EP1109773A1 - Procede de production d'acroleine et/ou d'acide acrylique a partir de propane - Google Patents

Procede de production d'acroleine et/ou d'acide acrylique a partir de propane

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Publication number
EP1109773A1
EP1109773A1 EP99941556A EP99941556A EP1109773A1 EP 1109773 A1 EP1109773 A1 EP 1109773A1 EP 99941556 A EP99941556 A EP 99941556A EP 99941556 A EP99941556 A EP 99941556A EP 1109773 A1 EP1109773 A1 EP 1109773A1
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European Patent Office
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vol
column
mixture
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EP99941556A
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German (de)
English (en)
Inventor
Otto Machhammer
Andreas Tenten
Harald Jachow
Susanne Haupt
Heiko Arnold
Signe Unverricht
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BASF SE
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BASF SE
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    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C51/00—Preparation of carboxylic acids or their salts, halides or anhydrides
    • C07C51/16—Preparation of carboxylic acids or their salts, halides or anhydrides by oxidation
    • C07C51/21—Preparation of carboxylic acids or their salts, halides or anhydrides by oxidation with molecular oxygen
    • C07C51/215—Preparation of carboxylic acids or their salts, halides or anhydrides by oxidation with molecular oxygen of saturated hydrocarbyl groups
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C45/00—Preparation of compounds having >C = O groups bound only to carbon or hydrogen atoms; Preparation of chelates of such compounds
    • C07C45/27—Preparation of compounds having >C = O groups bound only to carbon or hydrogen atoms; Preparation of chelates of such compounds by oxidation
    • C07C45/32—Preparation of compounds having >C = O groups bound only to carbon or hydrogen atoms; Preparation of chelates of such compounds by oxidation with molecular oxygen
    • C07C45/33—Preparation of compounds having >C = O groups bound only to carbon or hydrogen atoms; Preparation of chelates of such compounds by oxidation with molecular oxygen of CHx-moieties
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C45/00—Preparation of compounds having >C = O groups bound only to carbon or hydrogen atoms; Preparation of chelates of such compounds
    • C07C45/27—Preparation of compounds having >C = O groups bound only to carbon or hydrogen atoms; Preparation of chelates of such compounds by oxidation
    • C07C45/32—Preparation of compounds having >C = O groups bound only to carbon or hydrogen atoms; Preparation of chelates of such compounds by oxidation with molecular oxygen
    • C07C45/33—Preparation of compounds having >C = O groups bound only to carbon or hydrogen atoms; Preparation of chelates of such compounds by oxidation with molecular oxygen of CHx-moieties
    • C07C45/34—Preparation of compounds having >C = O groups bound only to carbon or hydrogen atoms; Preparation of chelates of such compounds by oxidation with molecular oxygen of CHx-moieties in unsaturated compounds
    • C07C45/35—Preparation of compounds having >C = O groups bound only to carbon or hydrogen atoms; Preparation of chelates of such compounds by oxidation with molecular oxygen of CHx-moieties in unsaturated compounds in propene or isobutene
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C51/00—Preparation of carboxylic acids or their salts, halides or anhydrides
    • C07C51/16—Preparation of carboxylic acids or their salts, halides or anhydrides by oxidation
    • C07C51/21—Preparation of carboxylic acids or their salts, halides or anhydrides by oxidation with molecular oxygen
    • C07C51/25—Preparation of carboxylic acids or their salts, halides or anhydrides by oxidation with molecular oxygen of unsaturated compounds containing no six-membered aromatic ring
    • C07C51/252—Preparation of carboxylic acids or their salts, halides or anhydrides by oxidation with molecular oxygen of unsaturated compounds containing no six-membered aromatic ring of propene, butenes, acrolein or methacrolein
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
    • Y02P20/00—Technologies relating to chemical industry
    • Y02P20/50—Improvements relating to the production of bulk chemicals
    • Y02P20/582—Recycling of unreacted starting or intermediate materials

