[go: up one dir, main page]

WO2011095563A1 - Procédé catalytique pour l'ammoximation de composés carbonyles - Google Patents

Procédé catalytique pour l'ammoximation de composés carbonyles Download PDF

Info

Publication number
WO2011095563A1
WO2011095563A1 PCT/EP2011/051600 EP2011051600W WO2011095563A1 WO 2011095563 A1 WO2011095563 A1 WO 2011095563A1 EP 2011051600 W EP2011051600 W EP 2011051600W WO 2011095563 A1 WO2011095563 A1 WO 2011095563A1
Authority
WO
WIPO (PCT)
Prior art keywords
process according
alkyl
catalytic component
catalyst
carbonyl compound
Prior art date
Legal status (The legal status 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 status listed.)
Ceased
Application number
PCT/EP2011/051600
Other languages
English (en)
Inventor
Nirappurackal Raveendran Shiju
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
Universiteit Van Amsterdam
Original Assignee
Universiteit Van Amsterdam
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
Priority claimed from US12/700,280 external-priority patent/US8278487B2/en
Priority claimed from EP10152633A external-priority patent/EP2354119A1/fr
Application filed by Universiteit Van Amsterdam filed Critical Universiteit Van Amsterdam
Priority to KR1020127022587A priority Critical patent/KR20120123117A/ko
Priority to CN201180008537.7A priority patent/CN103025708B/zh
Priority to JP2012551626A priority patent/JP2013518855A/ja
Publication of WO2011095563A1 publication Critical patent/WO2011095563A1/fr
Anticipated expiration legal-status Critical
Ceased legal-status Critical Current

Links

Classifications

    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C249/00—Preparation of compounds containing nitrogen atoms doubly-bound to a carbon skeleton
    • C07C249/04—Preparation of compounds containing nitrogen atoms doubly-bound to a carbon skeleton of oximes
    • 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
    • B01J23/00—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00
    • B01J23/16—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of arsenic, antimony, bismuth, vanadium, niobium, tantalum, polonium, chromium, molybdenum, tungsten, manganese, technetium or rhenium
    • B01J23/20—Vanadium, niobium or tantalum
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C251/00—Compounds containing nitrogen atoms doubly-bound to a carbon skeleton
    • C07C251/32—Oximes

