WO2000003963A1 - Method for oxidising cyclohexane in gas phase by means of solid micro- and mesoporous catalysts - Google Patents

Method for oxidising cyclohexane in gas phase by means of solid micro- and mesoporous catalysts Download PDF

Info

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
Authority
WO
WIPO (PCT)
Prior art keywords
bar
cyclohexane
gas phase
catalysts
mesoporous
Prior art date
Application number
PCT/EP1999/004891
Other languages
German (de)
French (fr)
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/en

Links

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 :

Abstract

The invention relates to a one-step catalytic method for selective oxidation of cyclohexane with atmospheric oxygen for producing cyclohexanol and cyclohexanone. The inventive method comprises using amorphous microporous catalysts as well as mesoporous catalysts with different transition metal ions as active centre in a continuously operated reactor, in the gas phase under high pressure.

Description

Verfahren zur Oxidation von Cyclohexan in der Gasphase unter Verwendung von festen mikro- und mesoporösen Katalysatoren Process for the oxidation of cyclohexane in the gas phase using solid micro- and mesoporous catalysts
Die vorliegende Erfindung betrifft ein einstufiges katalytisches Verfahren zur selektiven Oxidation von Cyclohexan mit Luftsauerstoff zur Herstellung von Cyclohexanol und Cyclohexanon. Das Verfahren umfaßt die Verwendung von amorphen mikroporösen als auch die von mesoporösen Katalysatoren mit unterschiedlichen Übergangsmetallionen als aktivem Zentrum in einem kontinuierlich betriebenem Reaktor in der Gasphase unter erhöhtem Druck.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.
Zur Herstellung von Cyclohexanol und Cyclohexanon gibt es eine Reihe von Verfahren, die von unterschiedlichen Rohstoffen ausgehen. Dabei handelt es sich um zweistufige Verfahren und/oder homogen katalysierte Reaktionen [US 3076810, (Kirk, Othmer, Encyclopedia of Chemical Technology, 3. Ed., Vol 7 (1981); Ullmann's Encyclopedia of Indusrial Chemistry, VCH, 5. Ed., A8; Weissermel, Arpe, Industrielle Organische Chemie, VCH, Weinheim 1994; US 3957876; Ger. Offen. 2154656; US 3404185; US 3598869; US 2851496; Ger. Offen. 2124124; Brit. 777087;SU 503846; SU 757513]. Nicht bekannt sind bisher heterogen katalysierte Gasphasenreaktionen bei Temperaturen über 200 °C zur Oxidation von Cyclohexan.There are a number of processes for the production of cyclohexanol and cyclohexanone that start from different raw materials. These are two-stage processes and / or homogeneously catalyzed reactions [US 3076810, (Kirk, Othmer, Encyclopedia of Chemical Technology, 3rd Ed., Vol 7 (1981); Ullmann's Encyclopedia of Industrial Chemistry, VCH, 5th Ed. , A8; Weissermel, Arpe, Industrielle Organische Chemie, VCH, Weinheim 1994; US 3957876; Ger. Offen. 2154656; US 3404185; US 3598869; US 2851496; Ger. Offen. 2124124; Brit. 777087; SU 503846; SU 757513] Heterogeneously catalyzed gas phase reactions at temperatures above 200 ° C. for the oxidation of cyclohexane are not yet known.
Wir haben gefunden, daß bei Verwendung von mikro- oder mesoporösen Katalysatoren Cyclohexan in einer einstufigen Gasphasenreaktion unter Druck mit Luft selektiv oxidiert werden kann. Als besonders geeignet für diese Reaktion erwiesen sich mikro- und mesoporöse Mischoxidkatalysatoren (z.B. Si02, Ti02, Al203 oder Zr02) mit einem geringen Gehalt von Co-, Cr oder V- lonen (maximal 10 %) oder anderen Übergangsmetallionen. Die Umsetzung erfolgt bei Temperaturen zwischen 150 und 350 °C und einem Druck von mindestens 2 bar. Beste Ergebnisse werden bei Drucken von 15 bis 25 bar erzielt. Eine deutliche Selektivitätsverbesserung kann erzielt werden, wenn die Reaktorwände aus katalytisch inertem Material bestehen, oder wenn metallische oder andere Reaktorinnenwände mit einem katalytisch inerten Material wie Gold, Teflon oder Quarz verkleidet, durch entsprechende Einbauten mit einem solchen Material abgedeckt sind, oder mit passivierendem Lack überzogen sind. Das Verfahren bietet neben den erzielbaren Umsätzen und der guten Selektivitäten den Vorteil der heterogenen Reaktionsführung in der Gasphase, die es erlaubt, im Gegensatz zu allen bisher eingesetzten technischen Verfahren, das Produktgemisch vom Katalysator sehr einfach abzutrennen. Ein weiterer Vorteil dieser Reaktionsführung liegt in der einfachen Rückführung des Cyclohexans.We have found that when using micro- or mesoporous catalysts, cyclohexane can be selectively oxidized with air in a single-stage gas phase reaction under pressure. Micro- and mesoporous mixed oxide catalysts (eg Si0 2 , Ti0 2 , Al 2 0 3 or Zr0 2 ) with 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. In addition to the achievable conversions and the good selectivities, 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.
