EP1989173A1 - Amination directe d'hydrocarbures - Google Patents

Amination directe d'hydrocarbures

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Publication number
EP1989173A1
EP1989173A1 EP07712212A EP07712212A EP1989173A1 EP 1989173 A1 EP1989173 A1 EP 1989173A1 EP 07712212 A EP07712212 A EP 07712212A EP 07712212 A EP07712212 A EP 07712212A EP 1989173 A1 EP1989173 A1 EP 1989173A1
Authority
EP
European Patent Office
Prior art keywords
catalyst
ammonia
amination
hydrogen
temperature
Prior art date
Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
Withdrawn
Application number
EP07712212A
Other languages
German (de)
English (en)
Inventor
Frederik Van Laar
Ekkehard Schwab
Joachim-Thierry Anders
Sven Crone
Karl HÖLEMANN
Wolfgang Mackenroth
Petr Kubanek
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BASF SE
Original Assignee
BASF SE
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Publication date
Application filed by BASF SE filed Critical BASF SE
Priority to EP07712212A priority Critical patent/EP1989173A1/fr
Publication of EP1989173A1 publication Critical patent/EP1989173A1/fr
Withdrawn legal-status Critical Current

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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
    • C07C209/02—Preparation of compounds containing amino groups bound to a carbon skeleton by substitution of hydrogen atoms by amino groups
    • 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
    • B01J23/00—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00
    • B01J23/70—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper
    • B01J23/72—Copper
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J23/00—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00
    • B01J23/70—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper
    • B01J23/74—Iron group metals
    • B01J23/745—Iron
    • 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
    • B01J23/00—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00
    • B01J23/70—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper
    • B01J23/74—Iron group metals
    • B01J23/755—Nickel

