WO2000009473A1 - Production d'amine - Google Patents

Production d'amine Download PDF

Info

Publication number
WO2000009473A1
WO2000009473A1 PCT/GB1999/002366 GB9902366W WO0009473A1 WO 2000009473 A1 WO2000009473 A1 WO 2000009473A1 GB 9902366 W GB9902366 W GB 9902366W WO 0009473 A1 WO0009473 A1 WO 0009473A1
Authority
WO
WIPO (PCT)
Prior art keywords
catalyst
process according
oxygen
ammonia
aromatic compound
Prior art date
Application number
PCT/GB1999/002366
Other languages
English (en)
Inventor
Hugh Edmund Stitt
Samuel David Jackson
Original Assignee
Imperial Chemical Industries Plc
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Priority claimed from PCT/GB1998/002453 external-priority patent/WO1999010311A1/fr
Priority claimed from GBGB9825704.1A external-priority patent/GB9825704D0/en
Priority claimed from GBGB9903599.0A external-priority patent/GB9903599D0/en
Application filed by Imperial Chemical Industries Plc filed Critical Imperial Chemical Industries Plc
Priority to AU50542/99A priority Critical patent/AU5054299A/en
Publication of WO2000009473A1 publication Critical patent/WO2000009473A1/fr

Links

Classifications

    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C209/00—Preparation of compounds containing amino groups bound to a carbon skeleton
    • C07C209/02—Preparation of compounds containing amino groups bound to a carbon skeleton by substitution of hydrogen atoms by amino groups

