WO2000003963A1 - Procede pour l'oxydation de cyclohexane en phase gazeuse a l'aide de catalyseurs micro- et mesoporeux solides - Google Patents

Procede pour l'oxydation de cyclohexane en phase gazeuse a l'aide de catalyseurs micro- et mesoporeux solides Download PDF

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Publication number
WO2000003963A1
WO2000003963A1 PCT/EP1999/004891 EP9904891W WO0003963A1 WO 2000003963 A1 WO2000003963 A1 WO 2000003963A1 EP 9904891 W EP9904891 W EP 9904891W WO 0003963 A1 WO0003963 A1 WO 0003963A1
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WO
WIPO (PCT)
Prior art keywords
bar
cyclohexane
gas phase
catalysts
mesoporous
Prior art date
Application number
PCT/EP1999/004891
Other languages
German (de)
English (en)
Inventor
Wilhelm Friedrich Maier
Matthias Hunnius
Original Assignee
Studiengesellschaft Kohle Mbh
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
Application filed by Studiengesellschaft Kohle Mbh filed Critical Studiengesellschaft Kohle Mbh
Publication of WO2000003963A1 publication Critical patent/WO2000003963A1/fr

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Classifications

    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C29/00—Preparation of compounds having hydroxy or O-metal groups bound to a carbon atom not belonging to a six-membered aromatic ring
    • C07C29/48—Preparation of compounds having hydroxy or O-metal groups bound to a carbon atom not belonging to a six-membered aromatic ring by oxidation reactions with formation of hydroxy groups
    • C07C29/50—Preparation of compounds having hydroxy or O-metal groups bound to a carbon atom not belonging to a six-membered aromatic ring by oxidation reactions with formation of hydroxy groups with molecular oxygen only
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J19/00—Chemical, physical or physico-chemical processes in general; Their relevant apparatus
    • B01J19/0053—Details of the reactor
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J19/00—Chemical, physical or physico-chemical processes in general; Their relevant apparatus
    • B01J19/02—Apparatus characterised by being constructed of material selected for its chemically-resistant properties
    • 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
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J2219/00—Chemical, physical or physico-chemical processes in general; Their relevant apparatus
    • B01J2219/00049—Controlling or regulating processes
    • B01J2219/00051—Controlling the temperature
    • B01J2219/00074—Controlling the temperature by indirect heating or cooling employing heat exchange fluids
    • B01J2219/00087—Controlling the temperature by indirect heating or cooling employing heat exchange fluids with heat exchange elements outside the reactor
    • B01J2219/00094—Jackets
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C2601/00—Systems containing only non-condensed rings
    • C07C2601/12—Systems containing only non-condensed rings with a six-membered ring
    • C07C2601/14—The ring being saturated

Definitions

  • the present invention relates to a single-stage catalytic process for the selective oxidation of cyclohexane with atmospheric oxygen for the production of cyclohexanol and cyclohexanone.
  • the process comprises the use of amorphous microporous as well as mesoporous catalysts with different transition metal ions as the active center in a continuously operated reactor in the gas phase under elevated pressure.
  • Micro- and mesoporous mixed oxide catalysts eg Si0 2 , Ti0 2 , Al 2 0 3 or Zr0 2
  • a low content of Co, Cr or V ions (maximum 10%) or other transition metal ions have proven to be particularly suitable for this reaction .
  • the reaction takes place at temperatures between 150 and 350 ° C and a pressure of at least 2 bar. The best results are achieved at pressures of 15 to 25 bar.
  • a significant improvement in selectivity can be achieved if the reactor walls consist of catalytically inert material or if metallic or other reactor inner walls are clad with a catalytically inert material such as gold, Teflon or quartz, are covered with such material by appropriate internals, or are coated with passivating lacquer.
  • the process offers the advantage of heterogeneous reaction control in the gas phase, which, unlike all technical processes used to date, allows the product mixture to be separated from the catalyst very easily. Another advantage of this reaction procedure is the simple recycling of the cyclohexane.
  • the reaction is carried out in a 1 m long reaction tube which is lined with a quartz tube.
  • the tube has a diameter of 0.5 cm and is brought to the appropriate reaction temperature using a heating jacket.
  • the catalyst bed (100 mg) is introduced into this vertically attached tube.
  • the catalyst is calcined in an air stream at 400 ° C before use.
  • the product mixture is removed after the reactor in the relaxed state and analyzed (gas chromatography).
  • Amorphous microporous and mesoporous mixed oxides with silicon dioxide as matrix material and Cr and V as active centers were used as exemplary catalysts (AMM: DE-A 195.450422.6, MCM-41: US 5108725).
  • the cyclohexane is metered continuously into the reactor with the help of an HPLC pump with a constant delivery volume of 2 ml / h to the carrier gas stream (air, 500 ml / h).
  • the resulting product compositions as a function of temperature and pressure are summarized in the following tables.
  • Example 1 Example 1 :

