WO2003089407A1 - Procede de preparation de nitriles insatures - Google Patents

Procede de preparation de nitriles insatures Download PDF

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Publication number
WO2003089407A1
WO2003089407A1 PCT/EP2003/004040 EP0304040W WO03089407A1 WO 2003089407 A1 WO2003089407 A1 WO 2003089407A1 EP 0304040 W EP0304040 W EP 0304040W WO 03089407 A1 WO03089407 A1 WO 03089407A1
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alkene
alkane
oxygen
ammonia
stream
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PCT/EP2003/004040
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German (de)
English (en)
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Götz-Peter SCHINDLER
Frank Rosowski
Frieder Borgmeier
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Basf Aktiengesellschaft
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Priority to AU2003229694A priority Critical patent/AU2003229694A1/en
Publication of WO2003089407A1 publication Critical patent/WO2003089407A1/fr

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    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C253/00—Preparation of carboxylic acid nitriles
    • C07C253/24—Preparation of carboxylic acid nitriles by ammoxidation of hydrocarbons or substituted hydrocarbons
    • C07C253/26—Preparation of carboxylic acid nitriles by ammoxidation of hydrocarbons or substituted hydrocarbons containing carbon-to-carbon multiple bonds, e.g. unsaturated aldehydes

Definitions

  • the invention relates to a process for the production of unsaturated nitriles from alkanes.
  • alkenes such as acrylonitrile and methacrylonitrile from the corresponding alkenes propene or isobutene by so-called ammoxidation of the alkenes with an ammonia / oxygen mixture in the presence of a suitable catalyst.
  • the relevant alkenes can be prepared in an upstream dehydrogenation stage from the corresponding alkanes.
  • acrylonitrile is obtained from propene and methacrylonitrile isobutene.
  • the corresponding ⁇ -unsaturated nitrile is obtained from a methyl-substituted olefin, the methyl group being converted into a nitrile group.
  • EP-A 0 193 310 describes a process for the preparation of acrylonitrile from propane, comprising the catalytic dehydrogenation of propane to propene, the ammoxidation of
  • the hydrogen formed in the dehydrogenation is selectively burned with oxygen on an oxidation catalyst to form water, a hydrogen-depleted, unreacted propane, propene, carbon oxides and low-boiling
  • a disadvantage of this method is the heat transport limitation associated with the heating of the reaction gases by external firing.
  • the object of the invention is to provide an improved process for the production of acrylonitrile from propane.
  • the task is solved by a process for the production of unsaturated nitriles from the corresponding alkanes with the steps
  • alkane and alkene containing alkane and alkene, water vapor and optionally one or more further gas constituents selected from the group consisting of hydrogen, oxygen, carbon oxides, ammomac, low-boiling hydrocarbons, nitrogen and noble gases,
  • a gas stream D which contains the unreacted alkane and alkene and optionally one or more gas components from the group consisting of hydrogen, oxygen, carbon oxides, ammonia, low-boiling hydrocarbons, nitrogen and noble gases, and an aqueous stream is obtained , which contains the nitrile and the by-products, and
  • the alkane and oxygen-containing gas are fed into a dehydrogenation zone and the alkane is dehydrogenated to the corresponding alkene in an autothermal catalytic dehydrogenation.
  • the required heat of reaction is generated directly in the reactor system by burning hydrogen formed during the dehydrogenation and optionally hydrocarbons in the presence of oxygen.
  • the oxygen can be fed into the dehydrogenation zone as a co-feed and / or contained in the recycle gas stream D.
  • the method according to the invention can be carried out in such a way that oxygen is only fed into the ammoxidation zone and the (excess) oxygen contained in the (recirculated) gas stream D functions as the exclusive oxygen source for the autothermal catalytic dehydrogenation. If necessary, a hydrogen-containing co-feed can also be added.
  • Alkanes from which the process according to the invention is based are generally C 3 -C 1 -alkanes, preference being given to propane and isobutane.
  • the latter can be obtained from LPG (liquefied petroleum gas) or LNG (liquefied natural gas), for example.
  • dehydrogenation produces cracked alkane products.
  • carbon oxides CO, CO 2
  • water and nitrogen can also be present in the product gas mixture of the alkane dehydrogenation.
  • the autothermal alkane dehydrogenation can in principle be carried out in all reactor types and procedures known from the prior art.
