-14 Basf Se Procédé de transformation de gaz naturel en hydrocarbures aromatiques avec séparation électrochimique d'hydrogène, et de transformation électrochimique de l'hydrogène en eau
WO2012095356A1 (fr) * 2011-01-11 2012-07-19 Bayer Materialscience Ag Procédé de production d'amines aromatiques

Patent Citations (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO2008034770A1 (fr) * 2006-09-19 2008-03-27 Basf Se Procédé pour produire des amines aromatiques dans un réacteur à lit fluidisé
WO2010115747A1 (fr) * 2009-04-06 2010-10-14 Basf Se Procédé de transformation de gaz naturel en hydrocarbures aromatiques avec séparation électrochimique d'hydrogène, et de transformation électrochimique de l'hydrogène en eau
WO2012095356A1 (fr) * 2011-01-11 2012-07-19 Bayer Materialscience Ag Procédé de production d'amines aromatiques

Similar Documents

Publication Publication Date Title
EP1943201B1 (fr) Procede de synthese d'hydrocarbures aromatiques a partir de c1-c4-alcanes et utilisation d'un flux de produit contenant des c1-c4-alcanes
EP2417058B1 (fr) Procédé de séparation électrochimique d'hydrogène présent dans un mélange de réaction
EP2417059B1 (fr) Procédé de transformation de gaz naturel en hydrocarbures aromatiques, avec séparation électrochimique d'hydrogène
DE60023132T2 (de) Verfahren zum herstellen von vinylacetatmonomer durch ethan- oder ethylenoxidation
EP2417084B1 (fr) Procédé de transformation de gaz naturel en hydrocarbures aromatiques avec séparation électrochimique d'hydrogène, avec production concomitante de courant électrique et d'hydrogène
EP2417083B1 (fr) Procédé de transformation de gaz naturel en hydrocarbures aromatiques avec séparation électrochimique d'hydrogène, et de transformation électrochimique de l'hydrogène en eau
DE3313573A1 (de) Verfahren zur herstellung eines ungesaettigten aldehyds aus dem entsprechenden alkan
EP1682468A1 (fr) Procede de fabrication de 1-butene
EP2945923B1 (fr) Procédé de déshydrogénation oxydative de n-butènes en butadiène
EP2291341B1 (fr) Procédé de production de benzène, de toluène (et de naphtaline) à partir d alcanes c1-c4 avec dosage conjoint localement séparé d hydrogène
EP1836146A1 (fr) Procede de production de propene a partir de propane
EP1537092B1 (fr) Procede integre pour la synthese d'oxyde de propylene
EP1794111B1 (fr) Procede de preparation de la cyclopentanone
DE102005000798A1 (de) Verfahren zur Herstellung von Propen aus Propan
EP2094627B1 (fr) Procede integre pour produire du benzole et de l'ammoniac a partir d'hydrocarbures aliphatiques et d'azote
WO2015132200A1 (fr) Procédé de production combinée d'hydrocarbures aromatiques et d'amino-hydrocarbures aromatiques
DE112017005411T5 (de) Neuartige prozessintegration eines pyrolyseschritts mit methan oder höheren kohlenwasserstoffen, um ethylen und methanol und/oder wasserstoff zu erzeugen
DE102005052094A1 (de) Verfahren zur Synthese von aromatischen Kohlenwasserstoffen aus C1-C4-alkanhaltigem Produktstrom
WO2023280947A1 (fr) Procédé et installation pour la production d'acétate de vinyle
EP4015495A1 (fr) Procédé et installation de fabrication d'un composé cible
WO2003029171A1 (fr) Procede de production de composes aromatiques alkyles
EP0861222A1 (fr) Catalyseur et procede pour la fabrication de styrene et d'ethylbenzene par deshydrogenation par oxydation avec catalyse en phase heterogene de vinylcyclohexenes
WO2003089407A1 (fr) Procede de preparation de nitriles insatures

Legal Events

Date Code Title Description
121 Ep: the epo has been informed by wipo that ep was designated in this application

Ref document number: 15709448

Country of ref document: EP

Kind code of ref document: A1

DPE1 Request for preliminary examination filed after expiration of 19th month from priority date (pct application filed from 20040101)
NENP Non-entry into the national phase

Ref country code: DE

122 Ep: pct application non-entry in european phase

Ref document number: 15709448

Country of ref document: EP

Kind code of ref document: A1