WO2021048365A1 - Procédé de fabrication d'un cyclohexane carbonitrile substitué par alkyle - Google Patents

Procédé de fabrication d'un cyclohexane carbonitrile substitué par alkyle Download PDF

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Publication number
WO2021048365A1
WO2021048365A1 PCT/EP2020/075485 EP2020075485W WO2021048365A1 WO 2021048365 A1 WO2021048365 A1 WO 2021048365A1 EP 2020075485 W EP2020075485 W EP 2020075485W WO 2021048365 A1 WO2021048365 A1 WO 2021048365A1
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WIPO (PCT)
Prior art keywords
process according
hydrogen peroxide
alkyl substituted
cyclohexanecarbonitrile
solvent
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PCT/EP2020/075485
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English (en)
Inventor
Karol Lorent
Original Assignee
Solvay Sa
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Publication date
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Publication of WO2021048365A1 publication Critical patent/WO2021048365A1/fr

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    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
    • C01B15/00—Peroxides; Peroxyhydrates; Peroxyacids or salts thereof; Superoxides; Ozonides
    • C01B15/01—Hydrogen peroxide
    • C01B15/022—Preparation from organic compounds
    • C01B15/023—Preparation from organic compounds by the alkyl-anthraquinone process
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C253/00—Preparation of carboxylic acid nitriles
    • C07C253/30—Preparation of carboxylic acid nitriles by reactions not involving the formation of cyano groups
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C255/00—Carboxylic acid nitriles
    • C07C255/45—Carboxylic acid nitriles having cyano groups bound to carbon atoms of rings other than six-membered aromatic rings
    • C07C255/46—Carboxylic acid nitriles having cyano groups bound to carbon atoms of rings other than six-membered aromatic rings to carbon atoms of non-condensed rings