Definitions

  • the present invention relates to a process for the preparation of acrolein and / or acrylic acid from propane, in which the propane is subjected to a partial homogeneous and / or heterogeneously catalyzed oxydehydrogenation with molecular oxygen to propene in a first reaction stage and then the propene formed in the first reaction stage containing product gas mixture used in at least one further reaction stage for the production of acrolein and / or acrylic acid by gas phase catalytic propene oxidation.
  • Acrolein and acrylic acid are important intermediates that are used, for example, in the manufacture of active ingredients and polymers.
  • the process currently mainly used on an industrial scale for the production of acrolein and / or acrylic acid is the gas-phase catalytic oxidation of propene (e.g. EP-A 575 897), the propene being predominantly produced as a by-product of ethylene production by steam cracking naphtha.
  • gas-phase catalytic oxidation of propene e.g. EP-A 575 897
  • the propene being predominantly produced as a by-product of ethylene production by steam cracking naphtha.
  • the product mixture containing propene is then subjected to heterogeneously catalyzed gas-phase oxidation.
  • a disadvantage of this procedure is that the catalyst required for the non-oxidative dehydrogenation of the propane is deactivated relatively quickly by carbon deposits and therefore frequently has to be regenerated.
  • Another disadvantage of this procedure is the hydrogen formation associated with the nonoxidative propane dehydrogenation.
  • EP-A 293 224, US-A 5 198 578 and US-A 5 183 936 teach that an increased N 2 content in the diluent gas is disadvantageous in the catalytic gas phase oxidation of propene to acrolein and / or acrylic acid.
  • EP-A 293 224 also suggests that
  • Moro-oka 30 et al combine in laboratory tests a homogeneous oxidative dehydrogenation of propane to propene with a subsequent heterogeneously catalyzed oxidation of the dehydrogenation product mixture to acrolein and / or acrylic acid. Moro-oka et al in Applied Catalysis, 70 (2), 1991, pp. 175 to 35 187 recommend the corresponding process combination.
  • Moro-oka et al use either pure molecular oxygen or air depleted in nitrogen as the oxygen source for the oxide dehydrogenation stage. For the latter case, Moro-oka does not provide for any separation of nitrogen introduced into the process in the further course of his process.
  • CN-A 110 5352 likewise discloses a homogeneous oxidative dehydrogenation of propane to propene with a subsequent heterogeneously catalyzed oxidation of the dehydrogenation product mixture to acrolein and / or acrylic acid. Since CN-A 110 5352 is a large-scale procedure to be carried out in CN-A 110 5352, following the recommendation of EP-A 293 224, US-A 5 198 578 and US-A 5 183 936, only pure molecular oxygen is used as the oxygen source.
  • WO 97/36849 relates to the combination of a catalytic oxidative dehydrogenation of propane to propene with a subsequent heterogeneously catalyzed oxidation of the dehydrogenation product mixture to acrolein and / or acrylic acid in an industrial version.
  • WO 97/36849 does not rule out the use of nitrogen-containing oxygen (e.g. air) as a source of the molecular oxygen required in the oxydehydrogenation, but advises against it.
  • nitrogen-containing oxygen e.g. air
  • WO 97/36849 only provides an outlet (purge) of circulating gas and no component separation from the circulating gas in the case of a continuous procedure with recycle gas to suppress undesired leveling of disadvantageous reaction gas mixture components.
  • the object of the present invention was therefore a process for the preparation of acrolein and / or acrylic acid from propane, in which the propane is subjected to a homogeneous and / or a heterogeneously catalyzed oxydehydrogenation with molecular oxygen to propene in a first reaction stage and then in the first reaction stage formed, containing propene, product gas mixture used in at least one further reaction stage for the production of acrolein and / or acrylic acid by gas phase catalytic propene oxidation, in which the restriction of the nitrogen content in the propene oxidation stage in a less energy-consuming manner than done in the prior art.
  • a process for the preparation of acrolein and / or acrylic acid from propane in which the propane is subjected to a partial homogeneous and / or heterogeneously catalyzed oxydehydrogenation with molecular oxygen to propene in a first reaction stage and then the one formed in the first reaction stage is subjected to Product gas mixture containing propene used in at least one further reaction stage for the production of acrolein and / or acrylic acid by gas-phase-catalyzed propene oxidation, which is characterized in that the reaction gas starting mixture of the first reaction stage requires the molecular oxygen different from cycle gas oxygen than that required in the first reaction stage Modified air containing nitrogen is added, provided that the nitrogen (expressed in mol%) of the modified air is smaller and the oxygen content of the modified air is larger than the corresponding contents of air (i.e.