  • a comparatively comprehensive description of dehydrogenation processes suitable according to the invention also contains "Catalytica® ® Studies Division, Oxidative Dehydrogenation and Alternative Dehydrogenation Processes" (Study Number 4192 OD, 1993, 430 Ferguson Drive, Mountain View, California, 94043-5272, USA).
  • a suitable reactor form is the fixed bed tube or tube bundle reactor. These contain the dehydrogenation catalyst and, if appropriate, also a special oxidation catalyst as a fixed bed in a reaction tube or in a bundle of reaction tubes. Usual reaction tube inner diameters are about 10 to 15 cm.
  • a typical dehydrogenation tube bundle reactor comprises approx. 300 to 1000 reaction tubes. The temperature in the interior of the reaction tube usually ranges from 300 to 1200 ° C, preferably in the range of 600 to 1000 ° C.
  • the working pressure is usually between 0.5 and 8 bar, often between 1 and 2 bar when using a low water vapor dilution (analogous to the Linde process for propane dehydrogenation), but also between 3 and 8 bar when using a high water vapor dilution (analog the so-called “steam active reforming process” (STAR process) for the dehydrogenation of propane or butane from Phillips Petroleum Co., see US 4,902,849, US 4,996,387 and US 5,389,342).
  • Typical catalyst loads (GHSV) are 500 to 2000 h "1 , based on the alkane to be dehydrogenated.
  • the catalyst geometry can be spherical or cylindrical (hollow or full), for example.
  • the catalytic alkane dehydrogenation can also, as in Chem. Eng. Be. 1992 b, 47 (9-11) 2313, heterogeneously catalyzed in a fluidized bed.
  • two fluidized beds are operated side by side, one of which is usually in the state of regeneration.
  • the working pressure is typically 1 to 2 bar, the dehydrogenation temperature usually 550 to 600 ° C.
  • the heat required for the dehydrogenation is introduced into the reaction system by preheating the dehydrogenation catalyst to the reaction temperature.
  • the preheaters can be dispensed with, and the heat required is generated directly in the reactor system by burning hydrogen and / or hydrocarbon in the presence of oxygen. If necessary, a hydrogen-containing co-feed can also be added.
  • the autothermal alkane dehydrogenation can be carried out in a tray reactor.
  • This contains one or more successive catalyst beds.
  • the number of catalyst beds can be 1 to 20, advantageously 1 to 6, preferably 1 to 4 and in particular 1 to 3.
  • the reaction beds preferably flow radially or axially through the catalyst beds.
  • Such a tray reactor is generally operated with a fixed catalyst bed.
  • the fixed catalyst beds are arranged axially in a shaft furnace reactor or in the annular gaps of centrally arranged cylindrical grids.
  • a shaft furnace reactor corresponds to a horde.
  • Carrying out the dehydrogenation in a single shaft furnace reactor corresponds to a preferred embodiment.
  • the dehydrogenation is carried out in a tray reactor with 3 catalyst beds.
  • reaction gas mixture of the alkane dehydrogenation in at least one reaction zone and the gas contained in the reaction gas mixture Hydrogen and / or the hydrocarbons contained therein are burned, whereby at least some of the heat of dehydrogenation required is generated in the at least one reaction zone directly in the reaction gas mixture.
  • the reaction gas mixture can be subjected to intermediate heating on its way from one catalyst bed to the next catalyst bed, for example by passing it over heat exchanger fins heated with hot gases or passing it through tubes heated with hot fuel gases.
  • the amount of oxygen-containing gas added to the reaction gas mixture is selected so that the combustion of the
  • Carbon is the amount of heat required to dehydrate the alkane.
  • the total amount of oxygen supplied based on the total amount of the alkane, is 0.001 to 0.5 mol / mol, preferably 0.005 to 0.2 mol / mol, particularly preferably 0.05 to 0.2 mol / mol.
  • Oxygen can be used either as pure oxygen or as an oxygen-containing gas in a mixture with inert gases.
  • the preferred oxygen-containing gas is the oxygen-containing gas stream D ′′ recirculated in step e), which
  • Inert gases and the resulting combustion gases generally have an additional dilution effect and thus promote heterogeneously catalyzed dehydrogenation.