Definitions

  • This invention relates to the production of amines, particularly aromatic amines by the direct reaction of an aromatic compound with ammonia and oxygen.
  • CA 553 988 proposes a vapour phase process using oxides of chromium, molybdenum, tungsten or niobium in combination with platinum, or reducible metal oxides such as oxides of iron, nickel, cobalt, tin, antimony, bismuth or copper.
  • US 2 948 755 discloses a mixed gas/liquid phase process using a mixture of a Group Vlb metal, especially molybdenum, chromium or tungsten, and an easily reduced oxide, especially copper, iron, nickel, silver or gold.
  • GB 1 327 494 and GB 1 463 997 disclose processes employing a sealed autoclave wherein high pressures, e.g. above about 300 bar, are achieved using nickel/nickel oxide, or nickel/nickel oxide/rare earth oxide catalysts.
  • vanadium oxides are particularly suitable catalysts. Vanadium forms a number of oxides: it is believed that the most active species has a composition corresponding to a mixture of V 2 0 5 and V 2 0 . It is therefore desirable to operate the process under such conditions that the average valency state of the vanadium is below 5. This may be achieved by limiting the amount of oxygen present in the reaction mixture.
  • the present invention provides a process for the production of an aromatic amine comprising contacting a gaseous mixture containing an aromatic compound and ammonia at an elevated temperature with a catalyst composition comprising at least one oxide of vanadium, there being, per mole of the aromatic compound, at least one mole of ammonia and a sub- stoichiometric amount of a hydrogen sink.
  • the aromatic compound is preferably an aromatic hydrocarbon, i.e. it is free from substituents other than hydrocarbyl groups, e.g. alkyl groups.
  • aromatic hydrocarbons are benzene, toluene and xylenes. Benzene is preferred.
  • At least one mole of ammonia per mole of aromatic compound is employed.
  • the reaction of the aromatic compound and ammonia is effected in the presence of a - hydrogen sink. The reaction is believed to be
  • H- H represents an aromatic compound
  • H-sink represents a hydrogen sink, i.e. a material capable of reacting with the hydrogen produced by the reaction of the aromatic compound and ammonia.
  • the stoichiometric amount of hydrogen sink is thus that which would react with 2 hydrogen atoms for each molecule of aromatic compound employed.
  • the amount of hydrogen sink used is sub-stoichiometric.
  • the amount of hydrogen sink is from 1 to 50%, particularly 2 to 50%, of the stoichiometric amount relative to the aromatic hydrocarbon.
  • the hydrogen sink normally comprises a source of available oxygen, but may also contain other elements capable of reacting with hydrogen.
  • the stoichiometric amount of available oxygen is thus one atom of available oxygen per molecule of the aromatic compound, i.e. one gram atom of available oxygen per mole of the aromatic compound.
  • Some or all of the hydrogen sink is available oxygen provided by the reduction of the vanadia from the higher valency, i.e. pentavalent, state to the lower valency, i.e. tetravalent, state, i.e.
  • the hydrogen sink is only the available oxygen so provided by the vanadia, there should thus be less than one mole, preferably less than 0.5 mole, of vanadium pentoxide per mole of aromatic hydrocarbon.
  • the amount of reaction i.e. yield per unit amount of catalyst, is therefore limited. It is therefore preferred to provide an additional hydrogen sink to react directly, i.e. to augment the hydrogen sink provided by reduction of the vanadia catalyst, and/or to provide a source of available oxygen for regeneration of the catalyst.
  • the additional hydrogen sink preferably is an oxygen-containing gas which may contain free gaseous oxygen or may have the oxygen in combined form.
  • gaseous oxygen preferably air
  • the overall reaction is believed to be
  • the stoichiometric amount of oxygen is 0.5 mole per mole of aromatic compound. Since some of the hydrogen sink is provided by the reduction of the vanadia, the amount of free oxygen fed to the reaction should be such that the total available oxygen fed to the reaction is sub- stoichiometric. Normally, the amount of free oxygen fed to the reaction is in the range 0.01 to 0.2, preferably 0.02 to 0.2, particularly 0.05 to 0.2, moles of oxygen per mole of aromatic compound.
  • the oxygen-containing gas may contain oxygen in combined form.
  • the oxygen-containing gas may be, or contain, carbon dioxide or carbon monoxide.
  • the oxygen-containing gas provides a hydrogen sink in the form of carbon in addition to the available oxygen.
  • steam is not suitable as a hydrogen sink as it does not contain available oxygen, the presence of steam is not precluded, although its presence is not preferred except as a reaction product.
  • the process is preferably operated continuously, particularly with recycle of unreacted gases after separation of the product amine.
  • the process is preferably operated at a pressure below 20 bar abs., more preferably below 10 bar abs., particularly at a pressure in the range 1 to 7 bar abs., most particularly between 2 and 5 bar abs.
  • the reaction is effected at an elevated temperature, preferably at a temperature below 600°C, more preferably in the range 200-550°C, particularly in the range 300-500°C, more particularly between 350 and 450°C.
  • the vanadium oxides may be supported on a suitable inert support material: suitable supports include non-reducible oxidic materials such as silica, zirconia, titania, alumina or calcium aluminate cement.
  • the supports may contain stabilising additives as is known in the art.
  • Alumina is the preferred support, particularly transition aluminas such as delta, theta or gamma alumina, especially those having a BET surface area of at least 100 m 2 /g, e.g. 100-200 m 2 /g.
  • the catalyst contains 1-15, preferably 5-15% by weight of vanadia, expressed as V 2 0 5 .
  • the catalyst may be unsupported, i.e. composed essentially of vanadia together with any activity promoters as described hereinafter, possibly with a small proportion, e.g. up to 10% by weight ⁇ f the catalyst of a suitable binder such as a calcium aluminate cement or a clay.
  • the catalyst may be in any suitable physical form, for example powder, pellets, extrudates, or may be monolithic, e.g. a honeycomb structure.
  • the physical form of the catalyst will depend on whether the process is designed to employ a fixed bed catalyst or a moving bed.