  • the principal advantage of the procedure according to the invention compared to the closest prior art processes is the result of in-depth research that the chemical bonding of the molecular oxygen which takes place in the course of the oxidative dehydrogenation of the propane using a nitrogen-containing oxygen source implicitly forms part of the Separation of atmospheric nitrogen and atmospheric oxygen to be carried out separating work.
  • the difference between the resulting oxygen-containing polar compounds (e.g. H 2 0) and N 2 is much more pronounced than the difference between N and 0 2 , which is why an at least partial subsequent N 2 separation from the oxidative dehydrogenation product mixture is significantly less is energy-consuming, as an anticipatory N 2 separation from air.
  • the first reaction stage is designed as a homogeneous oxide dehydrogenation in the process according to the invention, this can in principle be carried out, for example, as described in US Pat. Nos. 3,798,283, CN 1,105,352, Applied Catalysis, 70 (2), 1991, p 175 to 187, Catalysis Today 13, 1992, pp. 673 to 678 and the older appendix DE-A 1 96 22 331 can be seen from this from that according to the invention modified air is to be used as the oxygen source (apart from oxygen cycle gas).
  • the temperature of the homogeneous oxide dehydrogenation is expediently chosen to be in the range from 300 to 700 ° C., preferably in the range from 400 to 600 ° C., particularly preferably in the range from 400 to 500 ° C.
  • the working pressure can be 0.5 to 100 bar or 1 to 50 bar. Often it will be 1 to 20 bar or 1 to 10 bar.
  • the residence time of the reaction gas mixture under oxydehydrogenation conditions is usually 0.1 or 0.5 to 20 seconds, preferably 0.1 or 0.5 to 5 seconds.
  • a tube furnace or a tube bundle reactor can be used, e.g. a counterflow tube furnace with flue gas as the heat carrier, or a tube bundle reactor with molten salt as the heat carrier.
  • the propane to oxygen ratio in the reaction gas starting mixture to be used can be 0.5: 1 to 40: 1. It is advantageous according to the invention if the molar ratio of propane to molecular oxygen in the reaction gas starting mixture is ⁇ 6: 1 or ⁇ 5: 1. As a rule, the aforementioned ratio will be> 1: 1 or> 2: 1.
  • the nitrogen content in the reaction gas starting mixture is generally a consequence of the aforementioned requirement, since the reaction gas starting mixture normally does not comprise essentially any other gases besides propane and modified air.
  • the reaction gas starting mixture can also comprise further, essentially inert, constituents such as H0, C0 2 , CO, noble gases and / or propene.
  • Propene as a component of the reaction gas starting mixture is given, for example, if the C 3 fraction from the refinery or the C 3 fraction from the light hydrocarbons of the oil field, which have a propene content of up to 10% by weight, is used as the starting propane can. It can also be the case if the process according to the invention is carried out continuously and, after the last reaction step, unreacted propane and / or propene is returned to the oxydehydrogenation. Components returned to the oxydehydrogenation are generally referred to in this document as circulating gas. As a result of recycle gas recycle, the nitrogen content in the reaction gas starting mixture can be up to 60 mol% or up to 50 mol%.
  • Recycle gas recirculation can also lead to the reaction gas starting mixture having up to 5 mol% of gases such as CO, CO 2 , ethene and H 2 O in a continuous procedure. It is favorable for a homogeneous oxidative dehydrogenation of propane to propene if the ratio of the surface of the reaction space to the volume of the reaction space is as small as possible. This is a consequence of radical mechanism of homogeneous oxidative propane dehydrogenation, reaction chamber surfaces generally act as radical scavengers. Aluminum oxide, quartz glass, borosilicate, stainless steel and aluminum are particularly favorable surface materials.
  • the first reaction stage is designed as a heterogeneously catalyzed oxydehydrogenation in the process according to the invention, this can in principle be e.g. as in US-A 4, 788, 371, CN-A 10 733 893, Catalysis Letters 23 (1994) 103-106, W. Zhang, Gaodeng Xuexiao Huaxue Xuebao, 14
  • Oxydehydrogenation catalysts which are particularly suitable according to the invention are the multimetal oxide compositions or catalysts A of DE-A 1 97 53 817, the multimetal oxide compositions or catalysts A mentioned as preferred in the abovementioned publication being very particularly favorable. That , In particular, multimetal oxide compositions of the general formula I ⁇ MOi-M ⁇ Ox (I) come as active compositions
  • M 1 Co, Ni, Mg, Zn, Mn and / or Cu,
  • active compositions I suitable according to the invention can be prepared in a simple manner by generating an intimate, preferably finely divided, dry mixture composed of suitable elementary constituents according to their stoichiometry and calcining them at temperatures of 450 to 1000 ° C.
  • the calcination can take place both under inert gas and under an oxidative atmosphere such as air (mixture of inert gas and oxygen) and also under a reducing atmosphere (eg mixture of inert gas, oxygen and NH 3 , CO and / or H).