Definitions

  • the invention relates to a process for preferably continuous amination, preferably direct amination of hydrocarbons preferably by reacting hydrocarbons, particularly preferably aromatic hydrocarbons, in particular benzene, with ammonia, preferably in the presence of catalysts which catalyze the amination, wherein the ISb content in the mixture on Reactor output is less than 0.1% by volume, based on the total volume of the mixture at the reactor discharge.
  • the ISb content in the mixture at the reactor discharge is preferably less than 100 ppm, very particularly preferably less than 10 ppm.
  • ppm is to be understood as meaning ppm by volume which, assuming the ideal gas law, corresponds to mol ppm.
  • the present invention further provides processes for the preferably continuous amination, preferably directamination of hydrocarbons, preferably by reacting Hydrocarbons, particularly preferably aromatic hydrocarbons, in particular benzene, with ammonia, preferably in the presence of catalysts which catalyzes the amination, wherein the amination is carried out in the presence of at least two different catalysts (i) and (ii), for the amination, decomposition of
  • the invention relates to methods for the amination of hydrocarbons, preferably by reaction of aromatic hydrocarbons, more preferably benzene with ammonia in particular according to the following reaction, which is preferably catalyzed:
  • the invention further relates to processes for the amination of hydrocarbons, preferably direct amination of hydrocarbons, particularly preferably aromatic hydrocarbons, in particular benzene, with ammonia, the amination being carried out in the presence of at least two different catalysts (i) and (ii), wherein the catalyst (ii), preferably under identical conditions, has a lower activity in decomposition of ammonia to hydrogen and nitrogen compared to the catalyst (i).
  • aniline is usually prepared by converting benzene to a benzene derivative, eg, nitrobenzene, chlorobenzene, or phenol and then converting this derivative into aniline.
  • a benzene derivative eg, nitrobenzene, chlorobenzene, or phenol
  • More advantageous than such indirect processes for the preparation of particular aromatic amines are methods which allow direct preparation of the amines from the corresponding hydrocarbons.
  • a very elegant route is the heterogeneously catalyzed direct amination of benzene, first described in 1917 by Wibaut (reports, 50, 541-546).
  • CN 1555921 A discloses the oxido-amination of benzene in the liquid phase, where hydrogen peroxide functions as the "O" donor, but the use of H2O2 is only of limited suitability due to the price and the low selectivity due to subsequent reactions for bulk chemicals.
  • CA 553,988 discloses a process for the preparation of aniline from benzene wherein benzene, ammonia and gaseous oxygen are reacted at a temperature of about 1000 ° C on a platinum catalyst.
  • Suitable platinum-containing catalysts are platinum alone, platinum with certain specific metals and platinum together with certain specific metal oxides.
  • CA 553,988 discloses a process for producing aniline in which benzene is reacted in the gas phase with ammonia in the presence of a reducible metal oxide at temperatures of 100 to 1000 ° C, without the addition of gaseous oxygen.
  • Suitable reducible metal oxides are the oxides of iron, nickel, cobalt, tin, antimony, bismuth and copper.
  • No. 3,919,155 relates to the direct amination of aromatic hydrocarbons with ammonia, the catalyst used being nickel / nickel oxide, the catalyst additionally comprising oxides and carbonates of zirconium, strontium, barium, calcium,
  • US 3,929,889 also relates to the direct amination of aromatic hydrocarbons with ammonia on a nickel / nickel oxide catalyst, wherein the catalyst used was partially reduced to elemental nickel and then reoxidized to obtain a catalyst having a nickel: nickel oxide ratio of 0.001 : 1 to 10: 1.
  • US Pat. No. 4,001,260 discloses a process for the direct amination of aromatic hydrocarbons with ammonia, where again a nickel / nickel oxide catalyst is incorporated. which has been applied to zirconium dioxide and reduced with ammonia before use in the amination reaction.
  • No. 4,031,106 again relates to the direct amination of aromatic hydrocarbons with ammonia on a nickel / nickel oxide catalyst on a zirconia support, which further contains an oxide selected from lanthanides and rare earth metals.
  • DE 196 34 1 10 describes the non-oxidative amination at a pressure of 10 - 500 bar and a temperature of 50 - 900 ° C, wherein the reaction takes place in the presence of an acidic heterogeneous catalyst which is modified with light and heavy platinum metals.
  • WO 00/09473 describes a process for the preparation of amines by direct amination of aromatic hydrocarbons on a catalyst containing at least one vanadium oxide.
  • WO 99/1031 1 teaches a process for the direct amination of aromatic hydrocarbons at a temperature of ⁇ 500 ° C and a pressure of ⁇ 10 bar.
  • the catalyst used is a catalyst containing at least one metal selected from transition metals, lanthanides and actinides, preferably Cu, Pt, V, Rh and Pd.
  • the direct amination is preferably carried out to increase the selectivity and / or the conversion in the presence of an oxidizing agent.
  • WO 00/69804 relates to a process for the direct amination of aromatic hydrocarbons, wherein the catalyst used is a complex comprising a noble metal and a reducible metal oxide. Catalysts containing palladium and nickel oxide or palladium and cobalt oxide are particularly preferred.
  • the object of the present invention is to develop a particularly economical process for the amination of hydrocarbons, in particular processes for the reaction of benzene with ammonia, in which a preferably continuous process with the highest possible selectivity and / or highest possible conversion is made possible.
  • ammonia for example, is decomposed significantly into hydrogen and nitrogen with the nickel-nickel oxide systems. It would surprisingly be found that the use of two catalysts (i) and (ii), which differ in their activity in the amination, decomposition of ammonia and oxidation of hydrogen, with the same selectivity of the conversion to aniline could be increased.
