EP2046721A1 - Amination directe d'hydrocarbures - Google Patents

Amination directe d'hydrocarbures

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Publication number
EP2046721A1
EP2046721A1 EP07787621A EP07787621A EP2046721A1 EP 2046721 A1 EP2046721 A1 EP 2046721A1 EP 07787621 A EP07787621 A EP 07787621A EP 07787621 A EP07787621 A EP 07787621A EP 2046721 A1 EP2046721 A1 EP 2046721A1
Authority
EP
European Patent Office
Prior art keywords
catalyst
hydrogen
additive
amination
benzene
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Withdrawn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
EP07787621A
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German (de)
English (en)
Inventor
Joachim-Thierry Anders
Johann-Peter Melder
Petr Kubanek
Ekkehard Schwab
Wolfgang Mackenroth
Karl HÖLEMANN
Frederik Van Laar
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
BASF SE
Original Assignee
BASF SE
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Filing date
Publication date
Application filed by BASF SE filed Critical BASF SE
Priority to EP07787621A priority Critical patent/EP2046721A1/fr
Publication of EP2046721A1 publication Critical patent/EP2046721A1/fr
Withdrawn legal-status Critical Current

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    • 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
    • B01J21/00—Catalysts comprising the elements, oxides, or hydroxides of magnesium, boron, aluminium, carbon, silicon, titanium, zirconium, or hafnium
    • B01J21/06—Silicon, titanium, zirconium or hafnium; Oxides or hydroxides thereof
    • 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
    • B01J23/002—Mixed oxides other than spinels, e.g. perovskite
    • 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
    • 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
    • B01J23/76—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper combined with metals, oxides or hydroxides provided for in groups B01J23/02 - B01J23/36
    • B01J23/78—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper combined with metals, oxides or hydroxides provided for in groups B01J23/02 - B01J23/36 with alkali- or alkaline earth metals
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • 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
    • B01J23/76—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper combined with metals, oxides or hydroxides provided for in groups B01J23/02 - B01J23/36
    • B01J23/84—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper combined with metals, oxides or hydroxides provided for in groups B01J23/02 - B01J23/36 with arsenic, antimony, bismuth, vanadium, niobium, tantalum, polonium, chromium, molybdenum, tungsten, manganese, technetium or rhenium
    • B01J23/85—Chromium, molybdenum or tungsten
    • B01J23/88—Molybdenum
    • 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
    • B01J23/76—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper combined with metals, oxides or hydroxides provided for in groups B01J23/02 - B01J23/36
    • B01J23/84—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper combined with metals, oxides or hydroxides provided for in groups B01J23/02 - B01J23/36 with arsenic, antimony, bismuth, vanadium, niobium, tantalum, polonium, chromium, molybdenum, tungsten, manganese, technetium or rhenium
    • B01J23/85—Chromium, molybdenum or tungsten
    • B01J23/88—Molybdenum
    • B01J23/885—Molybdenum and copper
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C211/00—Compounds containing amino groups bound to a carbon skeleton
    • C07C211/43—Compounds containing amino groups bound to a carbon skeleton having amino groups bound to carbon atoms of six-membered aromatic rings of the carbon skeleton
    • C07C211/44—Compounds containing amino groups bound to a carbon skeleton having amino groups bound to carbon atoms of six-membered aromatic rings of the carbon skeleton having amino groups bound to only one six-membered aromatic ring
    • C07C211/45—Monoamines
    • C07C211/46—Aniline
    • 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
    • B01J2523/00—Constitutive chemical elements of heterogeneous catalysts

Definitions

  • the invention relates to a process for the preferably continuous amination, preferably direct amination of hydrocarbons, preferably by reacting hydrocarbons, more preferably aromatic hydrocarbons, in particular benzene, with ammonia, preferably in the presence of catalysts which catalyze the amination, wherein the amination in the presence of a Performs additional, which reacts with hydrogen, being used as an additive at least one organic chemical compound, N2O, hydroxylamine, hydrazine and / or carbon monoxide.
  • additive in this document means one or more additives which react with hydrogen or "hydrogen-reactive additive” which is to be understood below as meaning both organic-chemical compounds and carbon monoxide.