  • the catalyst may be made by co-precipitation of the support and a suitable vanadium compound or by precipitation of a vanadium compound in the presence of the support, e.g. with the latter suspended in the medium in which the precipitation is effected.
  • the catalyst may be formed by coating the support with a suspension containing a vanadium compound.
  • the catalyst is produced by impregnation of the support with a solution of a vanadium compound, e.g. ammonium metavanadate.
  • a vanadium compound e.g. ammonium metavanadate.
  • the composition is then heated if necessary to convert the vanadium compound to the oxidic state.
  • the catalyst composition may also contain other components such as activity promoters.
  • additives include compounds of alkali metal, such as potassium, e.g. in amounts of 1 to 5% by weight
  • the alkali metal oxide M 2 0 where M represents an alkali metal of the catalyst, which may be useful to minimise the deposition of carbon during use of the catalyst, and/or noble metals such as platinum, and/or compounds of transition metals such as chromium, manganese, iron, cobalt, nickel or copper in amounts of up to 1%, e.g. 0.05 to 0.2%, by weight (expressed as the metal) of the catalyst.
  • the vanadia catalyst is a partially reduced state.
  • a suitable reducing gas such as hydrogen or carbon monoxide.
  • the aromatic compound itself may exert sufficient reducing power, and/or sufficient of the ammonia fed may crack at the operating temperature to provide hydrogen to effect the reduction.
  • an oxygen-containing gas which may be substantially pure oxygen, enriched air, un- enriched air, or preferably air in admixture with an inert diluent, e.g.
  • the valency state of the vanadium may be controlled by controlling the proportion of oxygen-containing gas and/or by controlling the proportion of an inert diluent, e.g. nitrogen, which has the effect of modifying the partial pressure of the oxygen- containing gas.
  • the oxidation state of the vanadium may be controlled by feeding hydrogen or another reducing gas such as carbon monoxide, continuously, or intermittently, in a controlled manner to maintain the vanadium oxide in the desired state.
  • the process is preferably operated at a space velocity, i.e. total gas volume (expressed at NTP) fed per hour per volume of catalyst in the range 100 to 10,000 h "1 .
  • a space velocity i.e. total gas volume (expressed at NTP) fed per hour per volume of catalyst in the range 100 to 10,000 h "1 .
  • carbon is liable to be deposited on the catalyst as a result of side reactionsr e.g. decomposition of the aromatic compound. Such deposited carbon tends to de-activate the catalyst.
  • Such deposited carbon may be removed by regenerating the catalyst by contact with air or oxygen at an elevated temperature in the absence of the aromatic compound. Such regeneration may be effected periodically, e.g.
  • the catalyst may be provided in the form of a rotating bed which during one rotation passes through a zone wherein deposited carbon is burnt off, possibly a reduction zone where the catalyst is reduced to a lower valency state and then the reaction zone.
  • the catalyst is preferably in the form of a coating of vanadia on a monolithic honeycomb support.
  • a flowing, e.g. fluidised powder, catalyst may be employed.
  • the catalyst is cycled through a plurality of stages, including a reaction stage wherein the vanadia is reduced to the tetravalent state and the amine is formed, e.g.
  • the catalyst when used for the amine-forming reaction, in some cases a relatively large proportion of byproducts may initially be formed. This is believed to be the result of the presence of some "over-active" sites. Accordingly it is preferred that such "over-active" sites are subject to a reaction before contact of the catalyst with the aromatic compound.
  • the catalyst if a catalyst that has been used for the reaction and is largely in the tetravalent state, the catalyst is preferably oxidised to the pentavalent state and then subjected to partial reduction before contact with the aromatic compound.
  • a process operated in stages may also be applied to other catalysts having a variable oxidation state or that may be readily reduced to the elemental form, e.g. iron, cobalt, nickel, chromium, manganese, copper, platinum, silver and gold.
  • the present invention also provides a process for the production of an aromatic amine by contacting a gaseous mixture of an aromatic compound and ammonia at an elevated temperature with a catalyst composition comprising at least one metal that can be oxidised from a lower valency state to a higher valency state, said process comprising a plurality of stages including a reaction stage wherein the catalyst in the higher oxidation state is reacted with the aromatic compound and ammonia to form the amine with the reduction of the catalyst to said lower valency state, and a subsequent oxidation stage wherein the catalyst is contacted with an oxygen- containing gas to oxidise said catalyst to the higher valency, i.e. oxidation, state.
  • At least one mole of ammonia is used per mole of aromatic compound.
  • the amount of oxygen-containing gas, if any, employed in the reaction stage is preferably sub-stoichiometric relative to the aromatic compound. Indeed, may be desirable that the catalyst is partially reduced to the lower valency state before the reaction stage.
  • the catalyst in the higher oxidation state may first be contacted with ammonia and then the thus treated catalyst contacted with the aromatic compound.
  • the ammonia is adsorbed onto the catalyst and the aromatic compound reacts with the adsorbed ammonia at the same time effecting reduction of the catalyst to the lower valency state.
  • the catalyst is then contacted with the oxygen-containing gas, before and/or after separating the product amine and any unreacted ammonia and aromatic compound, to effect oxidation to the higher valency state.
  • the sequence of processes, using vanadia as the catalyst is as follows
  • a process employing sequential introduction of the reactants may be effected in a batch process or in a continuous process using a moving bed of catalyst.
  • a semi-continuous process may be adopted where there is periodic reversal of flow of the reactants through the catalyst bed.