  • the catalyst system according to the invention the decomposition of the ammonia to nitrogen and hydrogen can be reduced. The reduction of the hydrogen concentration in the reaction mixture has a direct influence on the conversion to aniline.
  • the catalyst (i) has high amination activity compared with the catalyst (ii)
  • the catalyst (ii) is characterized by high activity in removing hydrogen and low activity in decomposing ammonia into nitrogen and hydrogen ,
  • the benzene conversion to aniline can be significantly increased.
  • the catalyst (ii) used is a compound which decomposes ammonia into hydrogen and nitrogen only at a temperature of at least 360 ° C., preferably at least 375 ° C., more preferably less than 0.2 vol .-% of the ammonia used decomposed.
  • Particularly preferred as catalyst (ii) are compounds which, at a temperature of 380 ° C., decompose at most 1%, in particular not more than 0.8%, of the total amount of ammonia in the reaction mixture per reaction of the reaction mixture to hydrogen and nitrogen.
  • the different activity of the catalysts (i) and (ii) with respect to the decomposition of ammonia can also be illustrated by means of a temperature comparison.
  • the temperature at which the activity of the catalyst (ii) is the same with respect to the decomposition of ammonia to hydrogen and nitrogen with the activity of the catalyst (i) with respect to the decomposition of ammonia to hydrogen and nitrogen is at least 15K, preferably at least 20 K higher than the temperature at which the catalyst (i) preferably under otherwise identical conditions has the same activity with respect to the decomposition of ammonia to hydrogen and nitrogen.
  • the catalyst (ii) has a lower activity on decomposition of ammonia to hydrogen and nitrogen compared with the catalyst (i), and thus a higher overall efficiency in removal of hydrogen from the reaction mixture.
  • the catalyst (ii) preferably has a higher hydrogen uptake in the temperature-programmed reduction with a hydrogen-containing gas mixture in the temperature range from 50 to 250 ° C. compared to the catalyst (i) and, moreover, the maximum is hydrogen consumption compared to the catalyst (i) at a higher temperature, preferably at a temperature at least 15K higher.
  • the catalyst (ii) used is a compound which has a higher hydrogen uptake in the temperature range between 50 and 250 ° C. compared to the catalyst (i) higher, more preferably at least 1 mmol hydrogen / g catalyst.
  • the hydrogen uptake is understood as the absolute consumption of hydrogen during the preferably temperature-programmed reduction of the catalyst in mmol H 2 per g of catalyst.
  • catalysts (i) and (ii) are used in which the temperature within the temperature range between 50 and 250 ° C, at which the hydrogen uptake is maximum, for the catalyst (ii) is higher than that Catalyst (i).
  • the maximum of the hydrogen uptake within the temperature range between 50 and 250 ° C. is preferably at a temperature which is at least 15 ° C. higher than the temperature at which the catalyst (i) has the maximum of the hydrogen uptake ,
  • the catalysts known for the direct amination of hydrocarbons in particular those known for the direct amination of benzene with ammonia to aniline can be used.
  • the catalyst (i) has the above-described differences from the catalyst (ii), ie it is very active for the direct amination, but also leads more strongly than catalyst (ii) to a decomposition of ammonia into nitrogen and hydrogen.
  • Such catalysts are widely described in the patent literature and well known.
  • suitable catalysts are customary metal catalysts, for example those based on nickel, iron, cobalt, copper, precious metals or alloys of these metals.
  • noble metals all noble metals may be considered, for example, Ru, Rh, Pd, Ag, Ir, Pt and Au
  • the noble metals Ru and Rh are preferably not used alone, but in alloy with other transition metals, such as Co, Cu , Fe and nickel or their mixtures.
  • Such alloys are also preferably employed using the other noble metals, for example, supported NiCuEM; CoCuEM; NiCoCuEM, NiMoEM, NiCrEM, NiReEM, CoMoEM, CoCrEM, CoReEM, FeCuEM, FeCoCuEM, FeMoEM, FeReEM alloys of interest, in which case EM is a noble metal, particularly preferably Ag and / or Au.
  • the catalyst (i) can be used in a generally customary form, for example as a powder or as a system usable in a fixed bed (for example strands, spheres, tablets, rings, the catalytically active constituents optionally being able to be present on a support material inorganic oxides, for example ZrO.sub.2, SiO.sub.2, Al.sub.2O.sub.3, TiO.sub.2, B.sub.2O.sub.3, C.sub.2O.sub.2, CeO.sub.2, Y.sub.2O.sub.3 and mixtures of these oxides, preferably TiO.sub.2, ZrO.sub.2, Al.sub.2O.sub.3 and SiO.sub.2, particularly preferably ZrO.sub.2, being pure ZrO.sub.2 and ZrO.sub.2 understood normal Hf-containing ZrÜ2.
  • a support material inorganic oxides for example ZrO.sub.2, SiO.sub.2, Al.sub.2O.
  • the catalysts preferably used in the process according to the invention can be regenerated, e.g. by passing a reductive (eg, hb) atmosphere over the catalyst or by first passing an oxidative and then a reductive atmosphere over or through the catalyst bed.
  • a reductive e.g, hb
  • the catalyst (i) can be present both in its reduced and oxidized form, the catalyst (ii) is preferably present in its oxidized form.
  • catalyst (i) a compound which contains one or more elements selected from the group consisting of Ni, Cu, Fe, Co, preferably in combination with Mo or Ag, where the elements are each in reduced and / or oxidized form may be present.
  • catalysts (i) are the combinations Co-Cu, Ni-Cu and / or Fe-Cu, in particular their combinations with additional doping element Ni-Cu-X, Fe-Cu-X, Co-Cu-X where X Ag or Mo represents.
  • the weight fraction of the elements is Ni, Co and Fe together, i. the proportion of the total weight of these elements, wherein not all elements must be present in the catalyst, between 0.1 wt .-% and 75 wt .-%, particularly preferably between 1 wt .-% and 70 wt .-%, in particular between 2 wt .-% and 50 wt .-% and the weight fraction of Cu between 0.1 wt .-% and 75 wt .-%, preferably between 0.1 wt .-% and 25 wt .-%, particularly preferably between 0.1 wt .-% and 20 wt .-%, in particular between 2.5 wt .-% and 10 wt .-%, based on the total weight of the catalyst (i).
