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WO2010143195A1 - Procédé de fabrication à basse pression de cyclohexylamine - Google Patents

Procédé de fabrication à basse pression de cyclohexylamine Download PDF

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Publication number
WO2010143195A1
WO2010143195A1 PCT/IN2010/000075 IN2010000075W WO2010143195A1 WO 2010143195 A1 WO2010143195 A1 WO 2010143195A1 IN 2010000075 W IN2010000075 W IN 2010000075W WO 2010143195 A1 WO2010143195 A1 WO 2010143195A1
Authority
WO
WIPO (PCT)
Prior art keywords
reactor
catalyst
aniline
cyclohexylamine
pressure
Prior art date
Application number
PCT/IN2010/000075
Other languages
English (en)
Inventor
Sidram Shinde Bapurao
Chandra Shekhar Shukla
Amod Madhukar Sathe
Original Assignee
Hindustan Organic Chemicals Limited
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 Hindustan Organic Chemicals Limited filed Critical Hindustan Organic Chemicals Limited
Publication of WO2010143195A1 publication Critical patent/WO2010143195A1/fr

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Classifications

    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C209/00—Preparation of compounds containing amino groups bound to a carbon skeleton
    • C07C209/68—Preparation of compounds containing amino groups bound to a carbon skeleton from amines, by reactions not involving amino groups, e.g. reduction of unsaturated amines, aromatisation, or substitution of the carbon skeleton
    • C07C209/70—Preparation of compounds containing amino groups bound to a carbon skeleton from amines, by reactions not involving amino groups, e.g. reduction of unsaturated amines, aromatisation, or substitution of the carbon skeleton by reduction of unsaturated amines
    • C07C209/72—Preparation of compounds containing amino groups bound to a carbon skeleton from amines, by reactions not involving amino groups, e.g. reduction of unsaturated amines, aromatisation, or substitution of the carbon skeleton by reduction of unsaturated amines by reduction of six-membered aromatic rings
    • 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

  • Cyclohexylamine finds applications in Ae manufacture of insecticides, dyestuffs, emulsifying agents, metal corrosion inhibitors, plasticizers etc. It is commercially produced from cyclohexanone, cyclohexanol or phenol in presence of ammonia and hydrogen (Japanese Unexamined Patent Publication Nos. 45-19897, 45-19898, 51-41627).
  • An alternative method for the production of cyctohexylamine consists of hydrogenating aniline with some base metal catalysts like nickel, and cobalt, and some noble metal catalysts viz. ruthenium, palladium, rhodium etc. (US Patent No. 4,914,239, Japanese Examined Patent Publication No.45-28368).
  • ft is generally seen mat base metal catalysts are effective at elevated pressures and temperatures, where as noble metal catalysts require milder conditions (Paul N. Ryiander, Hydrogenation Methods, pp 123-126).
  • m a high pressure process using ruthenium catalyst, cyclohexylamine has been produced at 50 tolOO bar pressure (Unpublished results at Malawistan Organic Chemicals Ltd.).
  • m a low pressure process, this chemical has been produced at a hydrogen pressure of about 2 bar using an ahimina supported rhodium catalyst (Practical Catalytic Hydrogenation, Morris Freifelder, Wiley-mterscience, pp 556-557, 1970).
  • ft can be produced even at 1 bar with a carbon supported palladium catalyst (J. Organ. Chem. USSR, Volume 1, pp 769, 1965).
  • the objective of the present invention is to produce cyclohexylamine at lower pressure. More particularly, it is concerned with an economical process for making cyclohexylamine with considerably reduced safety risks.
  • This invention relates to a process for the production of cyclohexylamine from aniline and hydrogen at low pressure. More particularly, it is concerned with an economical process with considerably reduced safety risks.
  • the process consists of hydrogenating aniline m liquid phase in a batch reactor in presence of an alumina supported group Vm metal catalyst, at a hydrogen pressure of about 5 kg/cm 2 to 20 kg/cm 2 with either continuous or intermittent venting of the reactor. Under the said process conditions, an aniline conversion of about 90 % to 100 % with a cyclohexylamine content of about 85 % to 95 % is achieved.
  • the present invention describes an economical process to produce cyclohexylamine at low pressure by the hydrogenation of anfline in liquid phase in a batch reactor made of stainless steel and equipped with stirrer, pressure gauge, the ⁇ no couple and safety disc.
  • the reactor is heated electrically or by steam.
  • An automatic temperature controller is used for controlling the reactor temperature.
  • the reactor may be of laboratory scale (300 ml) or an industrial scale (5000 liters).
  • the said hydrogenation is carried out in the said batch reactor in presence of an alumina supported group Vm metal catalyst which is a finery divided powder of 30 micron to 90 micron size with a metal content of about 2.5 to 7.5 % by weight Aniline and the said catalyst (0.10 % to 3.50 %, weight by volume) are charged in the said reactor.
  • the reactor is first purged with nitrogen and then with hydrogen.
  • the reactor is then pressurized with hydrogen to about 5 to 10 kg/cm 2 and heated to 190° to 225° C.
  • the reactor pressure is adjusted to about 10 to 25 kg/cm 2 for 5 to 15 hrs under constant stirring by maintaining the stirrer speed at about 100 to 1200 revolutions per minute.
  • the vapors of the reactor are vented out either constantly at the rate of 1 to 20 Hters/hr or intermittently by depressurizing the reactor.
  • the conversion of aniline is about 90 % to 100% weight with a cyclohexylamine content of about 85 % to 95 % weight
  • TbJs experiment was carried out at high pressure for comparison.
  • 300 ml of aniline and 0.75 g of an alumina supported ruthenium catalyst (mmenium content, 5%) were charged in a 600 ml Parr reactor, model No. 4563, equipped with stirrer, internal cooling coil, thermocouple, pressure gauge, safety rupture disc, programmable temperature controller and solenoid valve with a water flow connection to the internal cooling coiL
  • the reactor was purged first with nitrogen and then with hydrogen.
  • the reactor was pressurized with hydrogen to 8 kg /cm 2 and was heated to 220 0 C.
  • the reactor pressure was then adjusted to 70 kg /cm 2 and was maintained at thus pressure and at the said temperature for 6 to 8 hrs under constant stirring at 1000 revolutions per minute.
  • This experiment was carried out in a 1000 liters stainless steel reactor equipped with steam jacket, internal cooling coil, stirrer, thermocouple, pressure gauge, safety verve and rupture disc.
  • the reactor was made by M/s Zschokke Wartmami A.G., Switzerland.
  • a stainless steel tube was connected at the top of the reactor. The other end of the said tube was connected through a control valve to a water trap with the help of another stainless steel tube.
  • the reactor was charged with 550 liters aniline and 4 kg of the saidn ⁇ t- «nium catalyst and was first purged with nitrogen and men with hydrogen.
  • the reactor was men pressurized with hydrogen to 10 kg/cm 2 .
  • the reactor contents were stirred at about 200 revolutions per minute and men heated to about 220° C by introducing steam in the jacket As me reactor pressure started falling, it was controlled at the hydrogen pressure of 17 kg /cm 2 .
  • the reactor temperature was maintained at 220° C by circulating cooled oil through the internal cooling coil when ever required.
  • the reaction was earned out at the said pressure and temperature for about 8 hrs with a constant venting of me reactor vapors at a rate of 8 -10 liters/hr. Under the said conditions, the conversion of aniline was found to be 99.63% weight with overall cyclohexylamine content of 93.28 % weight