Definitions

  • the present invention pertains to a catalytic process for the ammoximation of carbonyl compounds to form oximes using a catalyst .
  • Oximes in general, are important chemical intermediates.
  • a particularly important component in this respect is
  • cyclohexanone oxime which is a precursor for ⁇ -caprolactam, the monomer for nylon-6.
  • Other important oximes include cyclododecanone oxime, salicylaldoxime, and acetophenone oxime.
  • US 4,745,221 describes a catalytic process for preparing cyclohexanone oxime by reacting cyclohexanone with NH 3 and H 2 O 2 in the liquid phase in the presence of a catalyst comprising titanium-silicalite.
  • EP347926 describes a catalytic process for the manufacture of oximes from carbonyl compounds using as catalyst a solid composition consisting of silicon, titanium, and oxygen, which composition is an amorphous solid. The best results are obtained when the reaction is carried out in t-butanol or cyclohexanol .
  • titanium silicalite is a specialty chemical requiring a specified synthesis route which is complex and difficult.
  • t-Butanol and cyclohexanol are less attractive as solvents from an
  • GB1092899 describes a process for the ammoximation of cyclohexanone with ammonia and hydrogen peroxide in the liquid phase using a catalyst selected from phospotungstic acid, silicotungstic acid, borotungstic acid,
  • WO93/08160 describes an ammoximation reaction using a metal-peroxo catalyst. These catalysts are generally homogeneous catalysts dissolved in the reaction medium, which need to be recovered.
  • the present invention provides such a process.
  • a catalyst is used which requires no complex and difficult synthesis methods or post- treatments, and which shows high activity also in the
  • the present invention thus pertains to a process for
  • the catalyst comprises a catalytic component selected from the oxides of metals of group 5 and group 6, said catalytic component comprising at least 50 wt.% of niobium, calculated as oxide.
  • the reaction can be carried out in aqueous media.
  • the catalyst is a heterogeneous catalyst which does not dissolve in the reaction medium. It can therefore easily be separated from the reaction product and recycled if so desired.
  • the catalyst used in the present invention comprises a catalytic component selected from the oxides of metals of group 5 and group 6, said catalytic component comprising at least 50 wt.% of niobium, calculated as oxide.
  • the catalyst may comprise other catalytic components, viz., oxides of metals of other groups of the periodic table, such as group 4, and group 7-14.
  • the total of catalytic components present in the catalyst consist for at least 50 wt.% of oxides of metals of group 5 and group 6, more in particular for at least 70 wt.%, still more in particular for at least 90 wt.%.
  • the catalytic component consists essentially of oxides of metals of groups 5 and 6, wherein the wording consists essentially of means that other components are only present at contaminant levels.
  • the catalytic component selected from the oxides of metals of group 5 and group 6 comprises at least 50 wt.% of niobium, calculated as oxide. If so desired, other group 5 metals, e.g., vanadium may also be present.
  • chromium, molybdenum, and tungsten or combinations thereof is preferred, while the use of tungsten is particularly preferred.
  • the catalytic component selected from the oxides of metals of group 5 and group 6 comprises at least 70 wt.% of group 5 metal components, calculated as oxide, more in particular at least 80 wt.%, still more in particular at least 90 wt.%.
  • the catalytic component comprises at least 70 wt.% of niobium, calculated as oxide, more in particular at least 80 wt.%, still more in particular at least 90 wt.%. Still more in particular, the catalytic component may consist essentially of group 5 metal
  • the catalytic component selected from the oxides of metals of group 5 and group 6 comprises both niobia and vanadia, in particular at least 50 wt.% of niobium, calculated as oxide, more in particular at least 70 wt.%, still more in particular at least 90 wt.%, and up to 50 wt.%, in particular up to 30 wt.%, more in particular up to 10 wt.% of vanadia.
  • the catalyst used in the process according to the invention may have the following physical properties:
  • the surface area (determined via B.E.T) is generally at least 10 mVg, preferably at least 20 m 2 /g. In one embodiment, the catalyst has a surface area of at least 80 m 2 /g. A catalyst with a higher surface area will generally be more active.
  • the upper limit of the surface area is not critical to the present invention. As a general value, an upper limit of 500 m 2 /g may be mentioned.
  • the pore volume (determined via N 2 adsorption) is generally at least 0.05 cm 3 /g, preferably at least 0.10 cm 3 /g. If the pore volume is too low, the activity of the catalyst may decrease.
  • the upper limit of the pore volume is not critical to the present invention. As a general value, an upper limit of 2 cm 3 /g may be mentioned.
  • the average pore diameter (determined via N 2 adsorption) is generally at least 1 nm, preferably at least 2 nm. A range of 3-15 nm may be mentioned as preferred, more in particular 4- 10 nm.
  • the catalyst may be manufactured by processes known in the art.
  • the catalyst is manufactured by a process in which salts of the relevant metals are subjected to a calcination step in the presence of oxygen, which results in formation of the corresponding oxides.
  • the calcination step generally is carried out at a temperature of 300-900 °C, in particular at a temperature of 400-800 °C.
  • commercially available oxides are used as starting material. They may be used directly, but it may be preferred to subject them to a calcination step, for example to remove contaminants, or to change the catalyst morphology. Suitable calcination conditions include
  • the calcination takes place at a temperature of 350 to 450 °C.
  • Calcination time is generally not critical, and will depend on calcination temperature. A period of 10 minutes to 12 hours is generally suitable; 2-5 h is more preferable.
  • the catalytic component may or may not be present on a carrier material.
  • Suitable carrier materials are known in the art and comprise, for example, particles comprising one or more of silica or alumina or activated carbon. If the
  • catalytic component is present on a carrier, it may, for example, be present in an amount of 2-90 wt.%, calculated as oxide, more in particular in an amount of 20-90 wt.%, still more in particular in an amount of 40-90 wt.%.
  • the specific amount will depend on the selected process configuration.
  • Catalysts containing a carrier material may be manufactured by processes known in the art.