  • the catalyst can (i) contain carrier material.
  • the proportion by weight of the doping element X in the total weight of the catalyst (i) is preferably between 0.01% by weight and 8% by weight, particularly preferably between 0.1% by weight and 5% by weight, in particular between 0 , 5 wt .-% and 4 wt .-%.
  • activating the catalyst (i) before it is used in the process Preference is given to activating the catalyst (i) before it is used in the process.
  • Such activation which preferably takes place at a temperature between 200 and 600 ° C., particularly preferably at temperatures between 250 and 500 ° C., in particular Re is carried out at temperatures between 280 and 400 ° C, is preferably carried out with a mixture containing inert gas and hydrogen or ammonia.
  • the activation gas may contain other compounds.
  • the activation of catalyst (i) may preferably be carried out in the presence of catalyst (ii).
  • magnesium-aluminum oxide obtainable by calcination of LDH or LDH-like compounds is used as a carrier.
  • a suitable process for producing magnesium aluminum oxide comprising the step of calcining LDH or LDH-like compounds is, for example, in Catal. Today 1991, 11, 173 or in "Comprehensive Supramolecular Chemistry", (Ed. Alberti, Bein), Pergamon, NY, 1996, VoI 7,251.
  • catalyst (ii) a compound which contains one or more compounds selected from the group consisting of Ni, Cu, Fe and Mo, where these elements can be present in one or more oxidation states, preferably magnesium -Aluminum oxide as a carrier, particularly preferably NiO, CuO and / or, Fe2Ü3 on magnesium aluminum oxide as a carrier.
  • a compound which contains one or more compounds selected from the group consisting of Ni, Cu, Fe and Mo where these elements can be present in one or more oxidation states
  • magnesium -Aluminum oxide as a carrier
  • NiO, CuO and / or, Fe2Ü3 on magnesium aluminum oxide as a carrier.
  • NiO and / or CuO on magnesium-aluminum oxide as support.
  • the catalysts (i) and (ii) differ in their activities, in particular in their activity of decomposing ammonia into hydrogen and nitrogen.
  • catalyst (ii) preferably has a significantly lower activity to decompose ammonia and a high activity on removal of hydrogen from the reaction mixture.
  • the catalyst (ii) also catalyzes the reaction of benzene with ammonia to aniline, albeit with a lower activity than catalyst (i).
  • catalyst (ii) a compound which has a lower decomposition of ammonia compared to the catalyst (i).
  • the catalysts (i) and (ii) thus differ, more preferably, the catalysts (i) and (ii) differ materially, most preferably the catalyst contains (i) elements which does not contain the catalyst (ii).
  • the two different catalysts (i) and (ii) are preferably used in the process according to the invention; the various catalysts are particularly preferably already at the beginning of the process in the reactor (s) in which the process is carried out. in front.
  • the activity of the catalysts with respect to the decomposition of ammonia is preferably determined at temperatures between 50 ° C and 600 ° C, wherein the catalyst is heated at a heating rate 2 ° C / min in a mixture of 5% by volume of NH3 in argon and the concentration of ammonia, hydrogen and nitrogen in exhaust gas flow is tracked.
  • the beginning of ammonia decomposition is preferably given by a nitrogen concentration in the exhaust gas of greater than 50 ppm.
  • the implementation can be carried out in the sense of temperature-programmed reduction.
  • any hydrocarbons such as aromatic hydrocarbons, aliphatic hydrocarbons and cycloaliphatic hydrocarbons, which can be arbitrarily substituted and can have heteroatoms and double or triple bonds within their chain or their ring (s).
  • Aromatic hydrocarbons and heteroaromatic hydrocarbons are preferably used in the amination process according to the invention.
  • the corresponding products are the corresponding arylamines or heteroarylamines.
  • an aromatic hydrocarbon is to be understood as meaning an unsaturated cyclic hydrocarbon which has one or more rings and contains exclusively aromatic C-H bonds.
  • the aromatic hydrocarbon has one or more 5- or 6-membered rings.
  • heteroaromatic hydrocarbon those aromatic hydrocarbons in which one or more of the carbon atoms of the aromatic ring is replaced by a heteroatom selected from N, O and S.
  • the aromatic hydrocarbons or the heteroaromatic hydrocarbons may be substituted or unsubstituted.
  • a substituted aromatic or heteroaromatic hydrocarbon are meant compounds in which one or more hydrogen atoms bound to one carbon or heteroatom of the aromatic ring is / are replaced by another.
  • Such radicals are, for example, substituted or unsubstituted alkyl, alkenyl, alkynyl, heteroalkyl, heteroalkenyl, heteroalkynyl, cycloalkyl and / or cycloalkynyl radicals.
  • the following radicals are suitable: halogen, hydroxy, alkoxy, aryloxy, amino, amido, thio and phosphino.
  • Preferred radicals of the aromatic or heteroaromatic hydrocarbons are selected from Ci- ⁇ -alkyl, Ci-6-alkenyl, Ci-6-alkynyl, C3-8-cycloalkyl, C3-8-cycloalkenyl, alkoxy, aryloxy, amino and amido, wherein the term Ci- ⁇ refers to the number of carbon atoms in the main chain of the alkyl radical, the alkenyl radical or the alkynyl radical and the term C3-8 refers to the number of carbon atoms of the cycloalkyl or cycloalkenyl ring. It is also possible that the substituents (radicals) of the substituted aromatic or heteroaromatic hydrocarbon have further substituents.
  • the number of substituents (radicals) of the aromatic or heteroaromatic hydrocarbon is arbitrary. In a preferred embodiment, however, the aromatic or heteroaromatic hydrocarbon has at least one hydrogen atom bonded directly to a carbon atom or a heteroatom of the aromatic ring.
  • a 6-membered ring preferably has 5 or fewer substituents (groups) and a 5-membered ring preferably has 4 or fewer substituents (groups).
  • a 6-membered aromatic or heteroaromatic ring carries 4 or fewer substituents, very particularly preferably 3 or fewer substituents (radicals).
  • a 5-membered aromatic or heteroaromatic ring preferably carries 3 or fewer radicals, more preferably 2 or fewer radicals.