  • the process may be operated cyclically wherein, in a first stage, ammonia and the aromatic compound are fed through the catalyst bed in a first direction, then in a second stage, an oxygen-containing gas is fed through the catalyst bed in the direction opposite to the first direction, then in a third stage, ammonia and the aromatic compound are fed through the catalyst bed in the direction opposite to the first direction, and in a fourth stage the cycle is completed by feeding an oxygen-containing gas through the catalyst bed in the first direction.
  • ammonia is first fed through the catalyst bed and then the mixture of ammonia and the aromatic compound is fed through the catalyst bed.
  • Figures 1 and 2 are a diagrammatic flowsheets of alternative fluidised vanadia catalyst systems, and Figures 3a to 3d illustrate a process using a fixed catalyst bed with flow reversal.
  • Figure 4 is a cross section of a reactor for use in a variant of the flowsheets of Figures 1 and 2.
  • a reaction vessel 10 is provided with means (not shown) to remove a vanadia catalyst in a small particle form, e.g. a powder of average size 50-500 ⁇ m, from its lower end, and to return the catalyst particles, via line 12, to the upper end.
  • a gas containing free oxygen; e.g. air is fed to the vessel at the lower end of the vessel via line 14 and effects fluidisation of the catalyst particles and also effects removal of any deposited carbon by combustion, the carbon dioxide produced passing up through the reaction vessel 10.
  • the oxygen also effects oxidation of the vanadium in the catalyst to the pentavalent state in this region of the vessel (designated A in Figure 1 ).
  • ammonia and the aromatic compound e.g.
  • benzene are introduced via line 16 and pass up the vessel, reacting to form the amine, i.e. aniline where the aromatic compound is benzene.
  • This reaction region of the vessel is designated B.
  • the mixture of gaseous products viz.
  • the amine, water, excess aromatic compound and ammonia, nitrogen and carbon dioxide, is removed and sent, via line 18, to a separation unit (not shown) wherein the product amine is separated.
  • the excess of the aromatic compound and ammonia can also be separated and recycled to line 16.
  • the vessel is maintained at the requisite temperature by preheating the feeds thereto.
  • the catalyst is fluidised in the lower part D of the vessel by an oxygen-containing gas, e.g. air, fed to the bottom of the vessel via line 22.
  • the aromatic compound and ammonia are also fed to the bottom of the vessel via line 24.
  • the catalyst is taken from the bottom of the vessel via line 26, and fed to the lower end of a column 28 to the bottom of which an oxygen-containing gas, e.g. air, is fed via line 30.
  • the oxygen-containing gas fed to column 28 serves to oxidise the catalyst to the pentavalent state and to transport it to the upper end of the column from whence it is fed, via line 32, to the top of the vessel 20.
  • the excess of oxygen-containing gas is exhausted from the top of column 28 via line 34.
  • the upper portion E of vessel 20 has an enlarged cross section compared to the lower portion D so that, while the catalyst is fluidised in the lower portion D, it "rains" down through the upper portion E. Reduction of the catalyst takes place in the upper portion E.
  • the product stream leaves the top of vessel 20 via line 36.
  • T e arrangement of Figure 2 may also be adapted to provide for sequential introduction of the reactants.
  • the aromatic compound is introduced to the lower portion of zone D via line 24, and ammonia introduced at a location part way up zone D via line 38.
  • the oxygen-containing gas injected via line 22 may be omitted and an inert gas, e.g. nitrogen, may be fed via line 22 to the bottom of zone D to effect the fluidisation.
  • an inert gas e.g. nitrogen
  • the aromatic compound preferably in admixture with an inert diluent such as nitrogen, may be fed via line 22 to effect fluidisation.
  • the catalyst is disposed as a fixed bed in a vessel 40 provided with a number of inlet ports and with outlet ports at each end of the vessel and the process operated cyclically.
  • ammonia is fed to one (first) end of the vessel via line 41a and passes through the catalyst bed and leaves the vessel at the opposite (second) end via line 42b. While continuing to supply ammonia via line 41a, introduction of the aromatic compound to the first end of the vessel is then commenced via line 43a. The reaction proceeds with the reduction of the catalyst to the lower valency state, and the products are removed from the second end of the vessel through line 42b.
  • a number of catalyst-containing vessels may be employed in parallel but out of phase so that product formation is continuous.
  • a single port can be employed with valves to effect switching between the various streams.
  • the reactor comprises a cylindrical vessel 50 provided with an internal baffle in the form of an open-ended hollow cylinder 51. Air is introduced at the lower end of the vessel via ports 52 and 53 to effect fluidisation of the catalyst and circulation of the latter up through the cylinder 51 and then back down through the annulus 54 between the outer shell of the vessel 50 and the exterior surface of the cylinder 51.
  • a mixture of benzene and ammonia are supplied to the lower end of the annulus 54 via ports 55, and ammonia is supplied, via port 56 into the upper part of the interior of the cylinder 51.
  • the products are removed via outlet port 57.
  • the reaction of the benzene and ammonia is effected in the annulus 53 and the catalyst leaving the reaction zone at the lower end of the annulus and passing up through the cylinder 51 is oxidised by the air flowing up through the cylinder 51.
  • the catalyst is reduced by the ammonia injected through port 56, so that the catalyst leaving the inner cylinder 51 at the top thereof is in the active state.
  • an alternative reducing gas for example hydrogen, may be introduced through port 56.
  • the gas used to effect fluidisation and/or circulation may be an inert gas such as nitrogen and the requisite amount of oxygen may be introduced via port 52.
  • nitrogen may be introduced via ports 53 and air through port 52.
  • Example 1 ⁇ -alumina extrudates (AL 3992-ETM) of about 2-3 mm length and having a BET surface area of 180 m 2 /g were impregnated with an aqueous solution of ammonium metavanadate, dried, and calcined at 550°C for 3 h to give a catalyst containing 8% by weight of vanadia, expressed as V 2 0 5 . 12.68 g of the catalyst was placed in a fixed bed reactor of 1 cm internal diameter. The reactor was heated to about 450 C C and the catalyst was reduced to V 2 0 by passing a mixture of hydrogen and nitrogen through the bed for 16 h.