Landscapes

  • Chemical & Material Sciences (AREA)
  • Organic Chemistry (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
  • Catalysts (AREA)
  • Low-Molecular Organic Synthesis Reactions Using Catalysts (AREA)

Abstract

La présente invention concerne un procédé catalytique en une étape pour l'oxydation sélective de cyclohexane avec de l'oxygène atmosphérique en vue de la fabrication de cyclohexanol et de cyclohexanone. Ce procédé comporte l'utilisation de catalyseurs microporeux amorphes, ainsi que celles de catalyseurs mésoporeux avec différents ions de métaux de transition comme centre actif dans un réacteur fonctionnant en continu, en phase gazeuse sous haute pression.
PCT/EP1999/004891 1998-07-16 1999-07-10 Procede pour l'oxydation de cyclohexane en phase gazeuse a l'aide de catalyseurs micro- et mesoporeux solides WO2000003963A1 (fr)

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
DE19832016A DE19832016A1 (de) 1998-07-16 1998-07-16 Verfahren zur Oxidation von Cyclohexan in der Gasphase unter Verwendung von festen mikro- und mesoporösen Katalysatoren
DE19832016.7 1998-07-16

Publications (1)

Publication Number Publication Date
WO2000003963A1 true WO2000003963A1 (fr) 2000-01-27

Family

ID=7874300

Family Applications (1)

Application Number Title Priority Date Filing Date
PCT/EP1999/004891 WO2000003963A1 (fr) 1998-07-16 1999-07-10 Procede pour l'oxydation de cyclohexane en phase gazeuse a l'aide de catalyseurs micro- et mesoporeux solides

Country Status (2)

Country Link
DE (1) DE19832016A1 (fr)
WO (1) WO2000003963A1 (fr)

Cited By (9)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN1317247C (zh) * 2004-12-09 2007-05-23 中国石化集团巴陵石油化工有限责任公司 从环己烷氧化产物中得到高纯度环己醇的方法
CN100364663C (zh) * 2006-04-07 2008-01-30 浙江大学 负载型纳米金催化剂及制备方法
EP1970364A2 (fr) 2007-03-16 2008-09-17 Sumitomo Chemical Company, Limited Procédé pour la fabrication de cycloalkanol et/ou cycloalkanone
JP2008260746A (ja) * 2007-03-16 2008-10-30 Sumitomo Chemical Co Ltd シクロアルカノール及び／又はシクロアルカノンの製造方法
WO2009002765A1 (fr) * 2007-06-27 2008-12-31 H R D Corporation Procédé à cisaillement élevé pour production de cyclohexanol
EP2096100A1 (fr) 2008-02-29 2009-09-02 Sumitomo Chemical Company, Limited Procédé pour la fabrication de cycloalkanol et/ou cycloalkanone
US7692044B2 (en) 2007-08-03 2010-04-06 Sumitomo Chemical Company, Limited Process for producing cycloalkanol and/or cycloalkanone
CN102260136A (zh) * 2010-05-26 2011-11-30 北京石油化工学院 环己烷液相氧化制备环己酮和环己醇混合物的方法
CN101148396B (zh) * 2006-09-22 2013-04-24 住友化学株式会社 制备环烷醇和/或环烷酮的方法