Beispiele:Examples:
Reaktor:Reactor:
Die Reaktion wird in einem 1 m langen Reaktionsrohr durchgeführt, das innen mit einem Quarzrohr verkleidet ist. Das Rohr hat einen Durchmesser von 0,5 cm und wird mit Hilfe eines Heizmantels auf die entsprechende Reaktionstemperatur gebracht. In diesem senkrecht angebrachten Rohr wird die Katalysatorschüttung eingebracht (100 mg). Der Katalysator wird vor dem Einsatz bei 400 °C im Luftstrom kalziniert. Die Produktmischung wird nach dem Reaktor im entspannten Zustand entnommen und analysiert (gaschromato- graphisch).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).
ReaktionsführungReaction management
Als beispielhafte Katalysatoren wurden amorphe mikroporöse und mesoporöse Mischoxide mit Siliciumdioxid als Matrixmaterial und Cr und V als aktive Zentren eingesetzt (AMM: DE-A 195.450422.6, MCM-41 : US 5108725). Das Cyclohexan wird kontinuierlich mit Hilfe einer HPLC-Pumpe flüssig mit einem konstanten Fördervolumen von 2 ml / h zum Trägergasstrom (Luft, 500 ml/h) in den Reaktor dosiert. Die resultierende Prouktzusammensetzungen in Abhängigkeit von der Temperatur und dem Druck sind in den folgenden Tabellen zusammengefaßt. Beispiel 1 :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 :
Katalysator: 5 % Cr in SiO2 Catalyst: 5% Cr in SiO 2
Temperatur Druck Umsatz Cyclohexanol CyclohexanonTemperature pressure conversion cyclohexanol cyclohexanone
200 °C 15 bar 0,12% 33,8% 27,0%200 ° C 15 bar 0.12% 33.8% 27.0%
250 °C 15 bar 0,42% 28,5% 28,5%250 ° C 15 bar 0.42% 28.5% 28.5%
300 °C 15 bar 1 ,16% 25,8% 36,2%300 ° C 15 bar 1.16% 25.8% 36.2%
350°C 15 bar 0,99% 12,1% 31 ,3%350 ° C 15 bar 0.99% 12.1% 31.3%
200 °C 25 bar 1 ,72% 37,3% 33,8%200 ° C 25 bar 1.72% 37.3% 33.8%
250 °C 25 bar 1 ,33% 33,9% 17,3%250 ° C 25 bar 1.33% 33.9% 17.3%
300 °C 25 bar 2,39% 31 ,4% 31 ,0%300 ° C 25 bar 2.39% 31.4% 31.0%
350°C 25 bar 4,24% 28,3% 30,7%350 ° C 25 bar 4.24% 28.3% 30.7%
Beipiels 2:Example 2:
Katalysator: 5 % Cr in MCM-41Catalyst: 5% Cr in MCM-41
Temperatur Druck Umsatz Cyclohexanol CyclohexanonTemperature pressure conversion cyclohexanol cyclohexanone
200 °C 15 bar 0,26% 8,2% 47,0%200 ° C 15 bar 0.26% 8.2% 47.0%
250 °C 15 bar 0,46% 37,3% 50,5%250 ° C 15 bar 0.46% 37.3% 50.5%
300 °C 15 bar 3,45% 22,6% 32,2%300 ° C 15 bar 3.45% 22.6% 32.2%
350°C 15 bar 3,37% 23,1% 31 ,5%350 ° C 15 bar 3.37% 23.1% 31.5%
200 °C 25 bar 0,88% 41 ,0% . 26,2%200 ° C 25 bar 0.88% 41.0%. 26.2%
250 °C 25 bar 0,58% 29,5% 24,3%250 ° C 25 bar 0.58% 29.5% 24.3%
300 °C 25 bar 3,29% 32,5% 28,5%300 ° C 25 bar 3.29% 32.5% 28.5%
350°C 25 bar 2,98% 32,9% 27,5% Beispiel 3:350 ° C 25 bar 2.98% 32.9% 27.5% Example 3:
Katalysator: 5 % V in SiO2 Catalyst: 5% V in SiO 2
Temperatur Druck Umsatz Cyclohexanol CyclohexanonTemperature pressure conversion cyclohexanol cyclohexanone
200 °C 15 bar 0,78% 41 ,2% 20,6%200 ° C 15 bar 0.78% 41.2% 20.6%
250 °C 15 bar 1 ,86% 29,1 % 29,6%250 ° C 15 bar 1.86% 29.1% 29.6%
300 °C 15 bar 3,69% 28,2% 31 ,4%300 ° C 15 bar 3.69% 28.2% 31.4%
350°C 15 bar 3,96% 39,4% 32,5%350 ° C 15 bar 3.96% 39.4% 32.5%
200 °C 25 bar 0,87% 28,8% 18,4%200 ° C 25 bar 0.87% 28.8% 18.4%
250 °C 25 bar 1 ,89% 32,7% 25,3%250 ° C 25 bar 1.89% 32.7% 25.3%
300 °C 25 bar 4,23% 40,6% 34,5%300 ° C 25 bar 4.23% 40.6% 34.5%
350°C 25 bar 3,89% 31 ,4% 28,3%350 ° C 25 bar 3.89% 31.4% 28.3%
Beispiel 4:Example 4:
Katalysator: 5% V in MCM-41Catalyst: 5% V in MCM-41
Temperatur Druck Umsatz Cyclohexanol CyclohexanonTemperature pressure conversion cyclohexanol cyclohexanone
200 °C 15 bar 0,35% 31 ,6% 23,3%200 ° C 15 bar 0.35% 31.6% 23.3%
250 °C 15 bar 1 ,31% 15,2% 22,9%250 ° C 15 bar 1, 31% 15.2% 22.9%
300 °C 15 bar 1 ,92% 17,7% 19,3%300 ° C 15 bar 1, 92% 17.7% 19.3%
350°C 15 bar 3,00% 21 ,4% 28,4%350 ° C 15 bar 3.00% 21.4% 28.4%
200 °C 25 bar 1 ,52% 42,8% . . 23,7%200 ° C 25 bar 1.52% 42.8%. . 23.7%
250 °C 25 bar 2,27% 28,7% 31 ,3%250 ° C 25 bar 2.27% 28.7% 31.3%
300 °C 25 bar 2,03% 25,1 % 25,6%300 ° C 25 bar 2.03% 25.1% 25.6%
350°C 25 bar 1 ,64% 9,8% 16,5% 350 ° C 25 bar 1.64% 9.8% 16.5%