  • the hydrogen burned to generate heat is the hydrogen formed in the catalytic alkane dehydrogenation and, if appropriate, hydrogen additionally added to the reaction gas mixture.
  • Sufficient hydrogen should preferably be present so that the molar ratio H 2 / O 2 in the reaction gas mixture is 2 to 10 mol / mol immediately after oxygen has been fed in. In multi-stage reactors, this applies to every intermediate feed of oxygen and possibly hydrogen.
  • the hydrogen is burned catalytically.
  • the dehydrogenation catalyst used generally also catalyzes the combustion of the hydrocarbons and of hydrogen with oxygen, so that in principle no special oxidation catalyst different from this is required.
  • the process is carried out in the presence of one or more oxidation catalysts which selectively catalyze the combustion of hydrogen with oxygen in the presence of hydrocarbons.
  • the combustion of these hydrocarbons with oxygen to CO and CO 2 takes place only to a minor extent, which has a clearly positive effect on the selectivities achieved for the alkene formation.
  • the dehydrogenation catalyst and the oxidation catalyst are preferably present in different reaction zones. °
  • the oxidation catalyst can be present in only one, in several or in all reaction zones.
  • the catalyst which selectively catalyzes the oxidation of hydrogen, is preferably arranged at the points where there are higher oxygen partial pressures than at other points in the reactor, in particular in the vicinity of the feed point for the oxygen-containing gas.
  • Oxygen-containing gas and / or hydrogen can be fed in at one or more points in the reactor.
  • oxygen-containing gas and hydrogen are fed in before each tray except the first tray.
  • a layer of a special oxidation catalyst is present behind each feed point, followed by a layer of the dehydrogenation catalyst.
  • no special oxidation catalyst is present.
  • the dehydrogenation temperature is generally 400 to 1100 ° C.
  • the pressure in the last catalyst bed of the tray reactor is generally 0.2 to 5 bar, preferably 1 to 3 bar.
  • the load (GHSV) is generally 500 to 2000 h "1 , in the high-load mode also up to 100,000 h " , preferably 4000 to 16,000 h " , based on the alkane to be dehydrogenated.
  • a preferred catalyst that selectively catalyzes the combustion of hydrogen contains oxides or phosphates selected from the group consisting of the oxides or phosphates of germanium, tin, lead, arsenic, antimony, indium or bismuth.
  • Another preferred catalyst, which catalyzes the combustion of hydrogen contains a noble metal of subgroup VIII or I.
  • the dehydrogenation catalysts used generally have a support and an active composition.
  • the carrier consists of a heat-resistant oxide or Mixed oxide.
  • the dehydrogenation catalysts preferably contain a metal oxide, which is selected from the group consisting of zirconium dioxide, zinc oxide, aluminum oxide, silicon dioxide, titanium dioxide, magnesium oxide, lanthanum oxide, cerium oxide and mixtures thereof, as a carrier.
  • the mixtures can be physical mixtures or chemical mixed phases such as magnesium or zinc aluminum oxide mixed structures.
  • Preferred supports are zirconium dioxide and / or silicon dioxide, and mixtures of zirconium dioxide and silicon dioxide are particularly preferred.
  • the active composition of the dehydrogenation catalysts generally contains one or more elements of subgroup VIII, preferably platinum and / or palladium, particularly preferably platinum.
  • the dehydrogenation catalysts can be one or more
  • Main group preferably potassium and / or cesium.
  • the dehydrogenation catalysts can include one or more elements of III.
  • Subgroup including the lanthanides and actinides contain, preferably lanthanum and / or cerium.
  • the dehydrogenation catalysts can be one or more
  • Lead particularly preferably tin.
  • the dehydrogenation catalyst contains at least one element from subgroup VIII, at least one element from main group I and / or II, at least one element from III. and or IV. main group and at least one element of III. Subgroup including the lanthanides and actinides.
  • all dehydrogenation catalysts described in WO 99/46039, US 4,788,371, EP-A 705 136, WO 99/29420, US 5,220,091, US 5,430,220, US 5,877,369, EP 0 117 146, DE-A 199 37 106 can be used according to the invention , DE-A 199 37 105 and DE-A 199 37 107.
  • Particularly preferred catalysts for the above-described variants of the autothermal alkane dehydrogenation are the catalysts according to Examples 1, 2, 3 and 4 of DE-A 199 37 107.
