WO2003078374A1 - Procede de production de cyclohexanone - Google Patents

Procede de production de cyclohexanone Download PDF

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Publication number
WO2003078374A1
WO2003078374A1 PCT/RU2002/000438 RU0200438W WO03078374A1 WO 2003078374 A1 WO2003078374 A1 WO 2003078374A1 RU 0200438 W RU0200438 W RU 0200438W WO 03078374 A1 WO03078374 A1 WO 03078374A1
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WO
WIPO (PCT)
Prior art keywords
reaction
goodbye
cyclohexane
mixture
inert gas
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PCT/RU2002/000438
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English (en)
Russian (ru)
Inventor
Constantin Alexandrovich Dubkov
Gennady Ivanovich Panov
Valentin Nikolaevich Parmon
Evgeny Vladimirovich Starokon
Original Assignee
Institut Kataliza Imeni G.K. Boreskova Sibirskogo Otdeleniya Rossiiskoi Akademii Nauk
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.)
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Application filed by Institut Kataliza Imeni G.K. Boreskova Sibirskogo Otdeleniya Rossiiskoi Akademii Nauk filed Critical Institut Kataliza Imeni G.K. Boreskova Sibirskogo Otdeleniya Rossiiskoi Akademii Nauk
Priority to AU2002335569A priority Critical patent/AU2002335569A1/en
Priority to JP2003576383A priority patent/JP2005528357A/ja
Publication of WO2003078374A1 publication Critical patent/WO2003078374A1/fr

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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
    • C07C45/28—Preparation of compounds having >C = O groups bound only to carbon or hydrogen atoms; Preparation of chelates of such compounds by oxidation of CHx-moieties
    • 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
    • Y02P20/584—Recycling of catalysts