Claims

Patentansprüche claims
1. Verfahren zur selektiven katalytischen Oxidation von Cyclohexan, dadurch gekennzeichnet, daß bei Temperaturen über 200 °C in Gegenwart von mikro- oder mesoporösen Mischoxidkatalysatoren in einem Reaktionsgefäß mit katalytisch inerten Innenwänden Cyclohexan mit Sauerstoff in Berührung gebracht wird.1. A process for the selective catalytic oxidation of cyclohexane, characterized in that at temperatures above 200 ° C in the presence of micro- or mesoporous mixed oxide catalysts in a reaction vessel with catalytically inert inner walls cyclohexane is brought into contact with oxygen.
2. Verfahren nach Anspruch 1 , wobei der Sauerstoff in Form von Luft eingesetzt wird.2. The method according to claim 1, wherein the oxygen is used in the form of air.
3. Verfahren nach Anspruch 1 , wobei die Oxidation bei einem Druck über 5 bar durchgeführt wird.3. The method according to claim 1, wherein the oxidation is carried out at a pressure above 5 bar.
4. Verfahren nach Anspruch 1 , wobei die Oxidation bei einem Druck von mindestens 15 bar ausgeführt wird.4. The method of claim 1, wherein the oxidation is carried out at a pressure of at least 15 bar.
5. Verfahren nach Anspruch 1 , wobei die Innenwände des Reaktionsgefäßes mit Gold, Teflon, Glas, Kevlar oder Graphit ausgekleidet oder mit passivierendem Lack überzogen sind.5. The method according to claim 1, wherein the inner walls of the reaction vessel are lined with gold, Teflon, glass, Kevlar or graphite or are coated with passivating lacquer.
6. Verfahren nach Ansprüchen 1 - 5, wobei der Mischoxidkatalysator aus Si02, Ti02, AI203 oder Zr02 oder deren Mischungen, dotiert mit Übergangsmetali- Ionen, besteht.6. The method according to claims 1-5, wherein the mixed oxide catalyst from Si0 2 , Ti0 2 , Al 2 0 3 or Zr0 2 or mixtures thereof, doped with transition metal ions.
7. Verfahren nach Anspruch 6, wobei als Übergangsmetall-Ionen Co-, Cr- oder V-Ionen verwendet werden. 7. The method according to claim 6, wherein Co, Cr or V ions are used as transition metal ions.
PCT/EP1999/004891 1998-07-16 1999-07-10 Method for oxidising cyclohexane in gas phase by means of solid micro- and mesoporous catalysts WO2000003963A1 (en)