  • the alkane dehydrogenation is preferably carried out in the presence of steam.
  • the added water vapor serves as a heat carrier and supports the gasification of organic deposits on the catalysts, which counteracts the coking of the catalysts and increases the service life of the catalyst.
  • the organic deposits are converted into carbon monoxide and carbon dioxide.
  • the alkane dehydrogenation can also be carried out in the cycle gas procedure described in the unpublished German patent application P 102 11 275.4.
  • the dehydrogenation catalyst can be regenerated in a manner known per se. Steam can be added to the reaction gas mixture or an oxygen-containing gas can be passed over the catalyst bed at elevated temperature from time to time and the deposited carbon can be burned off. The dehydrogenation catalyst is then optionally reduced in an atmosphere containing hydrogen.
  • a gas mixture which contains secondary constituents in addition to alkene and unreacted alkane.
  • Common secondary components are hydrogen, water, nitrogen, carbon oxides (CO and CO 2 ) and low-boiling hydrocarbons such as methane, ethane and ethene.
  • the product gas mixture will have a comparatively high content of water and carbon oxides.
  • the product gas mixture leaving the dehydrogenation reactor contains at least the constituents propane, propene and water vapor and, in addition, also customarily also carbon oxides and molecular hydrogen.
  • the product gas mixture of the dehydrogenation will be under a pressure of 0.3 to 10 bar and will often have a temperature of 400 to 1200 ° C, in favorable cases 450 to 800 ° C.
  • a process step b the product gas stream A of the autothermal dehydrogenation, ammonia and oxygen-containing gas are fed into an oxidation zone and ammoxidation of the alkene to the corresponding unsaturated nitrile is carried out.
  • the product gas stream A is fed into the oxidation zone without any individual
  • the catalytic ammoxidation is carried out in a manner known per se.
  • the ammoxidation is usually carried out at temperatures from 375 to 550 ° C. and pressures from 0.1 to 10 bar with an ammonia to alkene molar ratio of 0.2: 1 to 2: 1.
  • Suitable catalysts are known to the person skilled in the art and are described, for example, in WO95 / 05241, EP-A 0 573 713, US 5,258,543 and US 5,212,137.
  • the ammoxidation can be carried out in a tubular reactor which contains the catalyst in particulate form and which is surrounded by a cooling liquid for removing the heat of reaction.
  • the ammoxidation is preferably carried out in a fluidized bed reactor.
  • the volume ratio of oxygen to alkene is usually from 1.6: 1 to 2.4: 1.
  • the volume ratio of ammonia to alkene is usually from 0.7: 1 to 1.2: 1.
  • Pure oxygen, air or oxygen-enriched air can be fed into the oxidation zone as the oxygen-containing gas.
  • the preferred oxygen-containing gas is pure oxygen.
  • oxygen is fed into the oxidation zone in a stoichiometric excess with respect to the ammoxidation.
  • a product gas stream B which contains the unsaturated nitrile, by-products of the ammoxidation, unreacted alkane and alkene, water vapor, optionally oxygen, optionally hydrogen, optionally carbon oxides, optionally ammonia, optionally low-boiling hydrocarbons and optionally nitrogen and noble gases.
  • the product gas stream contains excess residual oxygen. As a rule, it will also contain ammonia, low-boiling hydrocarbons and hydrogen from the alkane dehydrogenation. It will contain nitrogen and noble gases when air is fed in as an oxygen-containing gas.
  • the product gas stream B of the ammoxidation of propene to acrylonitrile may contain by-products of the ammoxidation of acrolein, acetonitrile and HCN and the product gas stream B of the ammoxidation of isobutene to methacrylonitrile as by-products of methacrolein, HCN, acetonitrile and acrylonitrile.
  • ammonia can be separated from the product gas stream B in a process step c), a product gas stream C which is strongly depleted in ammonia or freed from ammonia being obtained.
  • ammonia is separated off c) by bringing the hot product gas stream B from the ammoxidation into contact with aqueous sulfuric acid in a quench tower and thus washing ammonia out of the product gas stream B as ammonium sulfate.
  • An aqueous ammonium sulfate solution is obtained, which can contain dissolved unsaturated nitrile and by-products of ammoxidation. These can be stripped with steam from the aqueous ammonium sulfate solution in a downstream steam stripper and sent for further distillative workup.