  • A is independently aryl or heteroaryl, A is preferably selected from among phenyl, diphenyl, diphenylmethane, benzyl, dibenzyl, naphthyl, anthracene, pyridyl and quinone;
  • n is a number from 0 to 5, preferably 0 to 4, especially in the case when A is a 6-membered aryl or heteroaryl ring; in the case where A is a 5-membered aryl or heteroaryl ring, n is preferably 0 to 4; independently of the ring size, n is more preferably 0 to 3, most preferably 0 to 2 and especially 0 to 1; the other hydrocarbon substituents or heteroatoms of A carrying no substituents B carry hydrogen atoms or optionally no substituents;
  • B is independently selected from the group consisting of alkyl, alkenyl, alkynyl, substituted alkyl, substituted alkenyl, substituted alkynyl, heteroalkyl, substituted heteroalkyl, heteroalkenyl, substituted heteroalkenyl, heteroalkynyl, substituted heteroalkynyl, cycloalkyl, cycloalkenyl, substituted cycloalkyl , substituted cycloalkenyl, halogen, hydroxy, alkoxy, aryloxy, carbonyl, amino, amido, thio and phosphino; B is preferably selected independently of one another from C 1-6 -alkyl, C 1-6 -alkenyl, C 1-6 -alkynyl, C 3-8 -cycloalkyl, C 3-8 -cycloalkenyl, alkoxy, aryloxy, amino and amido.
  • the expression independently of one another means that when n is 2 or greater, the
  • Alkyl in the present application means branched or unbranched, saturated acyclic hydrocarbon radicals.
  • suitable alkyl radicals are methyl, ethyl, n-propyl, i-propyl, n-butyl, t-butyl, i-butyl, etc.
  • Alkenyl according to the present application is to be understood as meaning branched or unbranched acyclic hydrocarbon radicals which have at least one carbon-carbon double bond. Suitable alkenyl radicals are, for example, 2-propenyl, vinyl, etc.
  • the alkenyl radicals preferably have 2 to 50 carbon atoms, particularly preferably 2 to 20 carbon atoms, very particularly preferably 2 to 6 carbon atoms and in particular 2 to 3 carbon atoms.
  • the term alkenyl is to be understood as meaning those radicals which have either an cis or a trans orientation (alternatively E or Z orientation).
  • Alkynyl according to the present application is to be understood as meaning branched or unbranched acyclic hydrocarbon radicals which have at least one carbon-carbon triple bond.
  • the alkynyl radicals preferably have 2 to 50 carbon atoms, particularly preferably 2 to 20 carbon atoms, very particularly preferably 1 to 6 carbon atoms and in particular 2 to 3 carbon atoms.
  • Substituted alkyl, substituted alkenyl and substituted alkynyl are alkyl-alkenyl and alkynyl radicals in which one or more hydrogen atoms bound to one carbon atom of these radicals are replaced by another group.
  • Examples of such other groups are heteroatoms, halogen, aryl, substituted aryl, cycloalkyl, cycloalkenyl, substituted cycloalkyl, substituted cycloalkenyl and combinations thereof.
  • suitable substituted alkyl radicals are benzyl, trifluoromethyl and the like. a.
  • heteroalkyl, heteroalkenyl and heteroalkynyl are meant alkyl-alkenyl and alkynyl radicals wherein one or more of the carbon atoms in the carbon chain are replaced by a heteroatom selected from N, O and S.
  • the bond between the heteroatom and another carbon atom may be saturated or optionally unsaturated.
  • Cycloalkyl according to the present application is to be understood as meaning saturated cyclic nonaromatic hydrocarbon radicals which consist of a single ring or are constructed of several condensed rings.
  • Suitable cycloalkyl radicals are, for example, cyclopentyl, cyclohexyl, cyclooctanyl, bicyclooctyl, etc.
  • the cycloalkyl radicals preferably have between 3 and 50 carbon atoms, particularly preferably between 3 and 20 carbon atoms, very particularly preferably between 3 and 8 carbon atoms and in particular between 3 and 6 Carbon atoms on.
  • cycloalkenyl By cycloalkenyl, according to the present application, partially unsaturated, cyclic non-aromatic hydrocarbon radicals are to be understood which have a single or multiple condensed rings. Suitable cycloalkenyl radicals are, for example, cyclopentenyl, cyclohexenyl, cyclooctenyl etc.
  • the cycloalkenyl radicals preferably have 3 to 50 carbon atoms, particularly preferably 3 to 20 carbon atoms, very particularly preferably 3 to 8 carbon atoms and in particular 3 to 6 carbon atoms.
  • Substituted cycloalkyl and substituted cycloalkenyl radicals are cycloalkyl and cycloalkenyl radicals in which one or more hydrogen atoms of any carbon atom of the carbon ring are replaced by another group.
  • Such other groups are, for example, halogen, alkyl, alkenyl, alkynyl, substituted alkyl, substituted alkenyl, substituted alkynyl, aryl, substituted aryl, cycloalkyl, cycloalkenyl, substituted cycloalkyl, substituted cycloalkenyl, an aliphatic heterocyclic radical, a substituted aliphatic heterocyclic Radical, heteroaryl, substituted heteroaryl, alkoxy, aryloxy, boryl, phosphino, amino, SiIyI, thio, seleno and combinations thereof.
  • substituted cycloalkyl and cycloalkenyl radicals are 4-dimethylaminocyclohexyl, 4,5-dibromocyclohept-4-enyl and the like.
  • aryl is to be understood as meaning aromatic radicals which have a single aromatic ring or a plurality of aromatic rings which are condensed, linked via a covalent bond or are bonded by a suitable unit, e.g. a methylene or ethylene unit are linked.
  • suitable moieties may also be carbonyl moieties, such as in benzophenol, or oxygen moieties, such as in diphenyl ether, or nitrogen moieties, such as diphenylamine.
  • the aromatic ring or the aromatic rings are, for example, phenyl, naphthyl, diphenyl, diphenyl ether, diphenylamine and benzophenone.
  • the aryl radicals preferably have 6 to 50 carbon atoms, particularly preferably 6 to 20 carbon atoms, very particularly preferably 6 to 8 carbon atoms.
  • Substituted aryl radicals are aryl radicals wherein one or more hydrogen atoms attached to carbon atoms of the aryl radical are replaced by one or more other groups.
  • Suitable other groups are alkyl, alkenyl, alkynyl, substituted alkyl, substituted alkenyl, substituted alkynyl, cycloalkyl, cycloalkenyl, substituted cycloalkyl, substituted cycloalkenyl, heterocyclo, substituted heterocyclo, halogen, halogen-substituted alkyl (eg CF3), hydroxy, amino , Phosphino, Alkoxy, thio and both saturated and unsaturated cyclic hydrocarbons which may be condensed to the aromatic ring or to the aromatic rings or may be linked by a bond, or may be linked together via a suitable group.