Definitions

  • the present invention relates to a process for manufacturing an alkyl substituted cyclohexanecarbonitrile, to a specific alkyl substituted cyclohexanecarbonitrile and to its use as solvent in the manufacture of an aqueous hydrogen peroxide solution.
  • Hydrogen peroxide is one of the most important inorganic chemicals to be produced worldwide. Its industrial applications include textile, pulp and paper bleaching, organic synthesis (propylene oxide), the manufacture of inorganic chemicals and detergents, environmental and other applications.
  • Synthesis of hydrogen peroxide is predominantly achieved by using the Riedl-Pfleiderer process (originally disclosed in U.S. Pat. Nos. 2,158,525 and 2,215,883), also called anthraquinone loop process or AO (auto-oxidation) process.
  • Riedl-Pfleiderer process originally disclosed in U.S. Pat. Nos. 2,158,525 and 2,215,883
  • AO auto-oxidation
  • This well-known cyclic process makes use typically of the auto-oxidation of at least one alkylanthrahydroquinone and/or of at least one tetrahydroalkylanthrahydroquinone, most often 2-alkylanthraquinone, to the corresponding alkylanthraquinone and/or tetrahydroalkylanthraquinone, which results in the production of hydrogen peroxide.
  • the first step of the AO process is the reduction in an organic solvent (generally a mixture of solvents) of the chosen quinone (alkylanthraquinone or tetrahydroalkylanthraquinone) into the corresponding hydroquinone
  • alkylanthrahydroquinone or tetrahydroalkylanthrahydroquinone using hydrogen gas and a catalyst.
  • the mixture of organic solvents, hydroquinone and quinone species (working solution, WS) is then separated from the catalyst and the hydroquinone is oxidized using oxygen, air or oxygen-enriched air thus regenerating the quinone with simultaneous formation of hydrogen peroxide.
  • the organic solvent of choice is typically a mixture of two types of solvents, one being a good solvent of the quinone derivative (generally a non-polar solvent for instance a mixture of aromatic compounds) and the other being a good solvent of the hydroquinone derivative (generally a polar solvent for instance a long chain alcohol or an ester). Hydrogen peroxide is then typically extracted with water and recovered in the form of a crude aqueous hydrogen peroxide solution, and the quinone is returned to the hydrogenator to complete the loop.
  • DIBC di-isobutyl-carbinol
  • ETQH the reduced form of ETQ
  • ETQ the reduced form of ETQ
  • ETQ the reduced form of ETQ
  • ETQ the corresponding tetrahydroalkylanthraquinone
  • ETQ the corresponding tetrahydroalkylanthraquinone
  • ETQ is hydrogenated in ETQH to provide H202 after oxidation.
  • the quantity of EQH produced is marginal in regards of ETQH. It means that the productivity of the process is directly proportional to the amount of ETQH produced.
  • the reasoning is the same for a process working with AQ or BQ instead of EQ.
  • the hydrogenated quinone solubility issue is known from prior art and some attempts were made to solve it.
  • the present invention relates to a process for manufacturing an alkyl substituted cyclohexanecarbonitrile from the a, b- unsaturated cyclohexenone 3,3,5-trimethylcyclohex-2-enone also called isophorone, said process comprising the following steps:
  • the present invention also relates to a process for manufacturing an alkyl substituted cyclohexanecarbonitrile from cyanoisophorone, said process comprising the following steps:
  • said process comprising the additional step of synthesizing the cyanoisophorone through cyanation of isophorone.
  • the alkyl substituted cyclohexanecarbonitrile that can be obtained by the process according to the invention comprises 4 substituents namely: 3 methyl groups coming from the (cyano)isophorone and the alkyl group coming from the organometallic compound, which preferably is a methyl or an ethyl group, more preferably a methyl group.
  • the preferred alkyl substituted cyclohexane carbonitrile that can be obtained in the frame of the invention is 1, 3,3,5- tetramethyl cyclohexanecarbonitrile (Cl 1G).
  • An advantage of the process according to the invention is to start from a cheap and widely available chemical namely either isophorone which is produced on a multi-thousand ton scale by basic or acid catalysed condensation of acetone; or IPN which is also widely available on the market especially in China.
  • Cyanation preferably takes place in a polar solvent like DMF, DMSO or sulfolane.
  • the reaction temperature preferably is from 50 to 150°C, preferably between 100 and 140°C, most preferably about 120°C.
  • the reaction generally happens at a pressure from atmospheric pressure up till 10 bar, though preferably at atmospheric pressure and until full conversion is reached.
  • cyanation can take place in a non-polar organic solvent like toluene, at lower temperature, typically from -10°C until ambient temperature, preferably between 0 and 20°C.