  • a 3992-ETM ⁇ -alumina extrudates
  • a mixture of benzene, ammonia and oxygen diluted with nitrogen in molar proportions of 3 moles of ammonia, 0.05 moles of oxygen, and 2.45 moles of nitrogen per mole of benzene was then continually passed through the catalyst bed at a space velocity of 300 h "1 at a temperature of 450°C at a pressure of about 9 bar abs.
  • reaction products were then cooled below 10°C, and the organic phase collected for analysis.
  • the maximum amount of aniline produced expressed as a percentage of all carbon- containing products (excluding unreacted feed components), was about 71% by weight.
  • the catalyst had the vanadium in the valency state 5. It was observed that the activity increased with time and then decreased, passing through a peak corresponding to a vanadium valency state between 4 and 5.
  • Example 2 A vanadium oxide/alumina catalyst was prepared as described in Example 1 and the oxidation state before and after reduction was determined.
  • the catalyst as prepared was examined by X-ray diffraction (XRD) and the only vanadium oxide phase detected was that of V 2 0 5 .
  • the reduction of the catalyst was studied by thermogravimetric analysis (TGA), the catalyst being heated in a stream of 5% hydrogen in nitrogen was compared to heating in a stream of nitrogen.
  • TGA thermogravimetric analysis
  • a weight loss of 1 % was detected between 410 and 535°C when the sample was heated in the hydrogen-containing stream. This corresponded to the loss of one oxygen atom from each V 2 0 5 unit, i.e. reduction from V 2 0 5 to V 2 0 4 .
  • the extent of re-oxidation was also determined by pulsing oxygen over a reduced catalyst. Thus immediately after reduction at 500°C, a catalyst was subjected to aliquots of dioxygen while the catalyst bed was still at 500°C. The amount of dioxygen adsorbed was determined and hence the ratio of 0(ads):V 2 was calculated and found to be 1.1 :1.
  • Example_3 A catalyst was prepared as described in Example 1. The catalyst was reduced at 450°C in flowing hydrogen/nitrogen for 16 h. The catalyst was cooled to 400°C and the gas flow was then switched to a gas flow-containing ammonia/benzene/oxygen having a molar ratio of 150r24: 1 , at a pressure of 2 bar abs. and a space velocity of 300 h "1 . The variation of aniline yield with time is shown in the Table below.
  • Example 4 A catalyst was prepared as described in Example 1. The catalyst was reduced at 450°C in flowing hydrogen/nitrogen for 16 h. The catalyst was cooled to 350°C and the gas flow was then switched to a gas flow containing ammonia/benzene/oxygen having a molar ratio of 17: 8: 1, at a pressure of 2 bar abs. and a space velocity of 300 h "1 . The variation of aniline yield with time is shown in the following table.
  • Silica spheres (Fuji Sylisia, Q10) of about 5 mm diameter and having a BET surface area of 300 m 2 /g were impregnated with an aqueous solution of ammonium metavanadate, dried, and calcined at 873 K for 3 h to give a catalyst containing 12% by weight of vanadia, expressed as V 2 0 5 .
  • the catalyst was subjected to a flow of benzene, ammonia, and oxygen in the ratio 1 :3:0.05.
  • the contact time was 3.5 s, the temperature 723 K, and the pressure 7.5 bara. Under these conditions the initial molar selectivity, based on carbon containing products was 17%, as the run continued the selectivity increased to give a molar, selectivity of 87%.
  • Example 5 The catalyst in Example 5 was subjected to different ammonia ratios. When the benzene:ammonia:oxygen ratio was 1 :100:0.05 the selectivity increased from 87% to 96%.
  • T e catalyst in Example 5 was subjected to sequenced flows, such that individual flows of benzene, ammonia, and oxygen were passed over the catalyst.
  • the initial sequencing rate was such that each flow was on-line for 15 s.
  • the test was then repeated with a sequencing rate of 9 s.
  • aniline was produced.
  • the production of aniline was equivalent to the continuous flow system with a 15 s sequence, however with the shorter time sequence, the yield was increased by 30%.
  • Example 8 In a calculated example of the invention using the flowsheet of Figure 1 to produce aniline at a rate of 10 kmol/h, the catalyst consists of particles of vanadia supported on alumina of average size 250 ⁇ m.
  • the catalyst contains 8% by weight of vanadia expressed as V 2 0 5 and is circulated via line 12 at a rate of 12640 kg per hour (approx. 5.6 kmol/h of vanadia expressed as V 2 0 5 ). Air is fed via line 14 at 25°C and at a pressure of 3 bar abs. A mixture of benzene and ammonia (5 moles of ammonia per mole of benzene) is fed at 3 bar abs and at 210°C via line 16. For simplicity it is assumed that no carbon is deposited on the catalyst so that in the oxidation zone A, the catalyst is simply oxidised to the pentavalent state and no carbon dioxide is formed. In the reduction zone C, part of the vanadia is reduced to the tetravalent state.
  • zone B It is assumed that some oxidation/reduction occurs in zone B, but that most of the catalyst leaving the bottom of zone B is in the tetravalent rate and is oxidised in zone A to the pentavalent state.
  • the calculated flow rates and temperatures are set out in the following table.
  • Example 9 In a calculated example of the invention using the flowsheet of Figure 2 to produce aniline at a rate of 10 kmol/h, the catalyst consists of particles of vanadia supported on alumina of average size 250 ⁇ m.
  • the catalyst contains 8% by weight of vanadia expressed as V 2 0 and is circulated via line 32 at a rate of 12639 kg per hour (approx. 5.6 kmol/h of vanadia expressed as V 2 0 5 ).
  • Air is fed to vessel 20 via line 22 at 330°C and at a pressure of 5 bar abs.
  • a mixture of benzene and ammonia (5 moles of ammonia per mole of benzene) is fed at 5 bar abs. and at 200°C via line 24.
  • Air is fed to the base of column 28 at 330°C and at a pressure of 5 bar abs.
  • the catalyst is simply oxidised to the pentavalent state and no carbon dioxide is formed.
  • the reduction zone E part of the vanadia is reduced to the tetravalent state. It is assumed that some oxidation/reduction occurs in zone D, but that most of the catalyst leaving the bottom of zone D is in the tetravalent rate and is oxidised in column 28 to the pentavalent state.
  • the calculated flow rates and temperatures are set out in the following table.
  • the temperature of the catalyst leaving the zone D via line 26 is 375°C.