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
DE19832016A DE19832016A1 (en) 1998-07-16 1998-07-16 Selective oxidation of cyclohexane to cyclohexanol and cyclohexanone comprises reaction with oxygen on a micro- or meso-porous mixed oxide catalyst in a heated reactor with an inert lining
DE19832016.7 1998-07-16

Publications (1)

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

Family

ID=7874300

Family Applications (1)

Application Number Title Priority Date Filing Date
PCT/EP1999/004891 WO2000003963A1 (en) 1998-07-16 1999-07-10 Method for oxidising cyclohexane in gas phase by means of solid micro- and mesoporous catalysts

Country Status (2)

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

Cited By (9)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN1317247C (en) * 2004-12-09 2007-05-23 中国石化集团巴陵石油化工有限责任公司 Method of obtaining high purity cyclohexanol from cyclohexane oxidation product
CN100364663C (en) * 2006-04-07 2008-01-30 浙江大学 Supported nano Au catalyst and method for preparing the same
EP1970364A2 (en) 2007-03-16 2008-09-17 Sumitomo Chemical Company, Limited Method for Producing Cycloalkanol and/or Cycloalkanone
JP2008260746A (en) * 2007-03-16 2008-10-30 Sumitomo Chemical Co Ltd Method for producing cycloalkanol and/or cycloalkanone
WO2009002765A1 (en) * 2007-06-27 2008-12-31 H R D Corporation High shear process for cyclohexanol production
EP2096100A1 (en) 2008-02-29 2009-09-02 Sumitomo Chemical Company, Limited Method for Producing Cycloalkanol and/or Cycloalkanone
US7692044B2 (en) 2007-08-03 2010-04-06 Sumitomo Chemical Company, Limited Process for producing cycloalkanol and/or cycloalkanone
CN102260136A (en) * 2010-05-26 2011-11-30 北京石油化工学院 Method for preparing mixture of cyclohexanone and cyclohexanol by oxidazing cyclohexane liquid phase
CN101148396B (en) * 2006-09-22 2013-04-24 住友化学株式会社 Process for producing cycloalkanol and/or cycloalkanone

Families Citing this family (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
ES2704479T3 (en) * 2010-10-01 2019-03-18 Ube Industries Oxidation catalyst for hydrocarbon compound, and method and apparatus for producing hydrocarbon compound oxide using the same

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 (en) * 1995-12-02 1997-06-05 Studiengesellschaft Kohle Mbh Amorphous microporous mixed oxide catalysts with controlled surface polarity for selective heterogeneous catalysis adsorption and material separation