  • Suitable groups have already been mentioned above.
  • Heterocyclo in the present application means a saturated, partially unsaturated or unsaturated cyclic radical wherein one or more carbon atoms of the radical are represented by a heteroatom, e.g. N, O or S are replaced.
  • heterocyclo radicals are piperazinyl, morpholinyl, tetrahydropyranyl, tetrahydrofuranyl, piperidinyl, pyrolidinyl, oxazolinyl, pyridyl, pyrazyl, pyridazyl, pyrimidyl.
  • Substituted heterocyclo radicals are those heterocyclo radicals in which one or more hydrogen atoms which are bonded to one of the ring atoms are replaced by another group.
  • Other suitable groups include halogen, alkyl, substituted alkyl, aryl, substituted aryl, heteroaryl, substituted heteroaryl, alkoxy, aryloxy, boryl, phosphino, amino, silyl, thio, seleno, and combinations thereof.
  • Alkoxy radicals are radicals of the general formula -OZ 1 , where Z 1 is selected from alkyl, substituted alkyl, cycloalkyl, substituted cycloalkyl, heterocycloalkyl, substituted heterocycloalkyl, SiIyI and combinations thereof.
  • Suitable alkoxy radicals are, for example, methoxy, ethoxy, benzyloxy, t-butoxy, etc.
  • aryloxy means those radicals of the general formula -OZ 1 , wherein Z 1 is selected from aryl, substituted aryl, heteroaryl, substituted heteroaryl and Combinations of it.
  • Suitable aryloxy radicals are phenoxy, substituted phenoxy, 2-pyridinoxy, 8-quinolinoxy and others.
  • Amino radicals are radicals of the general formula -NZ 1 Z 2 , where Z 1 and Z 2 are independently selected from hydrogen, alkyl, substituted alkyl, cycloalkyl, substituted cycloalkyl, heterocycloalkyl, substituted heterocycloalkyl, aryl, substituted aryl, Heteroaryl, substituted heteroaryl, alkoxy, aryloxy, SiIyI and combinations thereof.
  • Aromatic or heteroaromatic hydrocarbons preferably used in the amination process according to the invention are selected from benzene, diphenylmethane, naphthalene, anthracene, toluene, xylene, phenol and aniline and also pyridine, pyrazine, pyridazine, pyrimidine and quinoline. It is also possible to use mixtures of said aromatic or heteroaromatic hydrocarbons. Particular preference is given to using the aromatic hydrocarbons, benzene, naphthalene, anthracene, toluene, xylene, pyridine, phenol and aniline, very particularly preferably benzene, toluene and pyridine. Benzene is particularly preferably used in the amination process according to the invention, so that aniline is formed as the product.
  • ammonia is particularly preferably used.
  • the hydrocarbons, in particular the benzene are more preferably reacted with ammonia.
  • compounds can also be used which split off ammonia under the reaction conditions.
  • (N) -substituted aromatic amines for example of mono- and / or dimethylaniline
  • mono- and di-alkylamines preferably mono- and di (m) ethylamine
  • reaction conditions in the amination process according to the invention are dependent inter alia on the aromatic hydrocarbon to be aminated and the catalyst used.
  • the amination preferably the amination of benzene, ie the reaction of benzene with ammonia, is generally carried out at temperatures of 200 to 800 ° C, preferably 300 to 700 ° C, more preferably 325 to 600 ° C and most preferably 350 to 500 0 C.
  • the reaction pressure is in the amination, preferably in the amination of benzene, i. the reaction of benzene with ammonia, preferably 1 to 900 bar, more preferably 1 to 300 bar, in particular 5 to 125 bar, particularly preferably 15 to 1 10 bar.
  • the residence time in the amination process according to the invention is generally from 15 minutes to 8 hours, preferably from 15 minutes to 4 hours, more preferably from 15 minutes to 1 hour, when carried out in a batchwise process.
  • the residence time is generally 0.1 second to 20 minutes, preferably 0.5 second to 10 minutes.
  • "residence time” in this context means the residence time on the catalyst, for fixed bed catalyst thus the residence time in the catalyst bed, for fluidized bed reactors is considered the synthesis part of the reactor (part of the reactor where the catalyst is located).
  • the relative amount of the hydrocarbon used and the amine component depends on the amination reaction carried out and the reaction conditions. Generally, at least stoichiometric amounts of the hydrocarbon and amine component are employed. Usually, however, it is preferable To use one of the reactants in stoichiometric excess to achieve a shift of equilibrium to the side of the desired product and thus a higher conversion. Preferably, the amine component is used in stoichiometric excess.
  • Suitable reactors are thus both stirred tank reactors and tubular reactors.
  • Typical reactors are, for example, high-pressure stirred tank reactors, autoclaves, fixed bed reactors, fluidized bed reactors, moving beds, circulating fluidized beds, salt bath reactors, plate heat exchangers as reactors, tray reactors with multiple trays with / without heat exchange or withdrawal / supply of partial streams between the trays possible embodiments as radial flow or axial flow reactors, continuously stirred boilers, bubble reactors, etc., wherein in each case for the desired reaction conditions (such as temperature, pressure and residence time) suitable reactor is used.
  • desired reaction conditions such as temperature, pressure and residence time
  • the reactors can each be used as a single reactor, as a series of individual reactors and / or in the form of two or more parallel reactors.
  • the reactors can be operated in an AB driving style (alterative driving style).
  • the process according to the invention can be carried out as a batch reaction, semi-continuous reaction or continuous reaction.
  • the particular reactor design and operation may vary depending on the amination process to be performed, the state of matter of the aromatic hydrocarbon to be aminated, the required reaction times, and the nature of the nitrogen-containing catalyst employed.
  • the process according to the invention for directamination is preferably carried out in a high-pressure stirred tank reactor, fixed bed reactor or fluidized bed reactor.
