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WO1995020560A1 - Procede de production de benzaldehyde - Google Patents

Procede de production de benzaldehyde Download PDF

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Publication number
WO1995020560A1
WO1995020560A1 PCT/NL1994/000020 NL9400020W WO9520560A1 WO 1995020560 A1 WO1995020560 A1 WO 1995020560A1 NL 9400020 W NL9400020 W NL 9400020W WO 9520560 A1 WO9520560 A1 WO 9520560A1
Authority
WO
WIPO (PCT)
Prior art keywords
toluene
process according
reaction mixture
benzaldehyde
metal ion
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/NL1994/000020
Other languages
English (en)
Inventor
Hendricus Johannes Rozie
Maria Louisa Christina Dsinter
Jihad Baka Dakka
Amikam Zoran
Yoel Sasson
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.)
Koninklijke DSM NV
Original Assignee
DSM NV
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 DSM NV filed Critical DSM NV
Priority to AU58926/94A priority Critical patent/AU5892694A/en
Priority to PCT/NL1994/000020 priority patent/WO1995020560A1/fr
Priority to EE9500004A priority patent/EE9500004A/xx
Publication of WO1995020560A1 publication Critical patent/WO1995020560A1/fr
Anticipated expiration legal-status Critical
Ceased legal-status Critical Current

Links

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
    • C07C45/32—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
    • C07C45/34—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 in unsaturated compounds
    • C07C45/36—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 in unsaturated compounds in compounds containing six-membered aromatic rings