  • the additive is preferably nitrobenzene.
  • the invention relates to processes 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 catalysed:
  • aniline is usually prepared by conversion of benzene to a benzene derivative, e.g. As nitrobenzene, chlorobenzene or phenol and subsequent conversion of this derivative into aniline.
  • CN 1555921 A discloses the oxidoamination of benzene in the liquid phase, wherein 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 secondary reactions for bulk chemicals.
  • CA 553,988 discloses a process for the production 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.
  • a process for the preparation of aniline is disclosed wherein benzene in the gas phase with ammonia niak is reacted in the presence of a reducible metal oxide at temperatures of 100 to 1000 0 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, wherein the catalyst used is nickel / nickel oxide, wherein the catalyst additionally contains oxides and carbonates of zirconium, strontium, barium, calcium, magnesium, zinc, iron, titanium, aluminum, silicon, cerium, Thorium, uranium and alkali metals may contain.
  • 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 subsequently reoxidized to yield a catalyst having a nickel: nickel oxide ratio of 0.001: 1 to 10: 1.
  • No. 4,001,260 discloses a process for the direct amination of aromatic hydrocarbons with ammonia, again using a nickel / nickel oxide catalyst which has been applied to zirconium dioxide and has been 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 0 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 99/10311 teaches a process for the direct amination of aromatic hydrocarbons at a temperature of ⁇ 500 0 C and a pressure of ⁇ 10 bar.
  • the catalyst used is a catalyst comprising 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.
  • the oxidizing agent is preferably an oxygen-containing gas, e.g. As air, 02-enriched air, 02 / inert gas mixtures or pure oxygen.
  • 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. This object is achieved by the method described above.
  • aniline is formed, but at the same time one mole of hydrogen is formed.
  • hydrogen may also be present in the reaction vessel as a result of the decomposition of ammonia.
  • ammonia for example, is decomposed significantly into hydrogen and nitrogen with the nickel-nickel oxide systems.
  • reaction equation 1 is an equilibrium reaction, the quotient of the product of the concentrations or partial pressures of the products and those of the reactants is a constant, see textbooks of physical chemistry: Peter Atkins; JuNo de Paula, Atkins' Physical Chemistry, 8th edition, Oxford: Oxford University Press, 2006, ISBN
  • organic-chemical substance (s) and / or carbon monoxide is used to minimize the hydrogen concentration instead of the metered addition of oxygen (WO 99/1031 1) or hydrogen peroxide (CN 1555921) cited in the prior art is selected as an addition.
  • organic chemical substance which, upon reaction with the hydrogen present in the system, simultaneously forms the same reaction product which is also formed in the direct laminating reaction.
  • the process according to the invention removes hydrogen from the reaction system, both from the direct amination reaction and from the ammonia decomposition, and reduces the repression of the equilibrium on the side of the starting materials or prevented, ie it is increased by reducing the proportion of hydrogen in equilibrium even the conversion of Metroamination reaction.
  • the reduction of the hydrogen concentration in the reaction mixture has a direct influence on the conversion to the desired product, since directamination is an equilibrium reaction.
  • the hydrogen is used productively by additional product of value being produced by the hydrogenation of the additive into the feed.
  • the reaction of hydrogen with the organic chemical additive if it is an additive that reacts with hydrogen to the same product as the hydrocarbon in the Sparamintechnik, also introduced no foreign product in the sense of a co-production - that is, that the Separation of the hydrogen scavenging product from Designaminleiterseck deleted and therefore the cost of working up the reaction product is significantly reduced.
  • This very elegant solution not only shifts the balance, it also uses the unwanted by-product to produce the desired value product.
  • the organic chemical additive reacts with hydrogen to form one of the educts.
  • the additives used in the process according to the invention can react with hydrogen.
  • it is organic chemical substances that can react with hydrogen.
  • Particularly preferred are organic chemical substances which form the same reaction product in the reaction with hydrogen, which is also formed in the direct amination of hydrocarbons.
  • the particularly preferred organic-chemical additive also forms aniline in the reaction with hydrogen, more preferably, the organic chemical additive is nitrobenzene.