Landscapes

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

Abstract

L'invention concerne des amines aromatiques, par exemple des anilines, produits par mise en contact, à une température élevée, d'un mélange gazeux contenant un agent aromatique, par exemple du benzène, et de l'ammoniac avec une composition de catalyseur, comprenant au moins un oxyde de vanadium par mole de composé aromatique, au moins un mole d'ammoniac et une quantité sous-stoichiométrique d'un puits d'hydrogène. Ce procédé peut être réalisé en plusieurs étapes et/ou avec une introduction séquentielle de réactifs.
PCT/GB1999/002366 1998-08-17 1999-07-21 Production d'amine WO2000009473A1 (fr)

Priority Applications (1)

Application Number Priority Date Filing Date Title
AU50542/99A AU5054299A (en) 1998-08-17 1999-07-21 Amine production

Applications Claiming Priority (8)

Application Number Priority Date Filing Date Title
PCT/GB1998/002453 WO1999010311A1 (fr) 1997-08-21 1998-08-17 Procede de production d'amines aromatiques
GBPCT/GB98/02453 1998-08-17
GBGB9825704.1A GB9825704D0 (en) 1998-08-17 1998-11-25 Amine production
GB9825704.1 1998-11-25
GB9900585.2 1999-01-13
GB9900585 1999-01-13
GB9903599.0 1999-02-18
GBGB9903599.0A GB9903599D0 (en) 1998-08-17 1999-02-18 Amine production