Definitions

  • the invention relates to a process for the oxidation of toluene in a liquid phase using an oxygen containing gas at a temperature between 120-200°C and a pressure between 2-50 atm in the presence of a catalyst comprising cobalt or manganese as a metal ion, further comprising bromide.
  • JP-A-50108231 Such a process is described in JP-A-50108231.
  • 4-15 vol.% water should be present in the reaction mixture in order to optimise the selectivity towards benzaldehyde and benzylalcohol.
  • the selectivity to benzaldehyde is about 20%, at 20% conversion.
  • substantial amounts of benzoic acid are formed.
  • the aim of the present invention is achieved by performing the process for the oxidation reaction in such a way that the amount of metal ion is between 0.2 and 5 wt% with respect to the reaction mixture; the molar ratio of bromide : metal ion is between 0.05 and 4 ; and that the reaction mixture further comprises an organic onium compound in a molar ratio with respect to the metal ion of 0.1 to 4, which compound is able to solubilize the metal ion-bromide complex, whereby the oxidation is carried out in such a way that at least 15 wt% of the converted toluene is benzaldehyde by limitation of the conversion of toluene, whereafter the reaction mixture is subjected to a separation step to separate toluene and benzaldehyde, the toluene being recycled to the reaction mixture.
  • the process according to the present invention obviates the need for an aliphatic carboxylic acid as co- solvent. It is preferred that the reaction mixture is essentially free of aliphatic carboxylic acid because this diminishes corrosion and precludes the necessity of additional equipment for recycling said acid. It should be noted that small amounts of e.g. acetic acid and formic acid are present because of side reactions during oxidation. These small amounts to not have a significant effect on the oxidation process.
  • JP-A-56108728 describes the use of a zinc compound in addition to cobalt, bromide and an aliphatic acid.
  • the temperature used according the examples is in general 100°C or lower. Such a low temperature has the disadvantage that reaction products like benzoic acid are not very well soluble. This may lead to difficulties in processing the resulting reaction mixture.
  • higher temperatures cannot be applied since these lead to much lower selectivities of benzaldehyde.
  • US- A-3931330 describes the use of an aliphatic acid, in order to increase the selectivity to benzaldehyde.
  • the process of the present invention gives rise to very little diphenyl-byproducts. This is a great advantage, since the diphenyl-byproducts are rather useless since these are formed in such low amounts that it is too expensive to recover these.
  • Another advantage of the present process is that only a low amount of organic bromide compounds is formed during the process. Thereby, the process circumvents a part of the problems of corrosion.
  • An essential component according to the present invention is an organic onium compound that is able to solubilize the metal ion-bromide complex.
  • the compound comprises 4-60 carbon atoms.
  • the onium compound is an ammonium, sulfonium, phosphonium, arsonium or stibium compound.
  • Very suitable onium compounds are trialkyl, tetraalkyl or aromatic onium compounds.
  • onium compounds examples include tetraethylammonium, tetraethylphosphonium, tetrabut lammoniurn, tetrabut lphosphonium, dimethyldidecylammonium, tetraphenylphosphonium, tetrapropylammonium, tetramethylammonium, trihexylammonium (i.e. protonated trihexylamine) , pyridinium (i.e.
  • N-methyl-pyridinium N,N- dimethylaniline, quinoline, dibenzylbutylsulphonium, diphenylbutylsulphonium, tetraphenylarsonium, triphenylbutylstibinium, and ⁇ -triethylammonium-( ⁇ '- triethylammonium)ethylpropionate.
  • the onium compound can be applied either as neutral compound, as in the case of pyridine, N,N- dimethylaniline or tri-hexylamine, or as onium salt of a cation such as for instance chloride, bromide, fluoride, acetate, propionate, benzoate, hydroxide or hydrogen sulphate.
  • the onium salt can be prepared in situ by reaction of an alkylating agent with an amine or phosphine compound.
  • EP-A-300921 The use of e.g. tetraalkylammonium salts with 17 carbon atoms or more in the oxidation of toluene is known from EP-A-300921.
  • EP-A-300921 describes the oxidation of toluene towards benzoic acid and describes that with the use of the onium salt a higher conversion and selectivity towards benzoic acid is achieved. This is apparent, in particular if cobalt or manganese are used as metal component of the catalyst. It is therefore unexpected, that the use of such an onium salt gives rise to a high selectivity to benzaldehyde at low conversion rates.
  • the catalyst for the oxidation of toluene with an oxygen containing gas comprises cobalt or manganese as a metal ion. Cobalt, manganese, or a mixture of these should be present in the reaction mixture in at least 0.2 wt.%.
  • Cobalt and/or manganese may be combined with other transition metals of groups IB, IIB, VB, VIB, VIIB, VIII of the periodic system, Ce and Th.
  • transition metal it is preferred to use for instance one or more of the metals selected from the group consisting of Cu, Cr , V, Pb, Fe, Ni , Ce, Th, Rh and Mo.
  • the amount is in general higher than 10 ppm, and lower than 5 wt.% with respect to the reaction mixture.
  • the metal ion can be provided as salt of inorganic acids such as for instance chloride, bromide or sulphate, or as salt of an organic acid such as the acetate, octanoate, stearate or benzoate.
  • inorganic acids such as for instance chloride, bromide or sulphate
  • organic acid such as the acetate, octanoate, stearate or benzoate.
  • a further essential component is bromide.
  • the bromide ion can be provided as salt of the metal ion, as part of the onium compound or as a separate component. In the latter case, bromide can be supplied e.g. as NaBr, KBr or HBr .
  • the amounts of the three components are important in order to achieve high selectivity to benzaldehyde.
  • the amount of cobalt and/or manganese should be higher than 0.2 wt.% (relative to the reaction mixture).
  • the amount - in general - will be lower than 5 wt.% because a higher amount generally does not have a positive effect.
  • the amount will be higher than 0.4 wt.% and most preferably, the amount is between 0.4-2 wt.%.
  • the required amount of bromide is related to the amount of metal ion, and the molar ratio bromide : metal ion is generally at least 0.05. Preferably, the molar ratio of bromide relative to the metal ion is higher than 0.2. In general, the molar ratio bromide : metal ion is less than 4, preferably less than 1.5. High amounts of bromide tend to increase corrosion.
  • the amount of onium compound on a molar basis relative to the metal ion is - in general - higher than 0.1, preferably higher than 0.4. In general the amount on molar basis relative to the metal ion is less than 5, and preferably less than 3, since higher amounts do not contribute significantly to a higher selectivity.
  • the amount of onium compound on a molar basis relative to bromide in general is higher than 0.2, and lower than 20.
  • the molar ratio onium compound : bromide is in between 0.5 : 10.
  • the oxygen containing gas generally contains between 3-22 vol.% oxygen, although pure oxygen gas may be used. Generally, air is used as the oxygen containing gas. It might be useful to apply gas with a relatively low amount of oxygen in order to decrease the risk of explosion.
  • the process according to the invention can be performed batchwise, or in a continuous way. Preferable, the process is performed continuously. In the course of the process water is formed as a result of the oxidation reaction. A certain amount of water may be useful in order to solubilize the onium salt. However, the presence of water is not critical.
  • the temperature of the reaction is between 120°C and 200°.
  • the reaction is performed at a temperature higher than 135°C in order to increase the reaction velocity.
  • the temperature preferably is lower than 180°C in order to diminish side reactions.
  • the pressure at which the process is performed is in between 2 and 50 atm (0.2-5 MPa). Preferably (because of the temperature which causes a certain pressure) the pressure is higher than 3 atm. The pressure is preferably lower than 30 atm.
  • the process according the invention can be carried out in a reaction vessel, equipped with a gas- inlet (sparger) and with an off-gas treatment section. Because of the heat evolving from the exothermic oxidation reaction, toluene may evaporate and can be cooled and recirculated, or cooled in a reflux-condensor or handled in another well known way.
  • the reaction is performed in such a way that a substantial part of the toluene remains unreacted, i.e. with a limited substrate conversion.
  • at least 30% (on molar basis) of the toluene remains unreacted, preferably at least 50% and most preferred at least 60% of the toluene remains unreacted.
  • a lower conversion generally leads to a higher selectivity towards benzaldehyde.
  • the reaction is performed in such a way that in a continuous process the continuously withdrawn part of the reaction mixture contains at least 2.5 wt.% benzaldhyde, preferably at least 3 wt.% benzaldehyde and very preferably at least 4 wt.% benzaldehyde.
  • the amount of benzaldehyde will be slightly higher.
  • the resultant reaction mixture or a continuously withdrawn part of the reaction mixture containing mainly toluene, benzaldehyde, benzoic acid, benzyl benzoate, benzylalcohol and catalyst is distilled to separate toluene.
  • the toluene is recycled to the reaction mixture.
  • the benzaldehyde that may be further purified if necessary is obtained by distillation as well.
  • the resulting residue consists mainly of benzoic acid, benzylalcohol, benzylbenzoate and the components of the catalyst. Benzoic acid can be separated, if desired, by destination or crystallisation.
  • Benzylalcohol together with a relatively small amount of benzylformiate and/or benzylacetate, can be separated and purified, or can be recirculated to the reaction mixture for instance together with the catalyst. It is also possible, to separate the catalyst by washing the reaction mixture or a resulting residue with water, at least in these cases where the onium compound is water soluble.
  • the components of the catalyst preferably are used again in the oxidation reaction.
  • the autoclave was heated at 160°C and air at a pressure of 6 atmospheres was introduced at a rate of 1.8 1/min (at standard conditions) for about 90 minutes.
  • reaction mixture (in percentage on molar basis) consisted of 63% toluene, 10% benzaldehyde, 16% benzoic acid, along with small amounts of benzyl alcohol and benzyl benzoate.
  • reaction mixture was separated by distillation at atmospheric pressure. The first fraction was water followed by a fraction at 109-111°C which consisted of the excess of toluene. The toluene was used in further oxidation reactions. The following fraction at 178-179°C consisted of benzaldehyde.
  • the yield of pure benzaldehyde obtained by distillation was 24 g. After 20% conversion of toluene the selectivity to benzaldehyde was about 40 mol%.
  • the autoclave was heated at 160°C and air at a pressure of 20 atmospheres was introduced at a rate of 2 1/min (at standard conditions) for about 80 minutes.
  • a sample was taken to a gas chromatograph and the composition found (on a molar basis without the catalyst) was as follows; 58% toluene; 13% benzaldehyde, 35% benzoic acid, and 4% of a mixture of benzylic alcohol and benzyl benzoate.
  • the toluene was again used in an oxidation reaction.
  • the benzaldehyde was separated by distillation as described in Example I and 33 g was obtained.
  • the condensor was provided with a vessel in which water was separated. Therefore, the amount of water in the reaction mixture was lower than 0.1 wt.%.
  • Example III and experiment A were also performed with a condensor without such vessel, which resulted in an increasing amount of water in the reaction mixture of up to 2 wt.% at 40% conversion of toluene. The presence of this amount did not have significant influence on the reaction rate nor on the selectivity.
  • DDOAB dimethyldioctadecylammoniumbromide
  • Example XII With respect to Example XII, a quantitative analysis appeared not possible due to the high concentration of metal. The results indicated high amounts of benzaldehyde, as in the other examples.