Definitions

  • Cyclohexane is an intermediate product for the synthesis of ⁇ -acid and adipic acid, which was used for a little 6. It also uses a wide range of fats, dyes, consumables, and synthetic smokers.
  • the main industrial process of cyclic acid production is in liquid oxidation of cyclic acid.
  • the process is conducted in the range of 145-180 ° ⁇ at a pressure of 8-12 atm., Using in the quality of the catalytic converter the salt [27]. ⁇ a ⁇ . ⁇ ° 3530185, 1970, ⁇ . ⁇ Economics ⁇ ]. With this, a mixture of cyclohexane and cyclohexane is produced, in which case for cyclohexane it is less than 50%.
  • the introduction of the process is non-catalytic.
  • the acid is added, which binds to the cyclohexane synthesized in the form of an ether, thereby suppressing the by-product of the by-product.
  • the disadvantage of the process variants is a significant decrease in the selectivity of the reaction with an increase in the conversion of cyclohexane. To maintain total selectivity for cyclohexan and cyclohexanole at an level of 85-90%, the incurrence for income should not exceed 3-5%. This leads to greater costs for the allocation of products and recirculation of cyclohexane.
  • Cyclohexane can also be obtained by selective catalytic dehydration of cyclohexane [ ⁇ .8. ⁇ a ⁇ . -4 ° 3998884, 1976, S. ⁇ . ⁇ ] or by hydrating the phenol [ ⁇ .8. ⁇ a ⁇ . ⁇ ° 3076810, 1963, ⁇ . 1. ⁇
  • ⁇ ⁇
  • ⁇ ⁇
  • ⁇ ⁇
  • ⁇ ⁇
  • Non-inert gas can play the flue gases of the reaction.
  • the autoloader is loaded cyclically in such a way that it is in the form of a reaction in the form of a liquid in the form of a reaction. Then, nitrous oxide or its mixture with inert gas is supplied, bringing the pressure to a predetermined value. There is only 2 ⁇ of this type, so that its pressure at the reaction temperature is 0.01-100 atm.
  • the reaction is carried out at a temperature of 20-350 ° C.
  • the response time is subject to the conditions for its use, and also the terms and conditions of the process, and may change for a few minutes. If necessary, to ensure a deeper conversion of the cyclohexene, the gas phase is replaced by a new nitrogen oxide transfer and the reaction to the reaction.
  • the proposed process may be carried out without solvents. However, with the use of the process and with the use of devices, some can be removed from the wide range of substances that are used in the process of synthesis. A product with a fairly high speed is available without a catalyst, although it can also be handled in a non-commercialized manner.
  • the proposed method for the production of cyclohexane does not offer a high number of original reagents.
  • the reserve of nitrogen may be used in its pure form, as well as with the addition of various gases that do not have an adverse effect on the performance of the process.
  • Cyclohexen also It may contain impurities that do not indicate an adverse effect on the performance of the process.
  • EXAMPLE 1 A volume of 100 cm (firm QAGG), made of stainless steel and equipped with a stirrer, is poured 25 cm 3 of cyclohexene (CRYSTAL, 99%). They blow off nitrous oxide and then bring its pressure to 25 atm. They pressurize, heat up to 250 ° ⁇ , and withstand it at this temperature for 5 hours. After terminating the reaction, they cool, measure pressure and analyze the final composition of the gas and liquid phase by means of the gas process and by the process.
  • CYSTAL cyclohexene
  • Example 2 is similar to Example 1 with the exception that the reaction takes place within 12 hours.
  • Example 3 is similar to Example 1 with the exception that the reaction is carried out at 150 ° C for 23 hours.
  • Example 4 is similar to Example 1 with the exception that the reaction is carried out at a temperature of 198 ° C for 15 hours.
  • Example 5 is similar to Example 1 with the exception that the reaction is carried out at 220 ° C for 12 hours.
  • Example 6 is similar to Example 1 with the exception that the reaction is carried out at 280 ° C for 3 hours.
  • Example 7 is comparative. The experiment is carried out in a similar manner to Example 1, which means that 4 ml of cyclohexen are loaded in the process. With such a load, the whole cycle is reactive in the gaseous phase. As a result of the experiment, the inversion of the cyclohexen was, at least, 0.5%. This means that, given these conditions, the reaction in the gas phase is practically not ideal.
  • Examples 8–9 in comparison with Examples 4 and 5 demonstrate the influence of the concentration of nitrous oxide on the indices of the process (Table 2).
  • the concentration of nitrous oxide in the reaction mixture is determined by the value of its initial pressure at the room temperature, ⁇ ⁇ 0 .
  • Example 8 is similar to Example 4 with the exception that the initial pressure of nitrous oxide in this experiment sets 40 atm.
  • Example 9 is similar to Example 5 with the exception that the initial pressure of nitrous oxide in this experiment sets 10 atm. Table 2
  • Example 10 is analogous to Example 1, with the exception that the oxidation of cyclohexene leads to 16.5 hours in the process of 0.21 g of the integral catalyst ⁇ 8 ⁇ -5.
  • Example 11 is similar to Example 4 with the exception that the reaction takes 12 hours in the case of 0.2 g Ge 2 ⁇ 3 / 8 ⁇ 2 (2.8 wt.% ⁇ réelle 2 ⁇ 3 ). It is prepared by the use of Zu 2 pulverized with CeC1 3 , it is dried at 110 ° ⁇ and it is heated at the temperature of 500 ° ⁇ for 2 hours.
  • Example 12 is similar to Example 4 with the exception that the reaction takes 12 hours in the case of 0.5 g of ⁇ / ⁇ ⁇ ⁇ g (1 wt.% ⁇ ). ⁇ a ⁇ aliza ⁇ g ⁇ vya ⁇ ⁇ u ⁇ em ⁇ i ⁇ i ⁇ g ⁇ 2 ⁇ as ⁇ v ⁇ m ⁇ 1 ⁇ ( ⁇ 3) 3, susha ⁇ ⁇ i 110 C and ⁇ alivayu ⁇ v ⁇ zdu ⁇ e ⁇ i at 500 ° C ⁇ echenie 2 hours. Table 3
  • Example 13 is similar to Example 5, which is the same as pouring 25 ml of a mixture of cyclohexene and heptane in a volumetric ratio of 1: 1 into the reaction.
  • Example 14 is similar to Example 13 with the exception that, instead of using cyclohexane, use is made of acetone.
  • Example 15 is similar to Example 13 with the exception that, instead of using a cyclohexane, the following is used.
  • Example 16 is similar to Example 13, which is used instead of cycling.
  • Examples 17-22 ⁇ are given in table. 5. These methods show the possibility of reacting with diluted nitrous oxide mixtures.
  • Example 17 anal ⁇ gichen ⁇ ime ⁇ u 1 ⁇ em ⁇ lichiem, ch ⁇ , vmes ⁇ chis ⁇ y za ⁇ isi az ⁇ a in ⁇ ea ⁇ ⁇ dayu ⁇ its mixture with ine ⁇ nym gaz ⁇ m - az ⁇ m in ⁇ y ⁇ ntsen ⁇ atsiya ⁇ 2 ⁇ s ⁇ s ⁇ avlyae ⁇ 70%.
  • the initial pressure in the process ( ⁇ °) is set to 45 atm.
  • Example 18 is similar to Example 17, with an exception, which is an accent
  • Example 19 is similar to Example 18 with the exception that the initial pressure in the process is set to 90 atm. It is produced at 220 ° ⁇ for 12 hours.
  • EXAMPLE 20 is similar to Example 19 with the exception that the accentuation
  • Example 21 is similar to Example 19 with the exception that, in the case of inert gas, instead of nitrogen, it uses argon, and a concentration of ⁇ 2 ⁇ in a mixture of 50%.
  • the initial pressure in the process is set to 30 atm.
  • Example 22 is similar to Example 21 with the exception that, instead of using argon, carbon dioxide is used.
  • Examples 17-22 indicate that a cyclohexane with a high 10 is selectively oxidized by a cyclohexane with a nitrogen oxide diluted with inert gas.
  • the content of ⁇ 2 ⁇ in a mixture with inert gas may vary in wide range, including a decrease in the concentration of nitrogen consumption of 25% or less, which is underestimated
  • examples 15-18 and 19 Table 5
  • the reaction of the oxidation of cyclohexane in cyclohexane in this region is highly efficient.
  • the present invention provides a new process for the production of cyclohexane, based on the reaction of a liquid oxidation of nitrous oxide or its mixture with nitrogen and its mixture.

