WO2007132011A1 - Procédé de fabrication de composés dioxo vicinaux par oxydation de composés dihydroxy vicinaux sur un lit de catalyseur structuré - Google Patents

Procédé de fabrication de composés dioxo vicinaux par oxydation de composés dihydroxy vicinaux sur un lit de catalyseur structuré Download PDF

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Publication number
WO2007132011A1
WO2007132011A1 PCT/EP2007/054735 EP2007054735W WO2007132011A1 WO 2007132011 A1 WO2007132011 A1 WO 2007132011A1 EP 2007054735 W EP2007054735 W EP 2007054735W WO 2007132011 A1 WO2007132011 A1 WO 2007132011A1
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WIPO (PCT)
Prior art keywords
catalyst
vicinal
zones
beds
compounds
Prior art date
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Ceased
Application number
PCT/EP2007/054735
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German (de)
English (en)
Inventor
Jobst Rüdiger VON WATZDORF
Gerhard KOPPENHÖFER
Michael Schreiber
Thomas Krug
Bernd Rumpf
Thorsten Johann
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BASF SE
Original Assignee
BASF SE
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Filing date
Publication date
Application filed by BASF SE filed Critical BASF SE
Publication of WO2007132011A1 publication Critical patent/WO2007132011A1/fr
Anticipated expiration legal-status Critical
Ceased legal-status Critical Current

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Classifications

    • 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
    • C07C45/37—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 >C—O—functional groups to >C=O groups
    • C07C45/39—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 >C—O—functional groups to >C=O groups being a secondary hydroxyl group
    • 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
    • C07C45/37—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 >C—O—functional groups to >C=O groups
    • C07C45/38—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 >C—O—functional groups to >C=O groups being a primary hydroxyl group

Definitions

  • the present invention relates to a process for the preparation of vicinal dioxo compounds by oxidation of vicinal dihydroxy compounds to a structured catalyst bed.
  • EP 1 169 1 19 discloses exothermic or endothermic catalyzed gas phase reactions, for example for the preparation of glyoxal from ethylene glycol, in a tube bundle reactor which contains a fixed bed of a catalytically active multimetal oxide arranged in the reactor tubes. To control the reaction, a structured bed located in the reactor tubes is described in this context, which has two different active catalysts in the longitudinal direction of the reactor tubes.
  • DE 19 23 048 discloses the preparation of glyoxal by oxidation of ethylene glycol over a catalyst obtained by oxidation of a copper-tin alloy, a copper-tin-phosphorus alloy or a copper-phosphorus alloy.
  • a catalyst obtained by oxidation of a copper-tin alloy, a copper-tin-phosphorus alloy or a copper-phosphorus alloy.
  • oxidation in the presence of an oxygen-containing gas and possibly a diluent gas are typically reaction temperatures of 300 to 450 ° C before.
  • the yields of glyoxal described here are comparatively low at 65 to 70%, based on the amount of ethylene glycol used.
  • the example of the glyoxal shows that despite a high to almost complete conversion of the educt of ethylene glycol, the yield of glyoxal is relatively low.
  • the high catalyst loading required for the economic efficiency of a technical synthesis which can lead to a rapid rise in the temperature in the reaction zone (hot spot), proves to be responsible for rapid aging and damage to the catalyst used.
  • a reduced catalyst loading which would slow down the temperature rise, is associated with a reduction in the amount of product and thus often uneconomical.
  • Preferred vicinal dihydroxy compounds are ethylene glycol and 1,2-propanediol.
  • the process for preparing vicinal dioxo compounds involves providing a starting material mixture containing the corresponding vicinal diols.
  • ethylene glycol can be converted into the gas phase in an evaporator and admixed with a cycle gas stream.
  • the recycle gas generally contains predominantly nitrogen and also fractions of oxygen, carbon dioxide, carbon monoxide and water.
  • the recycle gas may contain 0 to 5% by volume O 2 , 0 to 10% by volume CO 2 , 0 to 5% by volume CO, 0 to 15% by volume H 2 O.
  • the oxygen required for the oxihydrogenation of vicinal diols can be provided by admixing fresh air to the recycle gas saturated with vicinal diols.
  • the molar ratios of oxygen to ethylene glycol before entering the Rohrbündelre- actor are typically ⁇ 1, 5 moles of oxygen per mole of ethylene glycol.
  • the Eduktgasstrom is introduced into a tube bundle reactor in the upper, ie upstream reactor hood of the tube bundle reactor and passes from there into a plurality of catalyst fixed bed containing reactor tubes in which implement the reactants.
  • a tube bundle reactor used according to the invention is usually constructed as follows: The reactor tubes are sealingly secured with their open ends in tube sheets and open into the upper and lower reactor hood, respectively.
  • a preferably cylindrical section of the reactor has a reactor jacket surrounding the reactor tubes, which is connected sealingly at its upper and lower ends to the final reactor hoods.
  • a fluid heat transfer medium can be guided in order to supply or remove energy to the reaction system. Possible flow paths of the heat transfer medium are DC or countercurrent. By suitable installations a meandering flow can be achieved.
  • the heat transfer medium conducted via suitable supply and discharge means on the reactor jacket can be circulated by means of pumps and heat exchangers with a desired temperature.
  • the reactor tubes are made of ferritic steel or stainless steel and have a wall thickness of a few millimeters, preferably 1 to 3 mm. Its inner diameter is 10 to 70 mm, preferably 10 to 50 mm.
  • the tube length typically extends from 1 to 8 m, preferably 2 to 6 m, particularly preferably 2 to 4 m.
  • the number of reactor tubes forming the tube bundle is 1000 to 15,000 reactor tubes, preferably 2000 to 10,000.
  • the reactor tubes are arranged substantially homogeneously distributed.
  • the same filling is present in the substantially uniform reactor tubes, so that trouble-free operation is ensured as far as possible.
  • uniform reaction conditions prevail over the cross section of the tube bundle and the various reactor tubes are filled as uniformly as possible with catalyst and charged with reactant gas stream.
  • the catalysts used in the fixed catalyst bed are typically shaped bodies which can have very different geometries. For example, balls, tablets, strands, rings, spirals, pyramids, cylinders, prisms, cuboids or cubes can be used. Shaped bodies of copper sheet are preferably used, which preferably have a ring shape.
  • the metallic copper is preferably doped with phosphorus.
  • This can be achieved by a different geometry of the moldings used in the individual sections, which require a different packing density (bulk density) of the same, or by different dimensions of shaped catalyst bodies of the same geometry.
  • the specific surface area of the individual zones of the catalyst bed moves in the range from 900 to 1500 m 2 / m 3 .
  • the specific surface area of the catalyst bed preferably decreases from the first to the last zone by 5 to 50%, particularly preferably by 20 to 30%.
  • the catalyst bed may have two or more zones of different specific surface area.
  • the specific surface area of the bed changes almost continuously.
  • the bed will generally have 2 to 10, preferably 2 to 5, in particular 2 or 3 zones.
  • it has 2 zones, wherein in the first zone the specific surface area is in the range of 1200 to 1500 in 2 / in 3 and in the second zone in the range of 900 to 1100 in 2 / in 3 .
  • a structured bed in which two or more catalyst bed sections differ - with the same geometry of the shaped catalyst body - body by the dimension of the catalyst used.
  • annular shaped catalyst bodies made of copper sheet.
  • shaped catalyst bodies having a specific surface area of 1300 m 2 / m 3 are used in an upper catalyst bed section.
  • the height of this catalyst bed section is between 800 and 2000 mm.
  • another catalyst bed section joins, in which annular shaped catalyst bodies having a specific surface area of 970 in 2 / im 3 are used.
  • the height of this second catalyst charge section is between 800 and 2000 mm.
  • the smaller shaped catalyst bodies used in the first section have a higher bulk density than the larger shaped catalyst bodies of the same geometry used in the second section. At a constant proportion in the educt gas stream thus reduces the catalyst loading in the first section of the catalyst bed. This leads to longer service life of the catalyst.
  • the yield of dioxo compound also increases with the same conversion of dihydroxy compound. This yield increases, for example, in the production of glyoxal by 5 to 10%.
  • conversions of> 90%, preferably> 95%, particularly preferably> 98% can be achieved, starting from ethylene glycol or 1,2-propanediol.
  • a structured bed comprising a top zone of 1200 mm of a bed of 3.65 kg catalyst size 4 x 4 x 0.3 mm (specific surface area about 1300 m 2 / m 3 ) and a lower zone of 1300 mm of a bed of 3.1 kg catalyst of size 5 x 5 x 0.3 mm (specific surface area about 970 m 2 / m 3 ) installed.
  • the following synthesis conditions are set:

Landscapes

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

Abstract

Procédé de fabrication d'un composé dioxo vicinal par oxydation en phase gazeuse, à catalyse hétérogène, d'un composé dihydroxy vicinal en présence d'un gaz contenant de l'oxygène, sur des lits de particules catalytiques composées de cuivre métallique, les lits de particules étant disposés dans les tubes d'un réacteur à faisceau de tubes. Le procédé selon l'invention est caractérisé en ce que les lits de catalyseurs comportent respectivement au moins deux zones, la surface catalytique active par unité de volume des lits de catalyseurs diminuant dans le sens d'écoulement, de la première zone à la dernière zone.
PCT/EP2007/054735 2006-05-17 2007-05-16 Procédé de fabrication de composés dioxo vicinaux par oxydation de composés dihydroxy vicinaux sur un lit de catalyseur structuré Ceased WO2007132011A1 (fr)

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
EP06114094.3 2006-05-17
EP06114094 2006-05-17

Publications (1)

Publication Number Publication Date
WO2007132011A1 true WO2007132011A1 (fr) 2007-11-22

Family

ID=38377317

Family Applications (1)

Application Number Title Priority Date Filing Date
PCT/EP2007/054735 Ceased WO2007132011A1 (fr) 2006-05-17 2007-05-16 Procédé de fabrication de composés dioxo vicinaux par oxydation de composés dihydroxy vicinaux sur un lit de catalyseur structuré

Country Status (1)

Country Link
WO (1) WO2007132011A1 (fr)

Citations (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
GB1234766A (en) * 1967-09-15 1971-06-09 Laporte Chemical Vapour phase oxidation of diols
GB1272592A (en) * 1968-05-06 1972-05-03 Laporte Chemical Vapour phase oxidation of hydroxy compounds
WO2000054877A2 (fr) * 1999-03-16 2000-09-21 Basf Aktiengesellschaft Reacteur a faisceau de tubes destine notamment a des reactions en phase gazeuse catalytique
WO2007088118A1 (fr) * 2006-02-01 2007-08-09 Basf Aktiengesellschaft Procede de fabrication de composes dioxo vicinaux

Patent Citations (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
GB1234766A (en) * 1967-09-15 1971-06-09 Laporte Chemical Vapour phase oxidation of diols
GB1272592A (en) * 1968-05-06 1972-05-03 Laporte Chemical Vapour phase oxidation of hydroxy compounds
WO2000054877A2 (fr) * 1999-03-16 2000-09-21 Basf Aktiengesellschaft Reacteur a faisceau de tubes destine notamment a des reactions en phase gazeuse catalytique
WO2007088118A1 (fr) * 2006-02-01 2007-08-09 Basf Aktiengesellschaft Procede de fabrication de composes dioxo vicinaux

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