  • ammonia in the subsequent absorption step d) is largely, if not completely, separated from the product gas stream of the ammoxidation by absorption in the aqueous absorption medium.
  • ammonia can also be removed from the ammoxidation product gas mixture by feeding methanol into the upper part of the fluidized bed reactor in which the ammoxidation is carried out (between about 85 and 95% of the total length) and with ammonia to form HCN, Water and carbon dioxide react.
  • the unsaturated nitrile and optionally by-products of ammoxidation are separated from product gas stream B or C by absorption in an aqueous absorption medium.
  • the product gas stream B or C is brought into contact with the aqueous absorbent in a gas scrubber, an aqueous stream containing the unsaturated nitrile, optionally by-products of ammoxidation and optionally ammonia, and from which subsequently the Unsaturated nitrile is obtained, and an offgas stream D which contains unreacted alkane and alkene, optionally hydrogen, optionally oxygen, optionally carbon oxides, optionally ammonia, optionally low-boiling hydrocarbons such as methane, ethane and ethene and optionally nitrogen and noble gases.
  • the exhaust gas stream D will usually also contain oxygen, hydrogen, carbon oxides and low-boiling hydrocarbons.
  • ammonia is at least partially formed in the presence of carbon dioxide also contained in the product gas stream B. of ammonium carbonate dissolved in the aqueous absorbent.
  • the unsaturated nitrile is obtained by distillation from the aqueous stream obtained in the absorption step.
  • the aqueous stream obtained in the absorption step can be separated in a first distillation column into a top draw stream of crude acrylonitrile and a bottom draw stream containing acetonitrile, water and high boilers.
  • the crude acrylonitrile obtained as the top draw stream which in particular can still contain HCN, can be further purified by distillation. Pure acetonitrile can be obtained by distillation from the bottom draw stream.
  • methacrylonitrile production the processing is carried out analogously.
  • the gas stream D is separated into two partial streams D 'and D ", optionally unreacted alkane and alkene separated from the partial stream D', the partial stream D" and optionally unreacted alkane and alkene separated from the partial stream D ' returned to the dehydrogenation zone.
  • the ratio DVD is usually from 10 to 1/1000, preferably from 1 to 1/100, particularly preferably from 1/10 to 1/50.
  • a separation and recycling of alkane and alkene from the partial stream D ' is generally only then take place if the ratio DVD "is greater than 1/10. With a DVD ratio of less than 1/20, in all As a rule, separation and recycling of alkane and alkene contained in D 'are dispensed with.
  • the separation of a partial stream D ' creates a sink for carbon oxides formed, low-boiling hydrocarbons and for nitrogen and noble gases introduced by using air as the oxygen-containing gas in the autothermal dehydrogenation and / or ammoxidation.
  • This sink is also called "purge”.
  • Unreacted alkane and alkene can be separated off from partial stream D 'by cooling and condensing the condensable gas components in a condenser and then separating them from the non-condensable gas components in a separator.
  • Carbon oxides, hydrogen, oxygen, nitrogen, ammonia and low-boiling hydrocarbons such as methane, ethane and ethene are separated as non-condensable gas constituents - if they are contained in the gas stream D or D 'and discharged from the process. Rectification can follow the condensation in order to achieve as complete a separation as possible of unreacted alkane and alkene from low-boiling hydrocarbons.
  • a water phase and an organic phase from an alkane / alkene mixture form in the separator.
  • the alkane / alkene mixture can be separated from the water phase by simple phase separation.
  • Unreacted alkane and alkene can also be separated off from partial stream D 'in an absorption-Z-desorption cycle by means of a high-boiling absorption medium.
  • a high-boiling absorption medium essentially all of the non-condensable or low-boiling gas constituents (nitrogen, hydrogen, carbon oxides, oxygen, low-boiling hydrocarbons) contained in the partial stream D 'are removed from the process cycle.
  • the unreacted alkane and alkene are absorbed in an inert absorption medium, optionally under increased pressure, in an absorption stage, an absorption medium loaded with the alkane and alkene and an offgas containing the secondary components being obtained.
  • an absorption stage In a desorption stage at a lesser alkane and alkene released from the absorbent than the pressure prevailing during the absorption.