  • a suitable process comprises the steps of combining a precursor for a metal oxide with a carrier material, and calcining the material to convert the precursor into the corresponding oxide.
  • Suitable precursors are for example metal salts.
  • the step of combining a precursor for a metal oxide with a carrier material comprises contacting particles of a carrier material with an impregnation solution containing metal salts.
  • precursor for a metal oxide with a carrier material comprises comulling or otherwise mixing a precursor for a carrier material, e.g., aluminium trihydrate or aluminium monohydrate with a metal oxide, or a precursor for a metal oxide, followed by subjecting the combination to a calcination step to convert the precursor for the carrier material into an oxide.
  • a shaping step may be carried out before the precursor for the carrier material is converted into an oxide, e.g., via extrusion, tabletting, or other means known in the art. It is also possible to process the material in powder form.
  • ketones or aldehydes are ketones or aldehydes.
  • Suitable ketones generally are ketones of the formula R1-CO- R2, wherein R1 and R2 may be the same or different and are selected from alkyl, aryl, cycloalkyl, and heterocyclic aryl groups, optionally substituted with hydroxyl, alkyl, aryl, cycloalkyl, and heterocyclic aryl groups, R1 and R2 having 1- 20 carbon atoms, wherein R1 and R2 may be connected to form a cyclic alkyl or (hetero)aryl compound.
  • preferred ketones are cyclic alkylketones wherein the ring contains 5-12 carbon atoms, and wherein the ring may
  • ketones are cyclopentanone,
  • cyclohexanone cycloheptanone, cyclooctanone, t-butyl- cyclohexanone, and cyclododecanone.
  • ketones are ketones of the formula R1-CO-R2, wherein R1 and R2 are selected from C1-C6 alkyl and phenyl.
  • suitable ketones within this group include acetone, methyl-ethyl-ketone, acetophenone, and benzophenone .
  • Suitable aldehydes generally are aldehydes of the formula R3- CHO, wherein R3 is selected from alkyl, aryl, cycloalkyl, and heterocyclic aryl groups, optionally substituted with
  • R3 is selected from optionally substituted phenyl and C1-C10 alkyl.
  • preferred aldehydes may be mentioned benzaldehyde, p-tolualdehyde, and salycylaldehyde.
  • Preferred oximes that may be manufactured using the process according to the invention are the oximes corresponding to the preferred ketones and aldehydes mentioned above.
  • the following compounds may be mentioned cyclohexanone oxime, cyclododecanone oxime,
  • salicylaldoxime and acetophenone oxime, with cyclohexanone oxime being particularly preferred.
  • the reaction takes place in the liquid phase. This means that at least the carbonyl compound is in the liquid phase during the reaction.
  • the reaction is generally carried out in the presence of a liquid medium.
  • the liquid medium helps to ensure good contact between the various reactants, for example by providing a solvent for the H 2 0 2 and NH 3 .
  • the liquid medium may also help to prevent the formation of by-products by diluting the reactants.
  • the liquid medium may be selected from water, organic
  • liquid medium comprising water is preferred for environmental reasons. Particularly preferred is the use of a medium comprising at least 50 wt.% of water, preferably at least 70 wt.% of water, more preferably at least 90 wt.% of water.
  • the reaction is carried out at a temperature which is selected such that the carbonyl compound and the reaction medium are present in the liquid phase.
  • the upper limit is governed by the boiling point of these compounds under reaction conditions.
  • the use of a higher reaction temperature leads to an increased reaction velocity, but also to
  • the reaction is carried out at a temperature of at most 100°C, in particular at most 90 °C, more in particular at most 80 °C. In one embodiment, the reaction is carried out at a
  • the reaction preferably is carried out at atmospheric
  • a pressure of up to 5 bar may be applied to help to increase the concentration of NH 3 in the reaction medium.
  • the molar ratio between carbonyl compound and N3 ⁇ 4 generally is in the range of 1:5 to 5:1, in particular in the range of 1:2 to 2:1, more in particular in the range of 1:1 to 1:2.
  • the molar ratio between NH 3 and H 2 O 2 is generally in the range of 1:5 to 5:1, preferably in the range of 1:2 to 2:1. It may be preferred for the ratio between NH 3 and H 2 O 2 to be at least 1:1, more preferably at least 1,5:1, to prevent the
  • the process can be carried out in batch mode or in a continuous mode. Where the process is a batch process, it is preferred to use 0.1-100 parts per weight of catalytic component (calculated as oxide) , in particular 1-20 parts per weight, per 100 parts of carbonyl compound. Where the process is a continuous process, the liquid hourly space velocity of the carbonyl compound preferably is in the range of 0.1-100 kg of carbonyl compound per kg of catalytic component (calculated as oxide) . Expressed in moles, the carbonyl compound/catalyst molar ratio preferably is 50:1 to 2:1.
  • the catalyst may be in the form of a fixed bed, e.g., a trickle bed, an ebullated bed or fluid bed, or finely divided in the reaction medium.
  • the size and shape of the catalyst particle will be selected such that it is suitable for use in the selected process.
  • this generally means a particle diameter in the range of 0.1-15 mm.
  • a catalyst finely divided in the reaction medium this generally means a diameter of 1 to 1000, preferably 1-100 microns.
  • a process wherein the catalyst is finely divided in the reaction medium may be preferred. It is within the scope of the skilled person to select an appropriate process configuration.
  • Example 1 ammoximation of cyclohexanone - influence of catalyst calcination temperature
  • Cyclohexanone was subjected to an ammoximation process as described above.
  • the reaction medium was ethanol.
  • the molar ratio of cyclohexanone:NH 3 :H 2 O 2 was 1:2:2.
  • the molar ratio of cyclohexanone : Nb 2 O 5 was 5:1.
  • the catalyst was commercially available niobia which was subjected to calcination at different temperatures.
  • the starting material was niobia (Nb 2 O 5 ) with a surface area of 123 m 2 /g, a pore volume of 0.19 cm 3 /g, and a an average pore diameter of 5.2 nm.
  • the starting material was subjected to calcination in air for a period of 4 h, at different temperatures. Calcination temperatures and some catalyst properties are given in table
  • the catalyst was niobia calcined at a temperature of 400 °C as described above.
  • the reaction medium was ethanol.
  • the molar ratio of cyclohexanone : ⁇ 3 : ⁇ 2 O 2 was 1:2:2.
  • Example 3 ammoximation of cyclohexanone using various reaction media