  • the process is in the direct amination of hydrocarbons, preferably the direct amination of benzene with ammonia to aniline, the organic chemical additive used N2O, hydroxylamine and / or hydrazine.
  • organic chemical additives that react with hydrogen may be, but are not limited to, oxidants known as such. Rather, all molecules with reducible functionalities are suitable as organic-chemical additives, in particular those which contain multiple bonds. Preferably, these molecules or the products of their reaction with hydrogen should preferably not react directly with the hydrocarbon because this would interfere with the selectivity of the direct amination.
  • nitrobenzene are, for example, carbon monoxide, carbonyl compounds, nitriles, imines, amides, nitro compounds, nitroso compounds, olefins, alkynes, organic peroxides, organic acids, organic acid derivatives, hydrazine derivatives, hydroxylamines, quinones, aromatics, molecules with sp2-hybridized carbon atoms, as well as all others Molecules with reducible functionalities, in particular those which contain multiple bonds or combinations thereof, for use in the inventive method into consideration.
  • Examples of individual examples of organic-chemical additives according to the invention selected from the abovementioned substance groups are nitrobenzene, carbon monoxide, hydrocyanic acid, acetonitrile, propionitrile, butyronitrile, benzonitrile, imines from the reaction of benzaldehyde with ammonia or primary amines, imines from the reaction of aliphatic aldehydes with ammonia or primary amines, formamide, acetamide, benzamide, nitrosobenzene, ethene, propene, 1-butene, 2-butene, isobutene, n-pentene and pentene isomers, Cyclopentene, n-hexene, hexene isomers, cyclohexene, n-heptene, heptenoisomeres, cycloheptene, n-octene, octa
  • reducible nitrogen-containing compounds such as nitriles, nitro compounds, nitroso compounds, and amides
  • acetylene and short-chain alkynes preferably having 3 to 6 carbon atoms
  • short-chain olefins preferably having 2 to 6 carbon atoms, or combinations thereof for this purpose
  • the addition of the additive, which reacts with hydrogen, can take place anywhere in the process. Possible examples include the separate supply of hydrocarbon, preferably benzene, amine, preferably ammonia, and organic chemical additive, preferably nitrobenzene, in the reactor,
  • the combined supply of hydrocarbon, preferably benzene, and organic chemical additive, preferably nitrobenzene, in a common feed line, separate from the amine, preferably ammonia, into the reactor The common supply of amine, preferably ammonia, and organic chemical additive, preferably nitrobenzene, in a common feed line, separate from the hydrocarbon, preferably benzene, into the reactor,
  • the dosage of the additive which reacts with hydrogen, together with the hydrocarbon, preferably benzene, at the input of the reactor is very particular preference is given to metering a nitrobenzene / benzene mixture in a common feed line and ammonia in another feed line, in each case at the inlet of the reactor.
  • the hydrocarbon / organic chemical additive molar ratio can be chosen in a very wide range, since even small additions are effective, but even higher additions are not detrimental.
  • the molar ratio of hydrocarbon to organic chemical additive can thus be varied within a range of 10000: 1 to 1: 1000.
  • the weight fraction of the additive which reacts with hydrogen is particularly preferably between 0.001% by weight and 50% by weight, in particular between 0.1% by weight and 15% by weight, very particularly preferably between 0.5 Wt .-% and 3 wt .-%, in each case based on the total weight of the hydrocarbon used, preferably benzene, and the additive, preferably nitrobenzene, wherein in the process of direct amination of benzene preferably a mixture of benzene and nitrobenzene is used as aromatics.
  • reaction conditions can be selected according to the prior art. Is preferably conducted at temperatures between 300 0 C and 500 0 C gearbei- tet, more preferably between 350 and 400 0 C.
  • the reaction pressure is usually between 1 and 1000 bar, preferably between 2 and 300 bar, more preferably between 2 and 150 bar.
  • catalysts 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. Such catalysts are widely described in the patent literature and well known.
  • conventional metal catalysts in question for.
  • precious metals (EM) all precious metals may be considered, for.
  • Ru, Rh, Pd, Ag, Ir, Pt and Au wherein 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 mixtures thereof.