  • Inert absorption agents used in the absorption stage are generally high-boiling nonpolar solvents in which the alkane / alkene mixture to be separated off has a significantly higher solubility than the other constituents of the gas stream D '.
  • the absorption can be done by simply passing the gas flow through the absorption medium. However, it can also take place in columns or in rotary absorbers. You can work in cocurrent, countercurrent or crossflow.
  • Suitable Abso ⁇ tionskolonnen include plate columns having bubble, centrifugal and / or sieve trays, columns with structured packings, for example sheet metal packings with a specific surface area of 100 to 1000 m 2 / m 3 as Mellapak ® 250 Y, and Rudkö ⁇ erkolonnen.
  • trickle and spray towers graphite block absorbers, surface absorbers such as thick-film and thin-film absorbers as well as rotary columns, plate washers, cross-curtain washers and rotary washers can also be used.
  • Suitable absorbents are comparatively non-polar organic solvents, for example aliphatic C 8 -C 18 -alkenes, or aromatic hydrocarbons such as the middle oil fractions from paraffin distillation, or ethers with bulky groups, or mixtures of these solvents, these being a polar solvent such as 1,2- Dimethyl phthalate can be added.
  • Suitable absorption agents are further esters of benzoic acid and phthalic acid with straight-chain Ci-Cs-alkanols, such as n-butyl benzoate, methyl benzoate, ethyl benzoate, dimethyl phthalate, diethyl phthalate, and so-called heat transfer oils, such as biphenyl and chlorodenyl and diphenyl.
  • a suitable Abso ⁇ tionsstoff is a mixture of biphenyl and diphenyl ether, preferably in the azeotropic composition, for example, the commercially available Diphyl ®.
  • This solvent mixture often contains dimethyl phthalate in an amount of 0.1 to 25% by weight.
  • Suitable absorption agents are also octanes, nonanes, decanes, undecanes, dodecanes, tridecanes, tetradecanes, pentadecanes, hexadecanes, heptadecanes and octadecanes or fractions obtained from refinery streams which contain the linear alkanes mentioned as main components.
  • the loaded absorbent is heated and / or relaxed to a lower pressure.
  • the deodorization can also be carried out by stripping or in a Combination of relaxation, heating and stripping can be done in one or more process steps.
  • the absorbent regenerated in the desorption stage is returned to the absorption stage.
  • the presence of hydrogen from the recycle stream has a positive effect on the catalyst service life of the dehydrogenation catalyst and also causes higher propene and isobutene selectivities of the autothermal dehydrogenation.
  • Ammonia in the recycle gas stream D has no adverse effect in the autothermal alkane dehydrogenation and is oxidized to nitrogen or to nitrogen oxides.

Abstract

La présente invention concerne un procédé de préparation de nitriles insaturés à partir d'alcanes, comprenant les étapes suivantes: a) apport de l'alcane et de gaz comprenant de l'oxygène dans une zone de déshydratation, et déshydratation autothermique de l'alcane pour donner l'alcène correspondant, ce qui permet d'obtenir un flux de produits gazeux A qui contient l'alcène, de l'alcane non converti, de la vapeur d'eau et éventuellement un ou plusieurs composés gazeux appartenant au groupe qui comprend l'hydrogène, les oxydes de carbone, les hydrocarbures à point d'ébullition inférieur à celui de l'alcane et de l'alcène ( = à bas point d'ébullition), l'azote et les gaz rares; b) introduction du flux de produits gazeux A, d'ammoniac et de gaz contenant de l'oxygène dans une zone d'oxydation, et ammoxydation catalytique de l'alcène pour donner le nitrile insaturé correspondant, ce qui permet d'obtenir un flux de produits gazeux B qui contient le nitrile insaturé, des produits secondaires de l'ammoxydation, de l'alcane et de l'alcène non converti, de la vapeur d'eau et éventuellement un ou plusieurs autres composés gazeux appartenant au groupe qui comprend l'hydrogène, l'oxygène, les oxydes de carbone, l'ammoniac, les hydrocarbures à bas point d'ébullition, l'azote et les gaz rares; c) éventuellement séparation de l'ammoniac du flux de produits gazeux B, ce qui permet d'obtenir un flux de produits gazeux C appauvri en ammoniac; d) séparation du nitrile insaturé et des produits secondaires de l'ammoxydation à partir du flux de produits gazeux B ou C par absorption dans un agent d'absorption aqueux, ce qui permet d'obtenir un flux gazeux D qui contient l'alcane et l'alcène non converti et éventuellement un ou plusieurs composés gazeux appartenant au groupe qui comprend l'hydrogène, l'oxygène, les oxydes de carbone, l'ammoniac, les hydrocarbures à bas point d'ébullition, l'azote et les gaz rares, et un flux aqueux qui contient le nitrile et les produits secondaires, et récupération du nitrile insaturé à partir du flux gazeux; e) séparation du flux gazeux D en deux flux partiels D' et D'', éventuellement séparation de l'alcane et de l'alcène non converti à partir du flux gazeux D', et réintroduction du flux partiel D'' et éventuellement de l'alcane et de l'alcène non converti, séparé du flux D', dans la zone de déshydratation.