  • the calcination time can range from a few minutes to a few hours and usually decreases with temperature.
  • sources for the elementary tare constituents of the multimetal oxide active compositions I are those compounds which are already oxides and / or those compounds which can be converted into oxides by heating, at least in the presence of oxygen.
  • such starting compounds are, above all, halides, nitrates, formates, oxalates, citrates, acetates, carbonates, amine complex salts, ammonium salts and / or hydroxides (compounds such as NH 4 OH, (NH 4 ) 2 CO 3 , NH 4 N0 3 , NH 4 CH0 2 , CH 3 COOH, NH 4 CH 3 C0 2 and / or ammonium oxalate, which can decompose and / or decompose to form completely gaseous compounds at the latest during later calcination, can also be incorporated into the intimate dry mixture ).
  • halides nitrates, formates, oxalates, citrates, acetates, carbonates, amine complex salts, ammonium salts and / or hydroxides
  • the intimate mixing of the starting compounds for the production of multimetal oxide masses I can take place in dry or in wet form. If it is carried out in dry form, the starting compounds are expediently used as finely divided powders and, after mixing and optionally compacting, are subjected to the calcination. However, the intimate mixing is preferably carried out in wet form. Usually, the starting compounds are mixed together in the form of an aqueous solution and / or suspension. In the dry process described, particularly intimate dry mixtures are obtained if only sources of the elementary constituents present in dissolved form are used. Water is preferably used as the solvent. The aqueous mass obtained is then dried, the drying process preferably being carried out by spray drying the aqueous mixture at exit temperatures of 100 to 150 ° C.
  • Particularly suitable starting compounds of Mo, V, W and Nb are their oxo compounds (molybdates, vanadates, tungstates and niobates) or the acids derived from them. This applies in particular to the corresponding ammonium compounds (ammonium molybdate, ammonium vanadate, ammonium tungstate).
  • the multimetal oxide materials I can be used for the process according to the invention both in powder form and in the form of certain catalyst geometries, it being possible for the shaping to take place before or after the final calcination.
  • solid catalysts can be produced from the powder form of the active composition or its uncalcined precursor composition by compression to the desired catalyst geometry (for example by tableting, extrusion or extrusion), with auxiliaries such as graphite or stearic acid optionally being used as lubricants and / or molding aids and reinforcing agents such as microfibers Glass, asbestos, silicon carbide or ca lium titanate can be added.
  • Suitable full catalyst geometries are, for example, full cylinders or hollow cylinders with an outer diameter and a length of 2 to 10 mm. In the case of the hollow cylinder, a wall thickness of 1 to 3 mm is appropriate. Suitable hollow cylinder geometries are, for example, 7 mm x 7 mm x 4 mm or 5 mm x 3 mm x 2 mm or 5 mm x 2 mm x 2 mm (each length x outer diameter x inner diameter). Of course, the full catalyst can also have a spherical geometry, the spherical diameter being 2 to 10 mm.
  • the pulverulent active composition or its pulverulent, not yet calcined, precursor composition can also be shaped by application to preformed inert catalyst supports.
  • the coating of the support bodies for the production of the coated catalysts is usually carried out in a suitable rotatable container, such as that e.g. is known from DE-A 2909671 or from EP-A 293859.
  • the powder mass to be applied can expediently be moistened and, after application, e.g. by means of hot air.
  • the layer thickness of the powder mass applied to the carrier body is expediently selected in the range from 50 to 500 ⁇ m, preferably in the range from 150 to 250 ⁇ m.
  • carrier materials Conventional porous or non-porous aluminum oxides, silicon dioxide, thorium dioxide, zirconium dioxide, silicon carbide or silicates such as magnesium or aluminum silicate can be used as carrier materials.
  • the carrier bodies can have a regular or irregular shape, with regularly shaped carrier bodies with a clearly formed surface roughness, e.g. Balls or hollow cylinders are preferred. It is suitable to use essentially non-porous, rough-surface, spherical supports made of steatite, the diameter of which is 1 to 8 mm, preferably 4 to 5 mm.
  • the reaction temperature of the heterogeneously catalyzed oxydehydrogenation of the propane will suitably be in the range from 300 to 600 ° C., frequently in the range from 350 to 500 ° C.
  • 0.5 to 10 bar or 1 to 10 bar or 1 to 5 bar is recommended as the working pressure.
  • the heterogeneously catalyzed oxydehydrogenation of the propane takes place on a fixed catalyst bed.
  • the latter is expediently heaped up in the tubes of a tube bundle reactor, as described, for example, in EP-A 700 893 and in EP-A 700 714 and the literature cited in these documents.
  • the average residence time of the reaction gas mixture in the catalyst bed is normally from 0.5 to 20 seconds.