  • Such alloys are also preferably used when using the other noble metals, for example, supported NiCuEM, Co-CuEM, NiCoCuEM, NiMoEM, NiCrEM, NiReEM, CoMoEM, CoCrEM, CoReEM, Fe-CuEM, FeCoCuEM, FeMoEM, FeReEM alloys of interest EM is a noble metal, especially preferably Ag and / or Au.
  • the catalyst may be in a generally conventional form, e.g. B. can be used as a powder or as usable in a fixed bed system (such as strands, spheres, tablets, rings), wherein the catalytically active ingredients may optionally be present on a support material.
  • a carrier material z.
  • inorganic oxides such as ZrÜ2, SiÜ2, Al2O3, TiÜ2, B2O3, ThÜ2, CeÜ2, Y2O3 and mixtures of these oxides, preferably TiÜ2, ZrÜ2, Al2O3 and SiÜ2, more preferably ZrÜ2 in question. Under ZrÜ2 is meant both pure ZrÜ2 and the normal Hf-containing ZrÜ2.
  • the catalyst used catalyzes both the direct amination of the hydrocarbons and the hydrogenation of the organic chemical additive (including carbon monoxide), so that no further catalyst is needed for the hydrogenation of the additive.
  • the catalysts preferably used in the process according to the invention can be regenerated, for.
  • a reductive e.g., -A atmosphere
  • the catalyst may be in both its reduced and oxidized form, preferably in its oxidized form.
  • catalyst 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 can each be present in reduced and / or oxidized form.
  • catalysts 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 is Ag or Mo represents.
  • the weight fraction of the elements is Ni, Co and Fe together, d. H. the proportion of the total weight of these elements, where not all elements must be present in the catalyst, is between 0.1% by weight and 75%
  • Wt .-% more 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 .-%, more 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.
  • the catalyst may contain carrier material.
  • the proportion by weight of doping element X in the total weight of the catalyst is preferably between 0.01% by weight and 8% by weight, more preferably between 0.1% by weight and 5% by weight, in particular between 0, 5% by weight and 4% by weight.
  • 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 at temperatures between 280 and 400 ° C., is preferably carried out with a mixture comprising inert gas and hydrogen or ammonia , In this case, the activation gas may contain other compounds. Activation reduces metal oxides to metal.
  • magnesium-aluminum oxide obtainable by calcination of LDH or LDH-like compounds is used as a carrier.
  • a suitable process for preparing 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 Su- pramolecular chemistry ", (Ed. Alberti, Bein), Pergamon, NY, 1996, VoI 7,251.
  • the catalyst used is particularly preferably a compound which contains one or more compounds selected from the group consisting of Ni, Cu, Co, Fe and Mo, these elements being able to be present in one or more oxidation states, preferably zirconium oxide and / or magnesium-aluminum oxide as a carrier.
  • catalysts (a) to (d) can be used singly or in combination with each other.
  • the catalysts need not necessarily contain NiO in order to carry out the Miaminierung of hydrocarbons described herein according to the invention, but are often catalysts with NiO content in the performance foramideamination superior to those without NiO.
  • % oxygen-containing compounds of aluminum and / or manganese, calculated as Al2O3 or MnO2, contains, inter alia in EP 1 106 600.
  • 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.
  • 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 are suitable: halogen, hydroxy, alkoxy, Aryloxy, amino, amido, thio and phosphino.
  • Preferred radicals of the aromatic or heteroaromatic hydrocarbons are selected 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, where 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 designation C3-8 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 (residues) and a 5-membered ring preferably has 4 or fewer substituents (residues).
  • 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 quinoline.
  • 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, nyl, 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 -alkylene
  • Cycloalkyl C 3-8 -cycloalkenyl, alkoxy, aryloxy, amino and amido.
  • Alkyl in the present application means branched or unbranched, saturated acyclic hydrocarbon radicals.
  • suitable alkyl radicals are methyl, ethyl, n-propyl, isopropyl, n-butyl, tert-butyl, isobutyl, etc.
  • Preferred are alkyl radicals having 1 to 50 carbon atoms, more preferably 1 to 20 carbon atoms, very particularly preferably having 1 to 6 carbon atoms and in particular having 1 to 3 carbon atoms used.