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

Abstract

Procédé de fabrication de cyclohexylamine à parti d'aniline et d'hydrogène, sous basse pression et en phase liquide, au moyen d'un catalyseur d'hydrogénation contenant un métal du groupe VIII comme principe actif. Plus particulièrement, l'invention concerne un procédé économique de fabrication de cyclohexylamine qui permet de réduire très sensiblement les risques pesant sur la sécurité.
PCT/IN2010/000075 2009-06-09 2010-02-11 Procédé de fabrication à basse pression de cyclohexylamine WO2010143195A1 (fr)

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
IN1385MU2009 2009-06-09
IN1385/MUM/2009 2009-06-09

Publications (1)

Publication Number Publication Date
WO2010143195A1 true WO2010143195A1 (fr) 2010-12-16

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ID=43308493

Family Applications (1)

Application Number Title Priority Date Filing Date
PCT/IN2010/000075 WO2010143195A1 (fr) 2009-06-09 2010-02-11 Procédé de fabrication à basse pression de cyclohexylamine

Country Status (1)

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WO (1) WO2010143195A1 (fr)

Citations (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US2822392A (en) * 1954-09-20 1958-02-04 Abbott Lab Process for producing cyclohexylamine
US5023226A (en) * 1988-01-22 1991-06-11 Bayer Aktiengesellschaft Ruthenium supported catalyst, its preparation and its use in the preparation of substituted or unsubstituted cyclohexylamine and substituted or unsubstituted dicyclohexylamine
US20070066849A1 (en) * 2005-09-22 2007-03-22 Vedage Gamini A Hydrogenation of aromatic amines to alicyclic amines using a lithium aluminate-based catalyst

Patent Citations (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US2822392A (en) * 1954-09-20 1958-02-04 Abbott Lab Process for producing cyclohexylamine
US5023226A (en) * 1988-01-22 1991-06-11 Bayer Aktiengesellschaft Ruthenium supported catalyst, its preparation and its use in the preparation of substituted or unsubstituted cyclohexylamine and substituted or unsubstituted dicyclohexylamine
US20070066849A1 (en) * 2005-09-22 2007-03-22 Vedage Gamini A Hydrogenation of aromatic amines to alicyclic amines using a lithium aluminate-based catalyst

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