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

Abstract

L'invention se rapporte à un procédé de production de cyclohexanone. Le procédé selon l'invention est basé sur la réaction d'oxydation en phase liquide de cyclohexane en cyclohexanone à l'aide de l'oxyde d'azote ou de son mélange avec un gaz inerte. L'oxydation est effectuée à une température de 20-350 °C et une pression de l'oxyde d'azote de 0,01-100 atm. Le procédé assure une haute sélectivité aux produits cibles, la sécurité contre le risque d'explosion et se révèle prometteur à des fins industrielles.
PCT/RU2002/000438 2002-03-20 2002-09-30 Procede de production de cyclohexanone WO2003078374A1 (fr)

Priority Applications (2)

Application Number Priority Date Filing Date Title
AU2002335569A AU2002335569A1 (en) 2002-03-20 2002-09-30 Method for producing cyclohexanone
JP2003576383A JP2005528357A (ja) 2002-03-20 2002-09-30 シクロヘキサノンの製造方法

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
RU2002107019 2002-03-20
RU2002107019/04A RU2205175C1 (ru) 2002-03-20 2002-03-20 Способ получения циклогексанона

Publications (1)

Publication Number Publication Date
WO2003078374A1 true WO2003078374A1 (fr) 2003-09-25

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PCT/RU2002/000438 WO2003078374A1 (fr) 2002-03-20 2002-09-30 Procede de production de cyclohexanone

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JP (1) JP2005528357A (fr)
AU (1) AU2002335569A1 (fr)
RU (1) RU2205175C1 (fr)
WO (1) WO2003078374A1 (fr)