  • the propane to oxygen ratio in the reaction gas starting mixture to be used for the heterogeneously catalyzed propane oxydehydrogenation can, according to the invention, be from 0.5: 1 to 40: 1.
  • the molar ratio of propane to molecular oxygen in the reaction gas starting mixture is ⁇ 6: 1 or ⁇ 5: 1.
  • the aforementioned ratio will be> 1: 1 or 2: 1.
  • the nitrogen content in the reaction gas starting mixture is generally a consequence of the aforementioned requirement, since the reaction gas starting mixture normally does not comprise essentially any other gases besides propane and modified air.
  • the reaction gas starting mixture can also comprise further, essentially inert, constituents such as H 2 O, CO 2 , CO, noble gases and / or propene.
  • Propene as a component of the reaction gas starting mixture is given, for example, if the C 3 fraction coming from the refinery or the C 3 fraction from the light hydrocarbons of the oil field, which have a propene content of up to 10% by weight, is used as the starting propane can. It can also be the case if the process according to the invention is carried out continuously and, after the last reaction step, unreacted propane and / or propene is recycled into the heterogeneously catalyzed oxydehydrogenation. As a result of recycle gas recycle, the nitrogen content in the reaction gas starting mixture of the heterogeneously catalyzed propane oxydehydrogenation in the process according to the invention can be up to 60 mol% or up to 50 mol% when carried out continuously.
  • Recycle gas recirculation can also result in the reaction gas starting mixture having up to 5 mol% of gases such as CO, CO 2 , ethane, methane, ethene and / or H 2 0 in a continuous procedure.
  • the modified air to be used as an oxygen source according to the invention can contain, for example,> 0.05% by volume to ⁇ 78% by volume or> 0.1% by volume to ⁇ 75% by volume of N 2 .
  • the nitrogen content of the modified air to be used as an oxygen source according to the invention can be> 1% by volume to ⁇ 70% by volume or> 5% by volume to ⁇ 60% by volume or> 10% by volume to ⁇ 50% by volume .-% or> 15 vol.% to ⁇ 40 vol.% or> 20 vol.% to ⁇ 30 vol.%.
  • the oxygen content of the modified air to be used according to the invention as an oxygen source can be> 20.95
  • the modified air to be used according to the invention can also contain the other constituents, such as noble gases, carbon dioxide, water vapor, etc., which are usually present in small amounts.
  • the aforementioned components may also have been partially or completely removed as part of the modification.
  • the modified air to be used according to the invention as an oxygen source can e.g. by fractional distillation of air, preferably under pressure.
  • fractional distillation of air preferably under pressure.
  • EP-A 848 981 and EP-A 848639 can also be used.
  • both the 0 2 conversion of the homogeneous and the catalytic oxidative propane dehydrogenation in the process according to the invention should be> 70 mol%.
  • the aforementioned 0 conversion can> 75 mol. % or> 80 mol% or> 85 mol% or> 90 mol% or> 95 mol% or> 97 mol% or> 99 mol%.
  • the possible components of the product gas mixture of the propane oxide dehydrogenation may include, for example, the following components: CO 2 , CO, HO, N 2 ° 2 'propene, propane, ethane, ethene, methane, acrolein, acrylic acid, ethylene oxide, butane, acetic acid, formaldehyde, formic acid , Propylene oxide and butene.
  • the separation of at least part of the nitrogen contained therein required according to the invention prior to further use of the aforementioned propane-containing propane oxyhydrogen product gas mixture for the production of acrolein and / or acrylic acid from the same can, e.g. done in a simple manner by distillation.
  • fractional distillation preferably a fractional pressure distillation at low temperatures.
  • the pressure to be used can be, for example, 10 to 100 bar. Packing columns, tray columns or packing columns can be used as rectification columns. Tray columns with dual-flow trays, bubble trays or valve trays are suitable.
  • the reflux ratio can be, for example, 1 to 10.
  • Other possibilities for nitrogen separation are, for example, pressure swing absorption, pressure washing and pressure extraction. Based on the total amount of nitrogen contained in the propane oxide hydrogenation product gas mixture, the amount of nitrogen to be separated off according to the invention can be 5%, or 10%, or 20%, or 30%, or 40%, or 50%, or 60%, or 70%, or 80%, or 90% or 95 to 5 100%.
  • the nitrogen itself is also possible not to separate the nitrogen itself from the propane oxide hydrogenation product gas mixture, but together with other components of the propane oxide hydrogenation product gas mixture which may not be desired in the subsequent reaction stage.
  • These components will primarily be the carbon oxides CO and C0 2 as well as unreacted oxygen and ethylene and methane.
  • only a part of the above-mentioned components can be separated off together with the nitrogen.