Publications (1)

Publication Number Publication Date
WO2000009473A1 true WO2000009473A1 (fr) 2000-02-24

Family

ID=27451746

Family Applications (1)

Application Number Title Priority Date Filing Date
PCT/GB1999/002366 WO2000009473A1 (fr) 1998-08-17 1999-07-21 Production d'amine

Country Status (2)

Country Link
AU (1) AU5054299A (fr)
WO (1) WO2000009473A1 (fr)

Cited By (8)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US6933409B1 (en) 1999-05-13 2005-08-23 Symyx Technologies, Inc. Amination of aromatic hydrocarbons and heterocyclic analogs thereof
WO2007025882A1 (fr) * 2005-08-30 2007-03-08 Basf Se Amination directe d'hydrocarbures
WO2008009668A1 (fr) * 2006-07-21 2008-01-24 Basf Se Amination directe d'hydrocarbures
US7741522B2 (en) 2006-02-24 2010-06-22 Basf Aktiengesellschaft Direct amination of hydrocarbons
US7838702B2 (en) 2006-02-24 2010-11-23 Basf Se Direct amination of hydrocarbons
WO2011003964A3 (fr) * 2009-07-10 2011-05-05 Basf Se Procédé d'amination directe d'hydrocarbures en amino-hydrocarbures avec séparation électrochimique d'hydrogène
WO2016155948A1 (fr) * 2015-04-02 2016-10-06 Huntsman International Llc Amination directe d'hydrocarbures
CN106278904A (zh) * 2016-08-08 2017-01-04 河北工业大学 由苯一锅法制备环己胺的方法

Families Citing this family (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
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

Citations (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US2948755A (en) * 1958-03-07 1960-08-09 Universal Oil Prod Co Preparation of aromatic amines
JPS6239548A (ja) * 1985-08-16 1987-02-20 Mitsui Toatsu Chem Inc アミノ化合物の製法
DE19634110A1 (de) * 1996-08-23 1998-02-26 Hoechst Ag Verfahren zur Herstellung von aminosubstituierten aromatischen Kohlenwasserstoffen
WO1999010311A1 (fr) * 1997-08-21 1999-03-04 Huntsman Ici Chemicals, Llc Procede de production d'amines aromatiques

Patent Citations (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US2948755A (en) * 1958-03-07 1960-08-09 Universal Oil Prod Co Preparation of aromatic amines
JPS6239548A (ja) * 1985-08-16 1987-02-20 Mitsui Toatsu Chem Inc アミノ化合物の製法
DE19634110A1 (de) * 1996-08-23 1998-02-26 Hoechst Ag Verfahren zur Herstellung von aminosubstituierten aromatischen Kohlenwasserstoffen
WO1999010311A1 (fr) * 1997-08-21 1999-03-04 Huntsman Ici Chemicals, Llc Procede de production d'amines aromatiques

Non-Patent Citations (1)

* Cited by examiner, † Cited by third party
Title
PATENT ABSTRACTS OF JAPAN vol. 011, no. 222 (C - 435) 18 July 1987 (1987-07-18) *