  • the organometallic compound that can be used to transform the ketone group into a ternary alcohol can be a Grignard reagent (i.e. an organo-Mg compound), DMZ (DiMethylZinc)...
  • a Grignard reagent is preferred, more particularly methylMgBr or methylMgCl.
  • the reaction preferably takes place in an ether solvent (THF or methyl THF for instance), in anhydrous conditions.
  • the reaction temperature preferably is below 0°C.
  • the reaction is advantageously performed at atmospheric pressure.
  • the step of reducing the alcohol in order to obtain the alkyl substituted cyclohexanecarbonitrile preferably uses an organosilane reducing agent like Et3SiH, A1C13, TiC14 or Boron trifluoride etherate (strictly boron trifluoride diethyl etherate, or boron trifluoride-ether complex) preferably assisted by TFA (TriFluoroAcetic Acid).
  • the reaction temperature preferably is from 20 to 100°C, more preferably from 30 to 80°C, most preferably about 50°C.
  • the reaction if preferably conducted at atmospheric pressure and can be conducted solvent free or in a polar solvent like DCM or DCE.
  • the present invention also concerns a specific alkyl substituted cyclohexanecarbonitrile which can be obtained by the above described process namely compound Cl 1G described above. The synthesis of this compound has not been reported yet in literature. Finally, the present invention also relates to a process for manufacturing hydrogen peroxide comprising the following steps:
  • a working solution which comprises an alkylanthraquinone and/or tetrahydroalkylanthraquinone and a mixture of a non-polar organic solvent and a polar organic solvent;
  • alkylanthraquinone is intended to denote a 9,10-anthraquinone substituted in position 1, 2 or 3 with at least one alkyl side chain of linear or branched aliphatic type comprising at least one carbon atom. Usually, these alkyl chains comprise less than 9 carbon atoms and, preferably, less than 6 carbon atoms.
  • alkylanthraquinones examples include ethylanthraquinones like 2- ethylanthraquinone (EQ), 2-/.vopropylanthraquinone, 2 -sec- and 2-tert- butylanthraquinone (BQ), 1,3-, 2,3-, 1,4- and 2,7-dimethylanthraquinone, amylanthraquinones (AQ) like 2 -iso- and 2-/er/-amylanthraquinone and mixtures of these quinones.
  • EQ 2- ethylanthraquinone
  • BQ 2-tert- butylanthraquinone
  • AQ amylanthraquinones
  • tetrahydroalkylanthraquinone is intended to denote the 9, 10- tetrahydroquinones corresponding to the 9,10-alkylanthraquinones specified above.
  • EQ and AQ they respectively are designated by ETQ and ATQ, their reduced forms (tetrahydroalkylanthrahydroquinones) being respectively ETQH and ATQH.
  • an AQ or EQ is used, the latter being preferred.
  • the polarity of the solvent mixture is preferably not too high.
  • the non-polar solvent preferably is an aromatic solvent or a mixture of aromatic solvents.
  • Aromatic solvents are for instance selected from benzene, toluene, xylene, /cvV-butylbenzene, trimethylbenzene, tetramethylbenzene, naphthalene, methylnaphthalene mixtures of polyalkylated benzenes, and mixtures thereof.
  • the commercially available aromatic hydrocarbon solvent of type 150 from the Solvesso® series (or equivalent from other supplier) gives good results. S-150 (Solvesso®-150; CAS no.
  • Solvesso® aromatic hydro- carbons are available in three boiling ranges with varying volatility, e.g. with a distillation range of 165-181°C, of 182-207 °C or 232-295 °C. They may be obtained also naphthalene reduced or as ultra-low naphthalene grades.
  • the hydrogenation reaction takes place in the presence of a catalyst (like for instance the one object of WO 2015/049327 in the name of the Applicant) and as for instance described in WO 2010/139728 also in the name of the applicant (the content of both references being incorporated by reference in the present application).
  • a catalyst like for instance the one object of WO 2015/049327 in the name of the Applicant
  • the hydrogenation is conducted at a temperature of at least 45°C and preferably up to 120°C, more preferably up to 95°C or even up to 80°C only.
  • the hydrogenation is conducted at a pressure of from 0.2 to 5 bar.
  • Hydrogen is typically fed into the vessel at a rate of from 650 to 750 normal m3 per ton of hydrogen peroxide to be produced.
  • the oxidation step may take place in a conventional manner as known for the AO-process.
  • Typical oxidation reactors known for the anthraquinone cyclic process can be used for the oxidation.
  • Bubble reactors, through which the oxygen-containing gas and the working solution are passed co-currently or counter-currently, are frequently used.
  • the bubble reactors can be free from internal devices or preferably contain internal devices in the form of packing or sieve plates.
  • Oxidation can be performed at a temperature in the range from 30 to 70° C., particularly at 40 to 60° C. Oxidation is normally performed with an excess of oxygen, so that preferably over 90%, particularly over 95%, of the alkyl anthrahydroquinones contained in the working solution in hydroquinone form are converted to the quinone form.