  • 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 a 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.
  • 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 are composed of a single ring or 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.
  • 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, silyl, 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 can be replaced by a suitable moiety, eg. Example, 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 in diphenylamine.
  • the aromatic ring or the aromatic rings are, for example, phenyl, naphthyl, diphenyl, diphenyl ether, diphenylamine and benzophenone.
  • the aryl radicals Preferably have the aryl radicals have 6 to 50 carbon atoms, more preferably 6 to 20 carbon atoms, most 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 CF 3), 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 means a saturated, partially unsaturated or unsaturated cyclic radical in which one or more carbon atoms of the radical are represented by a heteroatom, e.g. B. 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 from that.
  • 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 the said aromatic or heteroaromatic hydrocarbons.
  • aromatic hydrocarbons benzene, naphthalene, anthracene, toluene, xylene, pyridine, phenol and / or aniline, very particularly preferably benzene, toluene and / or 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 depend 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 0 C, preferably 300 to 500 0 C, more preferably 350 to 400 0 C and most preferably 350 to 500 0 C.
  • the reaction pressure is in the amination, preferably in the amination of benzene, d. H. the reaction of benzene with ammonia, preferably 1 to 1000 bar, more preferably 2 to 300 bar, in particular 2 to 150 bar, particularly preferably 15 to 1 10 bar.
  • the residence time in the amination process according to the invention, preferably in the amination of benzene, when carried out in a batch process is generally from 15 minutes to 8 hours, preferably from 15 minutes to 4 hours, more preferably from 15 minutes to 1 hour.
  • the residence time is generally 0.1 second to 20 minutes, preferably 0.5 second to 10 minutes.
  • the residence time on the catalyst for fixed bed catalyst thus the residence time in the catalyst bed, for fluidized bed reactors, the synthesis part of the reactor is considered (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 preferred to use one of the reactants in stoichiometric excess to achieve equilibrium shift to the desired product side and thus 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 (alternating driving style).
  • the process according to the invention can be carried out as a batch reaction, semi-continuous reaction or continuous reaction.
  • the specific reactor design and the performance of the reaction may vary depending on the amination procedure to be performed, the state of matter of the aromatic hydrocarbon to be aminated, the reaction times required, and the nature of the 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 in each case on the amination carried out and the th reactor.
  • 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 moiety 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.
  • further co-reactants, cocatalysts or further reagents are added to the reaction zone of the reactor in the process according to the invention, 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.
  • the amination may preferably be carried out at a molar ratio of ammonia to hydrocarbon of at least 1.
  • the isolation of the desired product can be carried out by methods known to those skilled in the art.
  • the preparation of the catalyst is carried out according to DE-A 44 28 004.
  • An aqueous solution of nickel nitrate, copper nitrate and zirconium acetate, the 4.48 wt .-% Ni (calculated as NiO), 1, 52 wt .-% Cu (calculated as CuO and 2.82 wt% Zr (calculated as ZrO2) is simultaneously stirred in a stirred vessel in a constant stream with a 20% aqueous sodium carbonate solution at a temperature of 70 0 C precipitated 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 0 C in a drying oven or a spray dryer.
  • the obtained in this way hydroxide-carbonate mixture is then annealed at a temperature of 430 to 460 0 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 was mixed with 3% by weight of graphite and formed into tablets.
  • An aqueous solution of nickel nitrate, copper nitrate, magnesium nitrate and aluminum nitrate containing 11.1 Kg total solution 8.1 Kg NiO, 2.9 Kg CuO, 2.8 Kg MgO and 10.2 Kg Al2O3 is simultaneously in a stirred vessel in a constant stream with an aqueous solution of 7.75 Kg of sodium carbonate and 78 Kg of sodium hydroxide in 244 liters total volume at a temperature of 20 0 C so precipitated that the measured with a glass electrode pH of 9.5 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 0 C in a drying oven.
  • the resulting hydroxide-carbonate mixture is then tempered at a temperature of 430 to 460 0 C over a period of 4 hours.