  • the propane and unreacted propane-containing propane oxides and the mixture of propylene oxides which have been depleted in nitrogen and possibly the aforementioned secondary components, can be used directly for the production of acrolein and / or acrylic acid by catalytic propene oxidation, as used in the prior art, for example in WO 97 / 36849 or CN-A 11 05 352.
  • this gas phase catalytic propene oxidation can also be carried out as described in EP-A 117 146, US-A 5 198 578 or US-A 5 183 936 5. But you can also in analogy to DE-A 33 13 573, CA-A 12 17 502, US-A 3 161 670 or US-A 4 532 365 can be carried out.
  • the gas-phase catalytic oxidative conversion of the propene contained in the propane-oxydehydrogenation product gas mixture (hereinafter referred to as “residual product gas mixture”), which has been depleted in nitrogen, to acrolein and / or acrylic acid can take place, for example, in one or two subsequent oxidation stages.
  • the catalytic gas phase oxidation of the propene contained in the residual product gas mixture to an amount of acrolein which is predominant compared to acrylic acid is preferably described as described in EP-A 731 082, DE-A 44 31 957, DE-A 29 09 597 or EP-A 575 897 carried out.
  • the gas phase oxidation is expediently carried out in a multi-contact tube fixed bed reactor.
  • the volume (Nl) ratio is 1: (1.0 to 3.0): (5 to 25), preferably 1: (1.7 to 2.3 ): (10 to 15), worked.
  • molecular oxygen to the residual product gas mixture containing the propene before it is introduced into the propene oxidation stage.
  • This can be in the form of air, in the form of nitrogen-depleted air or in the form of pure oxygen.
  • additional dilution gases eg H0
  • the reaction temperature is expediently chosen to be 300 ° C. to 450 ° C., preferably 320 ° C. to 390 ° C.
  • the reaction pressure is usually 0.5 to 5 bar, preferably 1 to 3 bar.
  • the total space load is often 1500 to 2500 Nl / l / h.
  • Suitable catalysts for this oxidation stage are, for example, those of DE-A 29 09 592, especially those from Example 1 of this document.
  • the multimetal oxide catalysts II or II 'of DE-A 1 97 53 817 can also be used. This particularly applies to those in these
  • acrolein In the above-mentioned propene oxidation stage, no pure acrolein is obtained, but a mixture from whose secondary components the acrolein can be separated in a manner known per se.
  • the acrolein so separated can be used as an intermediate for the synthesis of various end products. Of course, it can also be used for gas phase catalytic oxidation for the production of acrylic acid.
  • the reaction gases of the propene oxidation stage containing the acrolein are generally transferred to this further oxidation stage without removal of secondary components. If necessary, they undergo intermediate cooling beforehand.
  • This further oxidation stage is also expediently implemented in a multi-contact tube fixed-bed reactor, as it is e.g. is described in DE-A 44 31 949, DE-A 44 42 346, DE-A 1 97 36 105 or EP-A 731 082.
  • molecular oxygen to the product gas mixture from the propene oxidation stage containing acrolein before it is introduced into the acrolein oxidation stage.
  • This can be in the form of air, in the form of nitrogen-depleted air or in the form of pure oxygen.
  • additional dilution gases known essentially as indifferent, can be added at this point as desired.
  • the reaction temperature is expediently chosen to be from 200 ° C. to 300 ° C., preferably from 220 to 290 ° C.
  • the reaction pressure is usually 0.5 to 5 bar, preferably 1 to 3 bar.
  • the total space load is preferably 1000 to 2500 Nl / l / h.
  • Suitable catalysts for this oxidation stage are, for example, those of the general formula I or I 'from DE-A 44 42 346.
  • the multimetal oxide catalysts of DE-A 1 97 36 105 in particular the exemplary embodiments mentioned in this document, can also be used become.
  • the multimetal oxide catalyst ACS-4 from Nippon Shokubai comprising Bi, Mo and Fe can also be used in the acrolein oxidation stage.
  • the gas mixture leaving the acrolein oxidation stage does not consist of pure acrylic acid, but of a gas mixture containing the latter, from which acrylic acid can be separated in a manner known per se.
  • the various known variants of acrylic acid separation are e.g. summarized in DE-A 1 96 00 955.
  • the acrolein could also be separated from the reaction gas mixture leaving the propene oxidation stage.
  • a common feature of the separation processes is that the desired product is separated from the reaction gas mixture of the acrolein oxidation stage either by absorption with a solvent (cf. also DE-A 43 08 087) or by absorption with water or by partial condensation (the resulting absorbate or Condensate is then distilled (if necessary with the addition of an azeotropic
  • the dividing line is drawn in all cases so that a residual gas stream essentially free of acrylic acid and / or acrolein is formed, the main components of which are carbon oxides (CO, C0 2 ), optionally N 2 , noble gases, 0, water vapor, propane and unreacted Are propene.
  • Carrying out the process according to the invention recycle the propane and propene contained in this residual gas stream into the oxydehydrogenation.