  • one or more fixed bed reactors is used in the amination of benzene to aniline.
  • the hydrocarbon and the amine component can be added in gaseous or liquid form to the reaction zone of the respective reactor.
  • the preferred phase depends on the amination carried out and the reactor used.
  • benzene and ammonia are preferably present as gaseous reactants in the reaction zone.
  • benzene is thereby added as a liquid which is heated and vaporized to form a gas, while ammonia is present either in gaseous form or in the supercritical phase in the reaction zone. It is also possible that benzene is in supercritical phase at least together with ammonia.
  • the hydrocarbon and the amine component may be added together to the reaction zone of the reactor, for example as a premixed reactant stream, or separately.
  • the hydrocarbon and amine component may be added to the reaction zone of the reactor either simultaneously, with a time lag or sequentially.
  • the addition of the amine component and the addition of the hydrocarbon take place with a time lag.
  • cocatalysts or further reagents are added to the reaction zone of the reactor, in each case depending on the amination carried out.
  • oxygen or an oxygen-containing gas may be added to the reaction zone of the reactor, as a co-reactant.
  • the relative amount of gaseous oxygen that can be added to the reaction zone is variable and depends, inter alia, on the catalyst system used.
  • the molar ratio of gaseous oxygen to aniline may be, for example, in the range of 0.05: 1 to 1: 1, preferably 0.1: 1 to 0.5: 1.
  • a layered construction preferably with at least 4 layers, wherein the catalysts (i) and (ii) are arranged alternately, i. on a layer with catalyst 1 followed by layer with catalyst 2, then again a layer with catalyst 1, then a layer with catalyst 2, etc.
  • catalysts wherein the amination takes place initially in a zone with catalyst (i) and in the course of the content of catalyst (ii) increases.
  • the increase of catalyst (ii) in the reaction zone can be continuous and / or stepped, linear or disproportionately increasing.
  • hydrogen can be increasingly pulled out of equilibrium and thus the benzene conversion can be increased.
  • Preference is given to processes in which the content of the catalyst (ii) increases linearly in the reaction zone.
  • the structured arrangement may preferably be such that first a zone with 100% catalyst (i), then a zone of 75% catalyst (i) and 25% of catalyst (ii), then zone with 50% catalyst (i) and 50 % of catalyst (ii), then a Zone of 25% catalyst. (i) and 75% catalyst (ii) and then zone of 100% catalyst (ii) is used.
  • the amination can preferably be carried out at a molar ratio of ammonia to the hydrocarbon of at least 1.
  • the isolation of the desired product can be carried out by methods known to those skilled in the art.
  • An aqueous solution of nickel nitrate, copper nitrate and zirconium acetate containing 4.48 wt% Ni (calculated as NiO), 1.52 wt% Cu (calculated as CuO) and 2.28 wt% Zr (calculated as ZrO 2) is simultaneously precipitated in a stirrer vessel in a constant stream with a 20% aqueous sodium carbonate solution at a temperature of 70 ° C so that the measured with a glass electrode pH of 7.0 is maintained.
  • the suspension obtained is filtered and the filter cake is washed with demineralized water until the electrical conductivity of the filtrate is about 20 ⁇ S.
  • the filter cake is dried at a temperature of 150 ° C in a drying oven or a spray dryer.
  • the hydroxide-carbonate mixture obtained in this way is then tempered at a temperature of 430 to 460 ° C over a period of 4 hours.
  • the oxidic species prepared in this way has the composition: 50% by weight of NiO, 17% by weight of CuO, 1.5% by weight of MoO 3 and 31.5% by weight of ZrO 2 .
  • the catalyst When heated in gas stream containing hydrogen in the temperature range of 50 to 250 ° C, the catalyst has a hydrogen uptake of 1.70 mmol hydrogen / g catalyst and the maximum of hydrogen consumption at a temperature of 140 ° C.
  • the resulting suspension is filtered and the filter cake washed with deionized water until the electrical conductivity of the filtrate is approx. 20 ⁇ S.
  • the filter cake is dried at a temperature of 150 ° C in a drying oven.
  • the thus obtained hydroxide-carbonate mixture is then annealed at a temperature of 430 to 460 ° C over a period of 4 hours.
  • the oxidic species thus prepared has the composition: 56.6% by weight of NiO, 19.6% by weight of CuO, 15.4% by weight of MgO, and 8.5% by weight of Al 2 O 3.
  • the catalyst has a hydrogen uptake of 2.41 mmol hydrogen / g catalyst and the maximum of hydrogen consumption at a temperature 159 ° C when heated in gas stream containing hydrogen in the temperature range of 50 to 250 ° C.
  • Example 3 Temperature programmed reduction of the catalyst in ammonia
  • catalyst powder 100 mg is heated in a 30 ml / min gas stream of 5 vol .-% ammonia in argon at a heating rate of 2 ° C per minute.
  • concentration of ammonia, hydrogen and nitrogen in reaction gas after the catalyst bed was monitored by mass spectroscopy.
  • the conversion of ammonia is given at a nitrogen concentration higher than 50 ppm.
  • the values for both catalysts (i) and (ii) are shown in the table.
  • Example 6 (Inventive): Amination on a Structured Mixture of Catalyst (i) and Catalyst (ii)
  • 220 ml of catalyst (i) in the form of 6x3 mm tablets is incorporated together with 220 ml of catalyst (ii) in the form of 6 ⁇ 3 mm tablets in a tubular reactor.
  • first zone 50 ml of catalyst (i) is installed, followed by a zone with 1 12 ml of catalyst (i) and 57 ml of catalyst (ii) homogeneously mixed, then there is a zone with 57 ml of catalyst (i) and 1 14th ml of catalyst (ii) mixed homogeneously and then a zone with 50 ml of catalyst (ii).
  • the reactor is heated to 350 ° C, then the reaction mixture is closed.
  • the catalyst is fed with 156 g / hour of benzene and 306 g / ammonia.
  • the effluent from the reactor is cooled at a temperature below 10 ° C and the organic phase of the condensate is analyzed by gas chromatography.
  • the content of aniline in wt% averaged over 5 hours is 6.08% and the space-time yield is 11.56 g aniline / Kg catalyst bed and hour.