PCT/EP2003/004040 2002-04-22 2003-04-17 Procede de preparation de nitriles insatures WO2003089407A1 (fr)

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DE2002117845 DE10217845A1 (de) 2002-04-22 2002-04-22 Verfahren zur Herstellung von ungesättigten Nitrilen

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US3678090A (en) * 1970-12-17 1972-07-18 Monsanto Co Ammoxidation of saturated hydrocarbons
US4609502A (en) * 1985-02-14 1986-09-02 The Halcon Sd Group, Inc. Process for preparing unsaturated nitriles from alkanes
US4754049A (en) * 1985-02-14 1988-06-28 Atlantic Richfield Company Process for preparing unsaturated nitriles from alkanes
EP0344884A2 (fr) * 1988-05-31 1989-12-06 The Standard Oil Company Procédé et système catalytique d'ammoxydation de paraffines
US5268497A (en) * 1992-02-24 1993-12-07 The Boc Group, Inc. Process for the production of nitriles
US5985788A (en) * 1993-12-03 1999-11-16 Nippon Shokubai Co Ltd Process for making (meth)acrylonitriles
WO2000014180A1 (fr) * 1998-09-03 2000-03-16 The Dow Chemical Company Procede autothermique permettant de produire des olefines
US6043185A (en) * 1999-04-02 2000-03-28 The Standard Oil Company Gallium promoted molybdenum vanadium-antimony-oxide based catalyst for selective paraffin ammoxidation
WO2003002520A1 (fr) * 2001-06-29 2003-01-09 Basf Aktiengesellschaft Procede de production de nitriles insatures a partir d'alcanes
EP1318127A2 (fr) * 2001-12-04 2003-06-11 Rohm And Haas Company Procédé amélioré de préparation d'oléfines, d'acides carboxyliques insaturés et de nitriles insaturés à partir d'alkanes

Patent Citations (10)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US3678090A (en) * 1970-12-17 1972-07-18 Monsanto Co Ammoxidation of saturated hydrocarbons
US4609502A (en) * 1985-02-14 1986-09-02 The Halcon Sd Group, Inc. Process for preparing unsaturated nitriles from alkanes
US4754049A (en) * 1985-02-14 1988-06-28 Atlantic Richfield Company Process for preparing unsaturated nitriles from alkanes
EP0344884A2 (fr) * 1988-05-31 1989-12-06 The Standard Oil Company Procédé et système catalytique d'ammoxydation de paraffines
US5268497A (en) * 1992-02-24 1993-12-07 The Boc Group, Inc. Process for the production of nitriles
US5985788A (en) * 1993-12-03 1999-11-16 Nippon Shokubai Co Ltd Process for making (meth)acrylonitriles
WO2000014180A1 (fr) * 1998-09-03 2000-03-16 The Dow Chemical Company Procede autothermique permettant de produire des olefines
US6043185A (en) * 1999-04-02 2000-03-28 The Standard Oil Company Gallium promoted molybdenum vanadium-antimony-oxide based catalyst for selective paraffin ammoxidation
WO2003002520A1 (fr) * 2001-06-29 2003-01-09 Basf Aktiengesellschaft Procede de production de nitriles insatures a partir d'alcanes
EP1318127A2 (fr) * 2001-12-04 2003-06-11 Rohm And Haas Company Procédé amélioré de préparation d'oléfines, d'acides carboxyliques insaturés et de nitriles insaturés à partir d'alkanes

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