Cited By (16)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US6933409B1 (en) 1999-05-13 2005-08-23 Symyx Technologies, Inc. Amination of aromatic hydrocarbons and heterocyclic analogs thereof
WO2007025882A1 (fr) * 2005-08-30 2007-03-08 Basf Se Amination directe d'hydrocarbures
US7741522B2 (en) 2006-02-24 2010-06-22 Basf Aktiengesellschaft Direct amination of hydrocarbons
US7838702B2 (en) 2006-02-24 2010-11-23 Basf Se Direct amination of hydrocarbons
WO2008009668A1 (fr) * 2006-07-21 2008-01-24 Basf Se Amination directe d'hydrocarbures
WO2011003964A3 (fr) * 2009-07-10 2011-05-05 Basf Se Procédé d'amination directe d'hydrocarbures en amino-hydrocarbures avec séparation électrochimique d'hydrogène
US9061961B2 (en) 2009-07-10 2015-06-23 Basf Se Method for direct amination of hydrocarbons to form amino hydrocarbons with the electrochemical separation of hydrocarbon
JP2018515430A (ja) * 2015-04-02 2018-06-14 ハンツマン・インターナショナル・エルエルシー 炭化水素の直接アミノ化
KR20170133438A (ko) * 2015-04-02 2017-12-05 헌트스만 인터내셔날, 엘엘씨 탄화수소의 직접 아미노화
CN107801392A (zh) * 2015-04-02 2018-03-13 亨茨曼国际有限公司 烃的直接胺化
WO2016155948A1 (fr) * 2015-04-02 2016-10-06 Huntsman International Llc Amination directe d'hydrocarbures
US10442753B2 (en) 2015-04-02 2019-10-15 Huntsman International Llc Direct amination of hydrocarbons
CN107801392B (zh) * 2015-04-02 2021-02-05 亨茨曼国际有限公司 烃的直接胺化
KR102574270B1 (ko) 2015-04-02 2023-09-05 헌트스만 인터내셔날, 엘엘씨 탄화수소의 직접 아미노화
CN106278904A (zh) * 2016-08-08 2017-01-04 河北工业大学 由苯一锅法制备环己胺的方法
CN106278904B (zh) * 2016-08-08 2018-03-27 河北工业大学 由苯一锅法制备环己胺的方法

Also Published As

Publication number Publication date
AU5054299A (en) 2000-03-06

Similar Documents

Publication Publication Date Title
US4962261A (en) Process for upgrading methane to higher carbon number hydrocarbons
US7345199B2 (en) Catalyst composition for the selective conversion of alkanes to unsaturated carboxylic acids, method of making and method of using thereof
EP0177327B1 (fr) Procédé pour la transformation d'alkanes de bas poids moléculaire
RU2259988C2 (ru) Катализатор и способ получения углеводородов
US5095161A (en) Process and catalyst for upgrading methane to higher carbon number hydrocarbons
JP2011116789A (ja) アルケン分離方法
KR20060132818A (ko) 메틸머캅탄의 제조방법
EP0894781A1 (fr) Procédé pour la préparation d'oléfines légères par déshydrogénation des paraffines correspondantes
WO2005051527A2 (fr) Catalyseurs modifies par du cuivre pour la deshydrogenation oxydative
KR20090015982A (ko) 염화수소 함유 기체의 산화 방법
WO2000009473A1 (fr) Production d'amine
RU2612305C1 (ru) Способ окислительной конверсии этана в этилен
AU701924B2 (en) Process for the manufacture of acrylic acid from acrolein by a redox reaction and use of a solid mixed oxides composition as redox system in the said reaction
US7261870B2 (en) Process for the reduction of carbon monoxide and carbonyl sulfide emissions
US3978200A (en) Process for reduction of sulfur dioxide to sulfur
KR101006038B1 (ko) 알케닐 카르복실레이트 또는 알킬 카르복실레이트의 제조방법
WO2005060442A2 (fr) Procede de production d'olefines a partir d'alkanes avec une charge de monoxyde de carbone et/ou de recyclage
EP1657290A1 (fr) nouveau catalyseur pour être utilisé dans un procédé en une étape pour la production d'essence à partir du gaz de synthèse et procédé amélioré de régénération de ce catalyseur
US20040221508A1 (en) Rare earth aluminates and gallates supported rhodium catalysts for catalytic partial oxidation of hydrocarbons
EP0232962B1 (fr) Catalyseur pour la conversion de gaz de synthèse, sa préparation et son utilisation
KR20080096686A (ko) 에탄-기재 공정에서 에탄으로부터 에틸렌을 분리하여 아세트산을 제조하기 위한 화학 반응의 용도
JPH04504728A (ja) クロロフォルムの製造方法
Guerrero-Ruiz et al. Effect of the basic function in Co, MgO/C catalysts on the selective oxidation of methane by carbon dioxide
EP0703889B1 (fr) Procede de production de styrene
US20060020152A1 (en) Method for the low temperature selective oxidation of hydrogen contained in a hydrocarbon stream

Legal Events

Date Code Title Description
AK Designated states

Kind code of ref document: A1

Designated state(s): AU BR CA CN CZ HU ID IN JP KR MX NO NZ PL RU SG TR US VN ZA

AL Designated countries for regional patents

Kind code of ref document: A1

Designated state(s): AT BE CH CY DE DK ES FI FR GB GR IE IT LU MC NL PT SE

DFPE Request for preliminary examination filed prior to expiration of 19th month from priority date (pct application filed before 20040101)
121 Ep: the epo has been informed by wipo that ep was designated in this application
122 Ep: pct application non-entry in european phase