Landscapes

  • Chemical & Material Sciences (AREA)
  • Organic Chemistry (AREA)
  • Engineering & Computer Science (AREA)
  • Materials Engineering (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 porte sur un procédé pour la préparation d'une oxime dans lequel un composé carbonyle est amené à réagir dans la phase liquide avec NH3 et H2O2 en présence d'un catalyseur pour former l'oxime correspondante, caractérisé en ce que le catalyseur comprend un composant catalytique choisi parmi les oxydes de métaux du groupe 5 et du groupe 6, ledit composant catalytique comprenant au moins 50 % en poids de niobium, en termes d'oxyde. Le procédé selon l'invention est approprié pour la fabrication de nombreuses oximes, en particulier de cyclohexanone-oxime.
PCT/EP2011/051600 2010-02-04 2011-02-03 Procédé catalytique pour l'ammoximation de composés carbonyles Ceased WO2011095563A1 (fr)

Priority Applications (3)

Application Number Priority Date Filing Date Title
KR1020127022587A KR20120123117A (ko) 2010-02-04 2011-02-03 카보닐 화합물의 암목시메이션을 위한 촉매적 방법
CN201180008537.7A CN103025708B (zh) 2010-02-04 2011-02-03 羰基化合物氨肟化的催化方法
JP2012551626A JP2013518855A (ja) 2010-02-04 2011-02-03 カルボニル化合物をアンモキシム化するための触媒法

Applications Claiming Priority (4)

Application Number Priority Date Filing Date Title
US12/700,280 2010-02-04
EP10152633.3 2010-02-04
US12/700,280 US8278487B2 (en) 2010-02-04 2010-02-04 Catalytic process for the ammoximation of carbonyl compounds
EP10152633A EP2354119A1 (fr) 2010-02-04 2010-02-04 Procédé catalytique pour la production d'oximes de composés carbonyles

Publications (1)

Publication Number Publication Date
WO2011095563A1 true WO2011095563A1 (fr) 2011-08-11

Family

ID=43795053

Family Applications (1)

Application Number Title Priority Date Filing Date
PCT/EP2011/051600 Ceased WO2011095563A1 (fr) 2010-02-04 2011-02-03 Procédé catalytique pour l'ammoximation de composés carbonyles

Country Status (4)

Country Link
JP (1) JP2013518855A (fr)
KR (1) KR20120123117A (fr)
CN (1) CN103025708B (fr)
WO (1) WO2011095563A1 (fr)

Families Citing this family (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN104513220A (zh) * 2013-09-27 2015-04-15 天津尚德药缘科技有限公司 一种4-氨基-6-卤代-3,4-二氢-2,2-二甲基-2h-1-苯并吡喃的制备方法

Citations (6)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
GB1092899A (en) 1966-02-03 1967-11-29 Toa Gosei Chem Ind Process for preparing cyclohexanoneoxime by ammoxidation of cyclohexanone
US3574750A (en) 1966-02-26 1971-04-13 Toa Gosei Chem Ind Process for the production of cyclohexanone oxime
US4745221A (en) 1985-07-10 1988-05-17 Montedipe S.P.A. Catalytic process for preparing cyclohexanone-oxime
EP0347926A2 (fr) 1988-06-23 1989-12-27 ENICHEM S.p.A. Procédé catalytique de préparation d'oximes
WO1993008160A1 (fr) 1991-10-24 1993-04-29 Dsm N.V. Procede de preparation d'une cetoxime
EP1142871A1 (fr) * 1998-12-25 2001-10-10 Mitsubishi Chemical Corporation CATALYSEURS D'OXYDE ET PROCEDE DE PRODUCTION D'$g(e)-CAPROLACTAME A L'AIDE DE CES CATALYSEURS