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

Abstract

Procédé d'oxydation de toluène en phase liquide au moyen d'un gaz renfermant de l'oxygène à une température comprise entre 120 et 200 °C et sous une pression comprise entre 2 et 50 atm, en présence d'un catalyseur comportant à titre d'ion métallique du cobalt ou du manganèse, ainsi que du bromure, la quantité d'ion métallique étant de 0,2 à 5 % en poids par rapport au mélange réactionnel, le rapport molaire entre le bromure et l'ion métallique étant compris entre 0,05 et 4, et le mélange réactionnel comportant également un composé onium organique selon un rapport molaire compris entre 0,1 et 4 par rapport à l'ion métallique. Ce composé peut solubiliser le complexe ion métallique-bromure, et l'oxydation s'effectue de telle sorte qu'au moins 15 % en poids du toluène converti est du benzaldéhyde, par limitation de la conversion du toluène. Ensuite, on soumet le mélange réactionnel à une étape de séparation du toluène et du benzaldéhyde, le toluène étant recyclé dans le mélange réactionnel.
PCT/NL1994/000020 1994-01-27 1994-01-27 Procede de production de benzaldehyde Ceased WO1995020560A1 (fr)

Priority Applications (3)

Application Number Priority Date Filing Date Title
AU58926/94A AU5892694A (en) 1994-01-27 1994-01-27 Process for the manufacture of benzaldehyde
PCT/NL1994/000020 WO1995020560A1 (fr) 1994-01-27 1994-01-27 Procede de production de benzaldehyde
EE9500004A EE9500004A (et) 1994-01-27 1995-01-24 Meetod bensaldehüüdi valmistamiseks