  • the hydrogen peroxide formed is separated from the working solution generally by means of an extraction step, for example using water, the hydrogen peroxide being recovered in the form of a crude aqueous hydrogen peroxide solution.
  • the working solution leaving the extraction step is then recycled into the hydrogenation step in order to recommence the hydrogen peroxide production cycle, eventually after having been treated/regenerated.
  • the crude aqueous hydrogen peroxide solution is washed several times i.e. at least two times consecutively or even more times as required to reduce the content of impurities at a desired level.
  • washing is intended to denote any treatment, which is well known in the chemical industry (as disclosed in GB841323A, 1956 (Laporte), for instance), of a crude aqueous hydrogen peroxide solution with an organic solvent which is intended to reduce the content of impurities in the aqueous hydrogen peroxide solution.
  • This washing can consist, for example, in extracting impurities in the crude aqueous hydrogen peroxide solution by means of an organic solvent in apparatuses such as centrifugal extractors or liquid/liquid extraction columns, for example, operating counter-current wise.
  • Liquid/liquid extraction columns are preferred.
  • the liquid/liquid extraction columns columns with random or structured packing (like Pall rings for instance) or perforated plates are preferred. The former are especially preferred.
  • a chelating agent can be added to the washing solvent in order to reduce the content of given metals.
  • an organophosphorus chelating agent can be added to the organic solvent as described in the above captioned patent application EP 3052439 in the name of the Applicant, the content of which is incorporated by reference in the present application.
  • the expression "crude aqueous hydrogen peroxide solution” is intended to denote the solutions obtained directly from a hydrogen peroxide synthesis step or from a hydrogen peroxide extraction step or from a storage unit.
  • the crude aqueous hydrogen peroxide solution can have undergone one or more treatments to separate out impurities prior to the washing operation according to the process of the invention. It typically has an H202 concentration within the range of 30- 50% by weight.
  • the solvents of the invention make it is possible to achieve a higher solubility and thus there is less polar solvent needed to achieve a higher partition coefficient. With this higher partition coefficient it is possible to reduce the capex (capital expenditure) required for the extraction sector.
  • the solvents of the invention are particularly suitable for the manufacture of hydrogen peroxide by the AO-process wherein said process has a production capacity of hydrogen peroxide of up to 100 kilo tons per year (ktpa).
  • said process is a small to medium scale AO-process operated with a production capacity of hydrogen peroxide of up to 50 kilo tons per year (ktpa), and more preferably with a production capacity of hydrogen peroxide of up to 35 kilo tons per year (ktpa), and in particular a production capacity of hydrogen peroxide of up to 20 kilo tons per year (ktpa).
  • the dimension ktpa (kilo tons per annum) relates to metric tons.
  • a particular advantage of such a small to medium scale AO-process is that the hydrogen peroxide can be manufactured in a plant that may be located at any, even remote, industrial end user site and the solvents of the invention are therefore especially suitable. It is namely so that since their partition coefficient is more favourable, less emulsion is observed in the process and a purer H202 solution can be obtained (namely containing less TOC) and this for a longer period of time compared to when solvents known from prior art are used.
  • the working solution is regenerated either continuously or intermittently, based on the results of a quality control, regeneration meaning conversion of certain degradates, like epoxy or anthrone derivatives, back into useful quinones.
  • the solvents of the invention are favourable because the quality of the H202 solution can be maintained within the specifications namely in terms of TOC for a longer period of time.
  • Step 1 Synthesis of IsoPhorone Nitrile (IPN): In a 21 jacketed reactor fitted with mechanical stirring, thermostatically controlled at 15-10°C,
  • the aqueous phase was extracted twice with 300 ml of MTBE and the organic phase was washed with 300 ml of water and then with 300 ml of water saturated with NaCl (26%). The organic phase was then dried over Mg sulfate and concentrated under vacuum.
  • the medium was stirred for one hour at -40 ° C.
  • the cold medium was poured onto ice (300 g) and 20 ml of concentrated HC1 were added.
  • the medium was diluted with 350 ml of MTBE.
  • the organic phase is set aside.
  • the medium was then poured into 250 ml of water; the organic phase was set aside and the aqueous phase extracted with 200 ml of DCM, generating a second organic phase.