Patent Citations (6)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
GB1092899A (en) 1966-02-03 1967-11-29 Toa Gosei Chem Ind Process for preparing cyclohexanoneoxime by ammoxidation of cyclohexanone
US3574750A (en) 1966-02-26 1971-04-13 Toa Gosei Chem Ind Process for the production of cyclohexanone oxime
US4745221A (en) 1985-07-10 1988-05-17 Montedipe S.P.A. Catalytic process for preparing cyclohexanone-oxime
EP0347926A2 (fr) 1988-06-23 1989-12-27 ENICHEM S.p.A. Procédé catalytique de préparation d'oximes
WO1993008160A1 (fr) 1991-10-24 1993-04-29 Dsm N.V. Procede de preparation d'une cetoxime
EP1142871A1 (fr) * 1998-12-25 2001-10-10 Mitsubishi Chemical Corporation CATALYSEURS D'OXYDE ET PROCEDE DE PRODUCTION D'$g(e)-CAPROLACTAME A L'AIDE DE CES CATALYSEURS

Also Published As

Publication number Publication date
KR20120123117A (ko) 2012-11-07
CN103025708B (zh) 2015-12-16
CN103025708A (zh) 2013-04-03
JP2013518855A (ja) 2013-05-23

Similar Documents

Publication Publication Date Title
EP0267362B1 (fr) Procédé catalytique de production d'oximes
US8133834B2 (en) Oxidation catalyst
US6514902B1 (en) Method for producing an oxide catalyst for use in producing acrylonitrile or methacrylonitrile from propane or isobutane
US6566555B2 (en) Process for preparing oximes
US6462235B1 (en) Process for production of oximes cocatalyzed by ammonium salts or substituted ammonium salts
JP4285980B2 (ja) オキシムの製造方法
EP1500432A1 (fr) Procede de preparation d'une alumine portant du ruthenium et procede d'oxydation d'un alcool
WO2011095563A1 (fr) Procédé catalytique pour l'ammoximation de composés carbonyles
US8278487B2 (en) Catalytic process for the ammoximation of carbonyl compounds
EP2354119A1 (fr) Procédé catalytique pour la production d'oximes de composés carbonyles
JP4522672B2 (ja) 環状脂肪族オキシムの製造法
EP1748042B1 (fr) Procédé servant à produire de l'acide adipique
JP2001019670A (ja) 転位反応による有機化合物の製造方法
JP4574348B2 (ja) カルボニル化合物のアンモオキシム化法
CN101928231A (zh) 用于制备肟的方法
JP4447255B2 (ja) 環状脂肪族オキシムの製法
TW201304859A (zh) 用於氨肟化羰基化合物之催化方法
JPH03505877A (ja) ３―メチルピリジンの選択的製造のための高温における製造方法
CN102850205A (zh) 一种生产1,2-环己二醇和己二酸的方法
EP0527642B1 (fr) Procédé de préparation simultanée d'un lactone et d'un acide aromatique carboxylique
JP2005015370A (ja) 環状脂肪族オキシムの製造方法
CN105524037B (zh) 一种环己酮氧化的方法
JPH0529378B2 (fr)
CN110128250A (zh) 制备环己酮的方法
JPH0761982A (ja) ラクトン類の製造方法

Legal Events

Date Code Title Description
WWE Wipo information: entry into national phase

Ref document number: 201180008537.7

Country of ref document: CN

121 Ep: the epo has been informed by wipo that ep was designated in this application

Ref document number: 11703647

Country of ref document: EP

Kind code of ref document: A1

WWE Wipo information: entry into national phase

Ref document number: 2012551626

Country of ref document: JP

WWE Wipo information: entry into national phase

Ref document number: 1201003914

Country of ref document: TH

NENP Non-entry into the national phase

Ref country code: DE

ENP Entry into the national phase

Ref document number: 20127022587

Country of ref document: KR

Kind code of ref document: A

122 Ep: pct application non-entry in european phase

Ref document number: 11703647

Country of ref document: EP

Kind code of ref document: A1