Applications Claiming Priority (1)

Application Number Priority Date Filing Date Title
PCT/NL1994/000020 WO1995020560A1 (fr) 1994-01-27 1994-01-27 Procede de production de benzaldehyde

Publications (1)

Publication Number Publication Date
WO1995020560A1 true WO1995020560A1 (fr) 1995-08-03

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PCT/NL1994/000020 Ceased WO1995020560A1 (fr) 1994-01-27 1994-01-27 Procede de production de benzaldehyde

Country Status (3)

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AU (1) AU5892694A (fr)
EE (1) EE9500004A (fr)
WO (1) WO1995020560A1 (fr)

Cited By (6)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US5990357A (en) * 1996-03-20 1999-11-23 Rutgers Kureha Solvents Gmbh Process for the oxidation of isoalkylaromatic hydrocarbons, and catalyst for the execution of the process
CN106699526A (zh) * 2016-11-07 2017-05-24 常州大学 一种2,4‑二氯甲苯连续氧化制备2,4‑二氯苯甲醛的方法
CN106699525A (zh) * 2016-11-07 2017-05-24 常州大学 一种2,3‑二氯甲苯连续氧化制备2,3‑二氯苯甲醛的方法
CN106748684A (zh) * 2016-11-07 2017-05-31 常州大学 一种间氟甲苯连续氧化制备间氟苯甲醛的方法
CN106748685A (zh) * 2016-11-07 2017-05-31 常州大学 一种对氯甲苯连续氧化制备对氯苯甲醛的方法
CN106854142A (zh) * 2016-11-07 2017-06-16 常州大学 一种2,5‑二氯甲苯连续氧化制备2,5‑二氯苯甲醛的方法

Citations (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
GB1291342A (en) * 1969-05-28 1972-10-04 Tenneco Chem Improvements in or relating to the production of benzaldehyde
FR2379500A1 (fr) * 1977-02-02 1978-09-01 Shell Int Research Oxydation de toluenes p-substitues et preparation de benzaldehydes p-substitues
SU789476A1 (ru) * 1978-08-23 1980-12-23 Предприятие П/Я А-7815 Способ получени толуиловых спирта, альдегида, кислоты

Patent Citations (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
GB1291342A (en) * 1969-05-28 1972-10-04 Tenneco Chem Improvements in or relating to the production of benzaldehyde
FR2379500A1 (fr) * 1977-02-02 1978-09-01 Shell Int Research Oxydation de toluenes p-substitues et preparation de benzaldehydes p-substitues
SU789476A1 (ru) * 1978-08-23 1980-12-23 Предприятие П/Я А-7815 Способ получени толуиловых спирта, альдегида, кислоты

Non-Patent Citations (3)

* Cited by examiner, † Cited by third party
Title
CHEMICAL ABSTRACTS, vol. 095, no. 1, 6 July 1981, Columbus, Ohio, US; abstract no. 006834, POKROVSKAYA I E ET AL: "Method of producing toluic alcohol, aldehyde and acid" *
CHEMICAL ABSTRACTS, vol. 104, no. 1, 6 January 1986, Columbus, Ohio, US; abstract no. 005361, HRONEC M ET AL: "The use of phase-transfer catalysis for the initiation of p-xylene oxidation" *
REACT. KINET. CATAL. LETT. (RKCLAU,03044122);85; VOL.27 (2); PP.231-3, SLOVAK TECH. UNIV.;FAC. CHEM.; BRATISLAVA; 812 37; CZECH. (CS) *

Cited By (6)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US5990357A (en) * 1996-03-20 1999-11-23 Rutgers Kureha Solvents Gmbh Process for the oxidation of isoalkylaromatic hydrocarbons, and catalyst for the execution of the process
CN106699526A (zh) * 2016-11-07 2017-05-24 常州大学 一种2,4‑二氯甲苯连续氧化制备2,4‑二氯苯甲醛的方法
CN106699525A (zh) * 2016-11-07 2017-05-24 常州大学 一种2,3‑二氯甲苯连续氧化制备2,3‑二氯苯甲醛的方法
CN106748684A (zh) * 2016-11-07 2017-05-31 常州大学 一种间氟甲苯连续氧化制备间氟苯甲醛的方法
CN106748685A (zh) * 2016-11-07 2017-05-31 常州大学 一种对氯甲苯连续氧化制备对氯苯甲醛的方法
CN106854142A (zh) * 2016-11-07 2017-06-16 常州大学 一种2,5‑二氯甲苯连续氧化制备2,5‑二氯苯甲醛的方法

Also Published As

Publication number Publication date
AU5892694A (en) 1995-08-15
EE9500004A (et) 1995-12-15

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