  • the oxidic species thus prepared has the composition: 56.6% by weight NiO, 19.6% by weight CuO, 15.4% by weight MgO and 8.5% by weight Al 2 O 3 .
  • the hydroxide-carbonate mixture obtained in this way was then tempered at a temperature of 450 to 500 0 C over a period of 4 hours.
  • the catalyst thus prepared had the composition Composition: 28 wt .-% NiO, 28 wt .-% CoO, 11 wt .-% CuO and 33 wt .-% ZrO 2 .
  • the catalyst was mixed with 3% by weight of graphite and formed into tablets. The oxidic tablets were reduced. The reduction was carried out at 280 0 C, with a heating rate of 3 ° C / minute.
  • the discharge from the reactor is cooled to a temperature of 2 0 C, the condensate homogenized with methanol and analyzed by gas chromatography with internal standard.
  • the amount of hydrogen in the exhaust gas increases continuously with the runtime and with increasing reduction of the catalyst: it is after 1, 4 h 3 mmol H2 / mol benzene and benzene hour, after 2.8 h 8 mmol H2 / mol zugeensem benzene and hour , after 4 h 11 mmol H2 / mol of benzene added and hour and after 4.6 h 14 mmol H2 / mol of benzene fed in and hour.
  • Example 5 (Inventive): Amination of benzene on catalyst with the addition of 0.5% nitrobenzene in the benzene feed
  • a tube reactor filled with 2-4 mm quartz glass chippings at the reactor inlet, 20 ml 23.6 g of catalyst from Example 1 in the form of 6 ⁇ 3 mm tablets and 2-4 mm quartz glass split at the reactor outlet, is heated to 350 0 C under air (50 Nl / h). After heating, the air supply is stopped, the reactor is purged with nitrogen, then the feed is started.
  • the catalyst per hour 59.6 g of an aromatic mixture consisting of 99.5% benzene and 0.5% nitrobenzene (ie 0.3 g nitrobenzene / h or 0.002 mol of nitrobenzene Ih) and 118 g of ammonia / hour.
  • the discharge from the reactor is cooled to a temperature of 2 0 C, the condensate homogenized with methanol and analyzed by gas chromatography with internal standard.
  • the aniline yield is in a bulk sample, for which the collection period was started after 3.5 h running time and ended after 4 h, 1 1, 3 mmol aniline / mol aromatics fed and hour. This corresponds to a space-time yield of 40.15 g aniline / liter of catalyst and hour.
  • the amount of hydrogen in the exhaust gas increases again in this example with the time and with increasing reduction of the catalyst, but at a much lower absolute level and slower than in Example 3: It is after 1, 2 h 1 mmol H2 / mol of aromatics fed in and Hour, after 2,1 h 2 mmol H 2 / mol of aromatics fed in and hour, after 4 h 4 mmol H 2 / mol of aromatics fed in and hour and after 4.8 h 5 mmol of H 2 / mol of added aromatics and hour.
  • Example 6 (Inventive): Amination of benzene on catalyst with the addition of 1, 0% nitrobenzene in the benzene feed
  • the catalyst per hour 59.1 g of an aromatic mixture consisting of 99.0% benzene and 1, 0% nitrobenzene (ie 0.6 g nitrobenzene / h or 0.005 mol nitrobenzene Ih) and 118 g ammonia / hour.
  • the discharge from the reactor is cooled to a temperature of 2 0 C, the condensate homogenized with methanol and analyzed by gas chromatography with internal standard.
  • the aniline yield is 17.8 mmol aniline / mole aromatics added and hour in a bulk sample for which the collection period was started after 3.5 h runtime and ended after 4 h.
  • the amount of hydrogen in the exhaust gas increases again in this example with the duration and with increasing reduction of the catalyst, but at an even lower absolute level and slower than in Example 4: It is after 1, 0 h 1 mmol H2 / mol aromatics fed and Hour, after 2.1 h 1 mmol H 2 / mol of aromatics fed in and hour, after 3.0 h 2 mmol H 2 / mol of aromatics fed in and hour, after 4 h 2 mmol H 2 / mol of added aromatics and hour and after 5.0 h 3 mmol H2 / mol aromatics fed and hour.