  • the at least partial nitrogen separation required according to the invention after the propoxide dehydrogenation is carried out in such a way that together with the nitrogen all gas components boiling less than propene are also separated off, it is expedient to separate the residual gas stream as such into the Attributed to propane oxide hydrogenation.
  • By cooling the residual gas stream it can also be used to comparatively easily condensable components such as water vapor, small amounts of acrylic acid and / or acrolein and small amounts of by-products such as, for example, before recycling Formaldehyde and acetic acid are separated (except water as so-called S).
  • reaction gas starting mixture 95.1 mol / h of reaction gas starting mixture and compressed to a pressure of 2.2 bar and heated to a temperature of 430.degree.
  • a 3.8 m long reaction tube made of V2A steel 2.0 mm wall thickness; 2.6 cm inside diameter was charged with the aforementioned reaction gas starting mixture, which was cooled over its entire length to a temperature of 430 ° C. using a salt bath.
  • the inlet pressure was 1.3 bar, the outlet pressure was 1.0 bar.
  • the product mixture (102.3 mol / h) leaving the reaction tube had the following composition:
  • the aforementioned product mixture was compressed to 36 bar, cooled to 70 ° C. and then fed in two phases to a rectification column operated under pressure, which had 51 trays.
  • the product mixture was fed onto the 30th floor from below.
  • the top pressure of the rectification column (a bell-bottom column, diameter 50 mm) was 36 bar.
  • the column head was cooled with the coolant Baysilone® KT3 (flow temperature -50 ° C).
  • the bottom temperature was 92 ° C.
  • part of the bottom liquid removed was returned as boiling vapor.
  • the bottom liquid continuously withdrawn was 84.9 mol / h. It was cooled to 35 ° C. and expanded to 10 bar in a storage container and brought to a temperature of 25 ° C.
  • the gas phase of the storage container was expanded to 2.3 bar via a throttle.
  • the aqueous liquid phase of the storage container was also continuously removed and, after evaporation, combined with the removed, relaxed gas phase.
  • 13.6 mol / h of a mixture of 90% by volume of O 2 and 10% by volume of N 2 and 9.1 mol / h of propane were added to the bottom liquid which had been continuously transferred into the gas phase, which made propene gas-catalytic - Oxidation resulted in a reaction mixture with the following composition:
  • a reaction tube (V2A steel; length 3.80 m; 2.0 mm wall thickness, 2.6 cm inner diameter) was initially charged in the outflow direction over a length of 50 cm with a bed of steatite balls (diameter: 4-5 mm) .
  • a contact tube length 3.00 m, a fill of the
  • the entire length of the reaction tube was kept at 350 ° C. with a salt bath and 107.6 mol / h of the aforementioned reaction gas starting mixture (which had a temperature of 200 ° C.) were charged.
  • the inlet pressure was 2.0 bar, the outlet pressure was 1.8 bar.
  • This reaction tube (V2A steel; length: 3.80 m; 2.0 mm wall thickness; 2.6 cm inner diameter) was initially at a length of 50 cm in the outflow direction with a bed of steatite balls (diameter: 4-5 mm) loaded.
  • a bed of the multimetal oxide catalyst according to Example b, Sl of DE-A 4 442 346 followed on a contact tube length of 2.70 m.
  • the entire length of the reaction tube was heated to 270 ° C. by means of a salt bath and charged with the reaction gas starting mixture described above.
  • the inlet pressure was 1.8 bar and the outlet pressure was 1.7 bar.
  • the product mixture leaving the reaction tube in an amount of 107.8 mol / h had the following composition:
  • the hot reaction gas leaving the acrolein oxidation stage was extracted from 57.4% by weight in a venturi scrubber (quench apparatus) by direct contact with quench liquid (140-150 ° C.) injected through slots in the narrowest cross section of the venturi tube.
  • quench liquid 140-150 ° C.
  • Diphenyl ether, 20.7% diphenyl and 20% by weight o-dimethyl phthalate cooled to a temperature of about 175 ° C.
  • the drop-like liquid portion of the quench liquid was separated from the gas phase consisting of reaction gas and evaporated quench liquid in a downstream droplet separator (feed container with gas pipe led away at the top) and returned in a circuit I to the venturi washer.
  • a partial stream of the recycled quench liquid was subjected to a solvent distillation, the quench liquid being distilled over and high-boiling secondary components which were burned up remaining.
  • the distilled quench liquid was fed to the outlet of the absorption column described below.
  • the gas phase which had a temperature of approximately 175 ° C., was fed into the lower part of a packed column (3 m high; double jacket made of glass; inner diameter 50 mm; three packed zones with lengths (from bottom to top) 90 cm, 90 cm and 50 cm ; the packing zones were thermostatted from bottom to top as follows: 90 ° C, 60 ° C, 20 ° C; the penultimate and the last packing zone were separated by a chimney tray; the packing units were stainless steel metal helices with a helix diameter of 5 mm and one Helix length of 5 mm; the absorbent was fed in directly above the central packing zone) and the