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

Abstract

L'invention concerne un procédé de fabrication d'un cyclohexanecarbonitrile substitué par alkyle, ledit procédé comprenant les étapes suivantes : - mise en réaction de la cyanoisophorone avec un composé organométallique comprenant un groupe alkyle pour transformer la fraction cétone en son alcool correspondant ; - réduction de l'alcool pour obtenir le cyclohexane carbonitrile substitué par alkyle.
PCT/EP2020/075485 2019-09-11 2020-09-11 Procédé de fabrication d'un cyclohexane carbonitrile substitué par alkyle WO2021048365A1 (fr)

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
EP19196600 2019-09-11
EP19196600.1 2019-09-11

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WO2021048365A1 true WO2021048365A1 (fr) 2021-03-18

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Citations (13)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US2158525A (en) 1935-10-10 1939-05-16 Ig Farbenindustrie Ag Production of hydrogen peroxide
US2215883A (en) 1937-04-07 1940-09-24 Walter H Duisberg Production of hydrogen peroxide
GB841323A (en) 1956-11-15 1960-07-13 Laporte Chemical Improvements in or relating to the manufacture of hydrogen peroxide
US3617219A (en) 1969-06-03 1971-11-02 Ppg Industries Inc Purification of hydrogen peroxide
US4299775A (en) 1979-10-26 1981-11-10 Pcuk Produits Chimiques Ugine Kuhlmann Process for the preparation of 3-cyano-3,5,5-trimethylcyclohexanone
EP0529723A1 (fr) 1991-08-27 1993-03-03 SOLVAY INTEROX (Société Anonyme) Procédé pour l'obtention de solutions aqueuses de peroxyde d'hydrogène
EP0965562A1 (fr) 1998-06-18 1999-12-22 SOLVAY (Société Anonyme) Procédé et installation pour la fabrication d'une solution aqueuse de peroxyde d'hydrogène et solution aqueuse de peroxyde d'hydrogène
WO2010011010A1 (fr) * 2008-07-22 2010-01-28 Dc Chemical Co., Ltd. Procédé et composition pour la préparation de peroxyde d'hydrogène
WO2010109011A1 (fr) * 2009-03-27 2010-09-30 Solvay Sa Procédé de production de peroxyde d'hydrogène
WO2010139728A1 (fr) 2009-06-05 2010-12-09 Solvay Sa Procédé et dispositif d'extraction de liquide d'un mélange multiphase
WO2011094953A1 (fr) * 2010-02-08 2011-08-11 F. Hoffmann-La Roche Ag Composés pour le traitement et la prévention de la grippe
WO2013053617A1 (fr) * 2011-10-11 2013-04-18 Solvay Sa Procédé pour la production de peroxyde d'hydrogène
WO2015049327A1 (fr) 2013-10-02 2015-04-09 Solvay Sa Procédé de fabrication d'une solution aqueuse purifiée de peroxyde d'hydrogène

Patent Citations (15)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US2158525A (en) 1935-10-10 1939-05-16 Ig Farbenindustrie Ag Production of hydrogen peroxide
US2215883A (en) 1937-04-07 1940-09-24 Walter H Duisberg Production of hydrogen peroxide
GB841323A (en) 1956-11-15 1960-07-13 Laporte Chemical Improvements in or relating to the manufacture of hydrogen peroxide
US3617219A (en) 1969-06-03 1971-11-02 Ppg Industries Inc Purification of hydrogen peroxide
US4299775A (en) 1979-10-26 1981-11-10 Pcuk Produits Chimiques Ugine Kuhlmann Process for the preparation of 3-cyano-3,5,5-trimethylcyclohexanone
EP0529723A1 (fr) 1991-08-27 1993-03-03 SOLVAY INTEROX (Société Anonyme) Procédé pour l'obtention de solutions aqueuses de peroxyde d'hydrogène
EP0965562A1 (fr) 1998-06-18 1999-12-22 SOLVAY (Société Anonyme) Procédé et installation pour la fabrication d'une solution aqueuse de peroxyde d'hydrogène et solution aqueuse de peroxyde d'hydrogène
WO2010011010A1 (fr) * 2008-07-22 2010-01-28 Dc Chemical Co., Ltd. Procédé et composition pour la préparation de peroxyde d'hydrogène
WO2010109011A1 (fr) * 2009-03-27 2010-09-30 Solvay Sa Procédé de production de peroxyde d'hydrogène
WO2010139728A1 (fr) 2009-06-05 2010-12-09 Solvay Sa Procédé et dispositif d'extraction de liquide d'un mélange multiphase
WO2011094953A1 (fr) * 2010-02-08 2011-08-11 F. Hoffmann-La Roche Ag Composés pour le traitement et la prévention de la grippe
WO2011095576A1 (fr) 2010-02-08 2011-08-11 F. Hoffmann-La Roche Ag Composés pour le traitement et la prévention de la grippe
WO2013053617A1 (fr) * 2011-10-11 2013-04-18 Solvay Sa Procédé pour la production de peroxyde d'hydrogène
WO2015049327A1 (fr) 2013-10-02 2015-04-09 Solvay Sa Procédé de fabrication d'une solution aqueuse purifiée de peroxyde d'hydrogène
EP3052439A1 (fr) 2013-10-02 2016-08-10 Solvay SA Procédé de fabrication d'une solution aqueuse purifiée de peroxyde d'hydrogène

Non-Patent Citations (3)

* Cited by examiner, † Cited by third party
Title
CHEMICAL ABSTRACTS, Columbus, Ohio, US; abstract no. 64742-94-5
DISCHINO ET AL., JOURNAL OF LABELLED COMPOUNDS AND RADIOPHARMACEUTICALS, vol. 42, 1999, pages 965 - 974
SHIVE ET AL., JACS, vol. 64, 1942, pages 385 - 389

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