  • Example 7 (Inventive): Amination of benzene on catalyst with the addition of 3.0% nitrobenzene in the benzene feed
  • the catalyst per hour 60.1 g of an aromatic mixture consisting of 97% benzene and 3% nitrobenzene (ie, 1.858 g nitrobenzene / h or 0.015 mol nitrobenzene / h), as well as 118 g ammonia / hour supplied.
  • the discharge from the reactor is cooled to a temperature of 2 0 C, the condensate homogenized with methanol and analyzed by gas chromatography with internal standard.
  • the aniline yield is 12.2 mmol aniline / mole of aromatics added per hour in a bulk sample for which the collection period was started after 3.5 h running time and ended after 4 h.
  • Example 8 (Inventive): Amination of benzene on catalyst with the addition of 1 1, 1% nitrobenzene in the benzene feed
  • the catalyst per hour 61, 3 g of an aromatic mixture consisting of 88.9% benzene and 1 1, 1% nitrobenzene (ie, 6.8 g nitrobenzene / h or 0.055 mol nitrobenzene / h) and 118 g ammonia / hour.
  • the training contract from the reactor is cooled to a temperature of 2 0 C, homogenized the condensate with methanol and analyzed by gas chromatography using an internal standard.
  • the aniline yield is 30.9 mmol aniline / mol of aromatics fed in and hour in a bulk sample for which the collection period was started after 3.5 h running time and ended after 4 h. This corresponds to a space-time yield of 120.78 g aniline / liter of catalyst and hour. The peak value was reached in this experiment already after 1 h and was 43.8 mmol aniline / mol aromatics fed and hour. This corresponds to a space-time yield of 171, 36 g aniline / liter of catalyst and hour.

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Abstract

Procédé d'amination d'hydrocarbures avec de l'ammoniac, caractérisé en ce que l'amination est réalisée en présence d'un additif qui réagit à l'hydrogène, cet additif étant au moins un composé chimique organique, N2O, de l'hydroxylamine, de l'hydrazine et/ou du monoxyde de carbone.
EP07787621A 2006-07-21 2007-07-17 Amination directe d'hydrocarbures Withdrawn EP2046721A1 (fr)

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PT2451770E (pt) 2009-07-10 2015-03-04 Basf Se Processo para a aminação direta de hidrocarbonetos em amino-hidrocarbonetos com a separação eletroquímica de hidrogénio e a transformação eletroquímica do hidrogénio em água
EP2451769B1 (fr) 2009-07-10 2015-01-07 Basf Se Procédé d'amination directe d'hydrocarbures en amino-hydrocarbures avec séparation électrochimique d'hydrogène
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
BR112013029294A2 (pt) * 2011-06-09 2017-04-18 Angus Chemical processo para remover excesso de formaldeído de um sistema aquoso e composição
WO2013131864A1 (fr) 2012-03-06 2013-09-12 Basf Se Procédé de préparation d'amino-hydrocarbures par amination directe d'hydrocarbures
WO2013131723A1 (fr) 2012-03-06 2013-09-12 Basf Se Procédé de préparation d'amino-hydrocarbures par amination directe d'hydrocarbures
CN103570553B (zh) * 2012-08-01 2016-08-10 中国科学院兰州化学物理研究所 一种通过催化烷基化制备n-取代胺类化合物的方法
CN104525240A (zh) * 2014-12-10 2015-04-22 河北工业大学 硝酸铁作为催化剂在苯与羟胺盐反应一步法制苯胺反应中的应用方法
KR102574270B1 (ko) * 2015-04-02 2023-09-05 헌트스만 인터내셔날, 엘엘씨 탄화수소의 직접 아미노화
CN108654594B (zh) * 2017-03-27 2021-01-29 万华化学集团股份有限公司 一种固体酸催化剂及其制备方法以及用途
WO2019060192A1 (fr) * 2017-09-19 2019-03-28 Dow Global Technologies Llc Procédé de production de méthacrylate de méthyle par estérification oxydante à l'aide d'un catalyseur hétérogène
CN112300005A (zh) * 2019-07-26 2021-02-02 中石化南京化工研究院有限公司 一种苯一步氨化制苯胺的方法

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