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  • Chemical & Material Sciences (AREA)
  • Organic Chemistry (AREA)
  • Engineering & Computer Science (AREA)
  • Oil, Petroleum & Natural Gas (AREA)
  • Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
  • Low-Molecular Organic Synthesis Reactions Using Catalysts (AREA)

Abstract

L'invention concerne un procédé de production d'acroléine et/ou d'acide acrylique à partir de propane, procédé selon lequel on soumet le propane, dans une première étape réactionnelle, à une oxydéshydrogénation partiellement homogène et/ou catalysée de manière hétérogène avec de l'oxygène moléculaire pour obtenir du propène, puis on utilise le mélange de gaz de produit, formé dans la première étape réactionnelle, pour produire de l'acroléine et/ou de l'acide acrylique par oxydation du propène par catalyse en phase gazeuse. Ce procédé est caractérisé en ce que l'on ajoute au mélange réactionnel de départ de la première étape réactionnelle l'oxygène moléculaire nécessaire dans la première étape réactionnelle, différent de l'oxygène du gaz recyclé, en tant qu'air modifié contenant de l'azote, à condition que la teneur en azote de l'air modifié soit inférieure et la teneur en oxygène de l'air modifié soit supérieure aux teneurs correspondantes de l'air. Ce procédé est en outre caractérisé en ce que l'on sépare du mélange de gaz de produit au moins une partie de l'azote moléculaire contenu dans le mélange de gaz de produit, avant l'utilisation ultérieure du mélange de gaz de produit formé dans la première étape réactionnelle et contenant du propène pour produire de l'acroléine et/ou de l'acide acrylique dans la ou les étapes réactionnelles ultérieures.
EP99941556A 1998-08-19 1999-08-10 Procede de production d'acroleine et/ou d'acide acrylique a partir de propane Withdrawn EP1109773A1 (fr)

Applications Claiming Priority (3)

Application Number Priority Date Filing Date Title
DE19837518A DE19837518A1 (de) 1998-08-19 1998-08-19 Verfahren zur Herstellung von Acrolein und/oder Acrylsäure aus Propan
DE19837518 1998-08-19
PCT/EP1999/005791 WO2000010960A1 (fr) 1998-08-19 1999-08-10 Procede de production d'acroleine et/ou d'acide acrylique a partir de propane

Publications (1)

Publication Number Publication Date
EP1109773A1 true EP1109773A1 (fr) 2001-06-27

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EP99941556A Withdrawn EP1109773A1 (fr) 1998-08-19 1999-08-10 Procede de production d'acroleine et/ou d'acide acrylique a partir de propane

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US (1) US6388129B1 (fr)
EP (1) EP1109773A1 (fr)
JP (1) JP2002523389A (fr)
CN (1) CN1312789A (fr)
AU (1) AU5512599A (fr)
BR (1) BR9914611A (fr)
DE (1) DE19837518A1 (fr)
WO (1) WO2000010960A1 (fr)

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Publication number Priority date Publication date Assignee Title
BR0111702B1 (pt) 2000-06-14 2012-01-10 processo para a preparação de acroleìna e/ou ácido acrìlico a partir de propano e/ou propeno.
DE10211275A1 (de) * 2002-03-13 2003-09-25 Basf Ag Verfahren der kontinuierlichen heterogen katalysierten partiellen Dehydrierung
GB0125493D0 (en) * 2001-10-24 2001-12-12 Gemstar Cambridge Ltd Modification of starch granule size and number
US7294734B2 (en) * 2003-05-02 2007-11-13 Velocys, Inc. Process for converting a hydrocarbon to an oxygenate or a nitrile
US7220390B2 (en) 2003-05-16 2007-05-22 Velocys, Inc. Microchannel with internal fin support for catalyst or sorption medium
TWI344953B (en) * 2004-07-01 2011-07-11 Basf Ag Preparation of acrolein or acrylic acid or a mixture thereof from propane
KR101259649B1 (ko) * 2004-07-01 2013-04-30 바스프 에스이 프로필렌의 불균질 촉매화 부분 기상 산화를 사용한아크롤레인, 아크릴산 또는 그의 혼합물의 제조 방법
ATE520640T1 (de) * 2004-07-01 2011-09-15 Basf Se Verfahren zur herstellung von acrylsäure durch heterogen katalysierte partielle gasphasen oxidation von propylen
US7388106B2 (en) * 2005-10-14 2008-06-17 Basf Aktiengesellschaft Process for preparing acrolein or acrylic acid or a mixture thereof from propane
DE102005052923A1 (de) * 2005-11-03 2007-05-10 Basf Ag Verfahren zum stabilen Betreiben eines kontinuierlich ausgeübten Herstellprozesses zur Erzeugung von Acrolein, oder Acrylsäure oder deren Gemisch aus Propan
DE102007006647A1 (de) 2007-02-06 2008-08-07 Basf Se Verfahren zur Regenerierung eines im Rahmen einer heterogen katalysierten partiellen Dehydrierung eines Kohlenwasserstoffs deaktivierten Katalysatorbetts
WO2009028292A1 (fr) * 2007-08-30 2009-03-05 Nippon Shokubai Co., Ltd. Procédé de production d'acide acrylique
EP3608305A1 (fr) 2018-08-10 2020-02-12 Röhm GmbH Procédé de production d'acide méthacrylique ou d'esters d'acide méthacrylique
US20220193640A1 (en) * 2019-05-02 2022-06-23 Dow Global Technologies Llc Aldehyde byproduct reduction in acrylic acid production using highly active and elective catalysts

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US6388129B1 (en) 2002-05-14
CN1312789A (zh) 2001-09-12
BR9914611A (pt) 2001-08-07
WO2000010960A1 (fr) 2000-03-02
JP2002523389A (ja) 2002-07-30
DE19837518A1 (de) 2000-02-24
AU5512599A (en) 2000-03-14

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