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 (en) * 2004-12-09 2007-05-23 中国石化集团巴陵石油化工有限责任公司 Method of obtaining high purity cyclohexanol from cyclohexane oxidation product
CN100364663C (en) * 2006-04-07 2008-01-30 浙江大学 Supported nano Au catalyst and method for preparing the same
CN101148396B (en) * 2006-09-22 2013-04-24 住友化学株式会社 Process for producing cycloalkanol and/or cycloalkanone
US7709685B2 (en) 2007-03-16 2010-05-04 Sumitomo Chemical Company, Limited Method for producing cycloalkanol and/or cycloalkanone
JP2008260746A (en) * 2007-03-16 2008-10-30 Sumitomo Chemical Co Ltd Method for producing cycloalkanol and/or cycloalkanone
EP1970364A2 (en) 2007-03-16 2008-09-17 Sumitomo Chemical Company, Limited Method for Producing Cycloalkanol and/or Cycloalkanone
WO2009002765A1 (en) * 2007-06-27 2008-12-31 H R D Corporation High shear process for cyclohexanol production
US7592493B2 (en) 2007-06-27 2009-09-22 H R D Corporation High shear process for cyclohexanol production
CN101679166B (en) * 2007-06-27 2012-12-05 Hrd有限公司 High shear process for cyclohexanol production
EA021462B1 (en) * 2007-06-27 2015-06-30 ЭйчАДи КОПЭРЕЙШН Process for cyclohexanol production
US7692044B2 (en) 2007-08-03 2010-04-06 Sumitomo Chemical Company, Limited Process for producing cycloalkanol and/or cycloalkanone
EP2096100A1 (en) 2008-02-29 2009-09-02 Sumitomo Chemical Company, Limited Method for Producing Cycloalkanol and/or Cycloalkanone
JP2009227653A (en) * 2008-02-29 2009-10-08 Sumitomo Chemical Co Ltd Method for producing cycloalkanol and/or cycloalkanone
US7923583B2 (en) 2008-02-29 2011-04-12 Sumitomo Chemical Company, Limited Method for producing cycloalkanol and/or cycloalkanone
CN102260136A (en) * 2010-05-26 2011-11-30 北京石油化工学院 Method for preparing mixture of cyclohexanone and cyclohexanol by oxidazing cyclohexane liquid phase

Also Published As

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

Similar Documents

Publication Publication Date Title
EP1038833B1 (en) Process for the preparation of hydrogen peroxide by direct synthesis
EP1308416B1 (en) Direct synthesis of hydrogen peroxide and its integration in oxidation processes
EP1399255A2 (en) Ruthenium catalysts on a si02-based carrier material for catalytic hydrogenation of saccharides
EP0723810A1 (en) Catalyst, his preparation process and use thereof to produce vinyl acetate monomer
US5536849A (en) Process for producing gamma-butyrolactone
EP0411455B1 (en) Process for continuous purification of caprolactam
WO2000003963A1 (en) Method for oxidising cyclohexane in gas phase by means of solid micro- and mesoporous catalysts
DE4205633A1 (en) PROCESS FOR CLEANING CYCLOHEXANONE
EP0096798B1 (en) Process for the preparation of cyclohexanol and cyclohexanone
DE3222143A1 (en) CARBON CATALYSTS CONTAINING COBALT, THEIR PRODUCTION AND USE
EP1161409B1 (en) Method of producing cyclic, alpha, beta-unsaturated ketones
EP0235804A2 (en) Improved process for the preparation of P-cymen and homologous alkylbenzenes
DE4333328A1 (en) Controlled decomposition of per-oxide(s) - is carried out by passing a soln. contg. peroxide over a metal oxide catalyst
EP0953558B1 (en) Process for the preparation of aromatic compounds containing hydroxyl groups
EP0268826B1 (en) Process for the treatment of reactive mixtures containing cyclohexyl hydroperoxide
EP0005293A1 (en) Process and apparatus for the production of cyclohexanone
DE2352378C2 (en) Process for the preparation of mixtures of cycloalkanones and cycloalkanols
EP1107931A1 (en) Method for producing a titanium silicate with rut structure
DE10009639A1 (en) Production of dinitrogen monoxide (laughing gas) by catalytic reduction of nitrogen monoxide with a reducing agent in the gas phase with heterogenic catalysis
EP0405485B1 (en) Process for the preparation of carbonyl compounds
DE2810856C2 (en) Process for the preparation of o-aminobenzonitrile
KR19980701242A (en) Process for Improving the Purity of Hexane Diol-1,6
DE3636056A1 (en) Process for working up reaction mixtures containing cyclohexyl hydroperoxide
DD218099B5 (en) Process for the preparation of propene oxide
DE1161558B (en) Process for the production of cyclohexanone

Legal Events

Date Code Title Description
AK Designated states

Kind code of ref document: A1

Designated state(s): CA JP US

AL Designated countries for regional patents

Kind code of ref document: A1

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

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

Ref country code: CA