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  • Chemical Kinetics & Catalysis (AREA)
  • Low-Molecular Organic Synthesis Reactions Using Catalysts (AREA)
  • Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)

Abstract

L'invention concerne un procédé servant à l'amination d'hydrocarbures au moyen d'ammoniac. Le procédé selon l'invention est caractérisé en ce que la teneur en N2 dans le mélange au niveau de la sortie du réacteur est inférieure à 0,1 % en volume, et ce par rapport au volume total du mélange à la sortie du réacteur. (Formule (I))
EP07712212A 2006-02-24 2007-02-13 Amination directe d'hydrocarbures Withdrawn EP1989173A1 (fr)

Priority Applications (1)

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EP07712212A EP1989173A1 (fr) 2006-02-24 2007-02-13 Amination directe d'hydrocarbures

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EP06110419 2006-02-24
EP07712212A EP1989173A1 (fr) 2006-02-24 2007-02-13 Amination directe d'hydrocarbures
PCT/EP2007/051376 WO2007099028A1 (fr) 2006-02-24 2007-02-13 Amination directe d'hydrocarbures

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KR (1) KR20080104336A (fr)
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WO (1) WO2007099028A1 (fr)

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DE102004062253A1 (de) * 2004-12-23 2006-07-06 Basf Ag Direktaminierung von Kohlenwasserstoffen
DE102005041140A1 (de) * 2005-08-30 2007-03-01 Basf Ag Direktaminierung von Kohlenwasserstoffen
US8411882B2 (en) * 2008-10-31 2013-04-02 Htc Corporation Electronic device with electret electro-acoustic transducer
JP5536207B2 (ja) * 2009-07-10 2014-07-02 ビーエーエスエフ ソシエタス・ヨーロピア 水素を電気化学的に除去しながら炭化水素をアミノ炭化水素に直接アミノ化する方法
HUE024550T2 (en) 2009-07-10 2016-02-29 Basf Se Process for direct amination of hydrocarbons to amino hydrocarbons by electrochemical separation of hydrogen and conversion of hydrogen into electrochemical water
WO2011003934A2 (fr) 2009-07-10 2011-01-13 Basf Se Procédé d'amination directe d'hydrocarbures en amino-hydrocarbures avec séparation électrochimique d'hydrogène
WO2011003932A2 (fr) 2009-07-10 2011-01-13 Basf Se Procédé d'amination directe d'hydrocarbures en amino-hydrocarbures avec séparation électrochimique d'hydrogène
WO2013131723A1 (fr) 2012-03-06 2013-09-12 Basf Se Procédé de préparation d'amino-hydrocarbures par amination directe d'hydrocarbures
WO2013131864A1 (fr) 2012-03-06 2013-09-12 Basf Se Procédé de préparation d'amino-hydrocarbures par amination directe d'hydrocarbures
WO2016050500A1 (fr) 2014-09-29 2016-04-07 Basf Se Ensemble d'électrode à membrane, réacteur pourvu de l'ensemble d'électrode à membrane et procede de séparation de l'hydrogene
WO2019076658A1 (fr) * 2017-10-16 2019-04-25 Basf Se Augmentation de la sélectivité catalytique lors de l'hydrogénation continue de composés nitro par addition d'ammoniac

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KR20080104336A (ko) 2008-12-02
US20090030234A1 (en) 2009-01-29
US7838702B2 (en) 2010-11-23
WO2007099028A1 (fr) 2007-09-07
CN101389593A (zh) 2009-03-18

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