Cited By (11)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US7649119B2 (en) 2006-06-29 2010-01-19 Basf Se Method for the production of cyclic ketones
US7692045B2 (en) 2004-09-23 2010-04-06 Basf Aktiengesellschaft Method for purifying and concentrating dinitrogen monoxide
US7714172B2 (en) 2006-06-29 2010-05-11 Basf Se Method for the production of cyclic ketones
US7754172B2 (en) 2005-11-22 2010-07-13 Basf Aktiengesellschaft Method for isolating N2O
US7803971B2 (en) 2004-09-23 2010-09-28 Basf Akiengesellschaft Method for the production of cyclopentanone
WO2012066296A2 (fr) 2010-11-19 2012-05-24 Invista Technologies S.A.R. L. Oxyde de diazote-contenant des liquides ioniques en tant que réactifs chimiques
US8404901B2 (en) 2008-04-02 2013-03-26 Basf Se Process for purifying dinitrogen monoxide
US8420866B2 (en) 2008-12-30 2013-04-16 Basf Se Process for preparing ketones by reacting 1,1-disubstituted olefins with N2O
US8449655B2 (en) 2006-12-11 2013-05-28 Basf Aktiengesellschaft Process for isolating N2O
US8461392B2 (en) 2008-08-29 2013-06-11 Basf Se Process for preparing cyclic ketones
US8808430B2 (en) 2008-04-02 2014-08-19 Basf Se Process for purifying N2O

Families Citing this family (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP5650121B2 (ja) * 2008-11-11 2015-01-07 ビーエーエスエフ ソシエタス・ヨーロピアＢａｓｆ Ｓｅ 環状ジアミンの製造方法
BRPI1012877A2 (pt) * 2009-05-15 2016-04-05 Genomatica Inc organismo para produção de ciclohexanona
RU2618273C1 (ru) * 2015-11-10 2017-05-03 Федеральное государственное бюджетное образовательное учреждение высшего образования "Московский технологический университет " Способ выделения циклогексанона из реакционной смеси вода - ацетонитрил - циклогексен - циклогексанон

Citations (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
SU692826A1 (ru) * 1978-06-12 1979-10-25 Ленинградский Ордена Трудового Красного Знамени Технологический Институт Им. Ленсовета Способ получени циклогексанона
DE3203286A1 (de) * 1981-03-20 1982-12-09 The Agency of Industrial Science and Technology, Tokyo Verfahren zur herstellung von zyklohexanon
EP0340827A1 (fr) * 1988-04-21 1989-11-08 Dsm N.V. Procédé pour la préparation de cyclohexanol et/ou cyclohexanone

Patent Citations (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
SU692826A1 (ru) * 1978-06-12 1979-10-25 Ленинградский Ордена Трудового Красного Знамени Технологический Институт Им. Ленсовета Способ получени циклогексанона
DE3203286A1 (de) * 1981-03-20 1982-12-09 The Agency of Industrial Science and Technology, Tokyo Verfahren zur herstellung von zyklohexanon
EP0340827A1 (fr) * 1988-04-21 1989-11-08 Dsm N.V. Procédé pour la préparation de cyclohexanol et/ou cyclohexanone

Cited By (11)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US7692045B2 (en) 2004-09-23 2010-04-06 Basf Aktiengesellschaft Method for purifying and concentrating dinitrogen monoxide
US7803971B2 (en) 2004-09-23 2010-09-28 Basf Akiengesellschaft Method for the production of cyclopentanone
US7754172B2 (en) 2005-11-22 2010-07-13 Basf Aktiengesellschaft Method for isolating N2O
US7649119B2 (en) 2006-06-29 2010-01-19 Basf Se Method for the production of cyclic ketones
US7714172B2 (en) 2006-06-29 2010-05-11 Basf Se Method for the production of cyclic ketones
US8449655B2 (en) 2006-12-11 2013-05-28 Basf Aktiengesellschaft Process for isolating N2O
US8404901B2 (en) 2008-04-02 2013-03-26 Basf Se Process for purifying dinitrogen monoxide
US8808430B2 (en) 2008-04-02 2014-08-19 Basf Se Process for purifying N2O
US8461392B2 (en) 2008-08-29 2013-06-11 Basf Se Process for preparing cyclic ketones
US8420866B2 (en) 2008-12-30 2013-04-16 Basf Se Process for preparing ketones by reacting 1,1-disubstituted olefins with N2O
WO2012066296A2 (fr) 2010-11-19 2012-05-24 Invista Technologies S.A.R. L. Oxyde de diazote-contenant des liquides ioniques en tant que réactifs chimiques

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JP2005528357A (ja) 2005-09-22
AU2002335569A1 (en) 2003-09-29
RU2205175C1 (ru) 2003-05-27

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