Families Citing this family (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
ES2704479T3 (es) * 2010-10-01 2019-03-18 Ube Industries Catalizador de oxidación para compuesto hidrocarburo, y método y aparato para producir óxido de compuesto hidrocarburo usando el mismo

Family Cites Families (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US5414157A (en) * 1990-10-17 1995-05-09 Sun Company, Inc. (R&M) Catalytic oxidation of alkanes
US5220080A (en) * 1992-06-29 1993-06-15 Sun Company, Inc. (R&M) Chromia on metal oxide catalysts for the oxidation of methane to methanol
US5345011A (en) * 1993-09-20 1994-09-06 Sun Company, Inc. (R&M) New manganese catalyst for light alkane oxidation
DE19545042A1 (de) * 1995-12-02 1997-06-05 Studiengesellschaft Kohle Mbh Amorphe mikroporöse Mischoxidkatalysatoren mit kontrollierter Oberflächenpolarität für die selektive heterogene Katalyse Adsorption und Stofftrennung

Non-Patent Citations (2)

* Cited by examiner, † Cited by third party
Title
GONGXUEN LU ET AL.: "Catalytic oxidation of cyclohexane into cyclohexanol and cyclohexanone over a TiO2/TS-1 system by dioxygen under UV irradiation", J.CHEM.SOC.CHEM.COMMUN., vol. 21, 1994, pages 2423 - 2424, XP002120975 *
SANG-BUM KIM ET AL.: "A new system for alkane oxidation. Modification of Gif-type reactions using O2/H2 with a Pd catalyst", CHEMISTRY LETTERS, no. 7, 1995, pages 535 - 536, XP002120976 *

Cited By (15)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN1317247C (zh) * 2004-12-09 2007-05-23 中国石化集团巴陵石油化工有限责任公司 从环己烷氧化产物中得到高纯度环己醇的方法
CN100364663C (zh) * 2006-04-07 2008-01-30 浙江大学 负载型纳米金催化剂及制备方法
CN101148396B (zh) * 2006-09-22 2013-04-24 住友化学株式会社 制备环烷醇和/或环烷酮的方法
US7709685B2 (en) 2007-03-16 2010-05-04 Sumitomo Chemical Company, Limited Method for producing cycloalkanol and/or cycloalkanone
JP2008260746A (ja) * 2007-03-16 2008-10-30 Sumitomo Chemical Co Ltd シクロアルカノール及び／又はシクロアルカノンの製造方法
EP1970364A2 (fr) 2007-03-16 2008-09-17 Sumitomo Chemical Company, Limited Procédé pour la fabrication de cycloalkanol et/ou cycloalkanone
WO2009002765A1 (fr) * 2007-06-27 2008-12-31 H R D Corporation Procédé à cisaillement élevé pour production de cyclohexanol
US7592493B2 (en) 2007-06-27 2009-09-22 H R D Corporation High shear process for cyclohexanol production
CN101679166B (zh) * 2007-06-27 2012-12-05 Hrd有限公司 用于环己醇生产的高剪切方法
EA021462B1 (ru) * 2007-06-27 2015-06-30 ЭйчАДи КОПЭРЕЙШН Способ получения циклогексанола
US7692044B2 (en) 2007-08-03 2010-04-06 Sumitomo Chemical Company, Limited Process for producing cycloalkanol and/or cycloalkanone
EP2096100A1 (fr) 2008-02-29 2009-09-02 Sumitomo Chemical Company, Limited Procédé pour la fabrication de cycloalkanol et/ou cycloalkanone
JP2009227653A (ja) * 2008-02-29 2009-10-08 Sumitomo Chemical Co Ltd シクロアルカノール及び／又はシクロアルカノンの製造方法
US7923583B2 (en) 2008-02-29 2011-04-12 Sumitomo Chemical Company, Limited Method for producing cycloalkanol and/or cycloalkanone
CN102260136A (zh) * 2010-05-26 2011-11-30 北京石油化工学院 环己烷液相氧化制备环己酮和环己醇混合物的方法

Also Published As

Publication number Publication date
DE19832016A1 (de) 2000-01-20

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