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WO1993015035A1 - Oxydation amelioree de chaines d'hydrocarbures satures - Google Patents

Oxydation amelioree de chaines d'hydrocarbures satures Download PDF

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Publication number
WO1993015035A1
WO1993015035A1 PCT/EP1993/000186 EP9300186W WO9315035A1 WO 1993015035 A1 WO1993015035 A1 WO 1993015035A1 EP 9300186 W EP9300186 W EP 9300186W WO 9315035 A1 WO9315035 A1 WO 9315035A1
Authority
WO
WIPO (PCT)
Prior art keywords
catalyst
process according
saturated hydrocarbon
carbon atoms
oxidation
Prior art date
Application number
PCT/EP1993/000186
Other languages
English (en)
Inventor
Philip Luc Buskens
Diane Renata Cornelia Huybrechts
Original Assignee
Exxon Chemical Patents Inc.
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 Exxon Chemical Patents Inc. filed Critical Exxon Chemical Patents Inc.
Publication of WO1993015035A1 publication Critical patent/WO1993015035A1/fr

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Classifications

    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C29/00—Preparation of compounds having hydroxy or O-metal groups bound to a carbon atom not belonging to a six-membered aromatic ring
    • C07C29/48—Preparation of compounds having hydroxy or O-metal groups bound to a carbon atom not belonging to a six-membered aromatic ring by oxidation reactions with formation of hydroxy groups
    • 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
    • B01J29/00—Catalysts comprising molecular sieves
    • B01J29/89—Silicates, aluminosilicates or borosilicates of titanium, zirconium or hafnium
    • 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
    • C—CHEMISTRY; METALLURGY
    • C12—BIOCHEMISTRY; BEER; SPIRITS; WINE; VINEGAR; MICROBIOLOGY; ENZYMOLOGY; MUTATION OR GENETIC ENGINEERING
    • C12C—BEER; PREPARATION OF BEER BY FERMENTATION; PREPARATION OF MALT FOR MAKING BEER; PREPARATION OF HOPS FOR MAKING BEER
    • C12C11/00—Fermentation processes for beer
    • C12C11/02—Pitching yeast
    • 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
    • Y02P20/52—Improvements relating to the production of bulk chemicals using catalysts, e.g. selective catalysts

Definitions

  • the present invention relates to the oxidation of saturated hydrocarbon chains and in particular to the use of a certain catalyst system which has been found to enable the selective oxidation of aliphatic compounds and alkyl aromatic compounds.
  • These catalysts are based on crystalline synthetic material comprising silicon and titanium oxides and are characterised by an Infra red absorption band at around 950 cm" 1 . They are typically of the general formula : xTiO 2 (l-x)SiO 2
  • x is from 0.0001 to 0.04.
  • the catalysts are typically prepared from a mixture containing a source of silicon oxide, • a source of titanium oxide, a nitrogenated organic base and water as described in United Kingdom Patent 2071071 which is concerned with the catalysts themselves or by the dealumination of ZSM-5 and reaction with titanium tetrachloride vapour as described by B. Kraushaar and J.H.C. Van Hoof in Catalysis Letters 1 (1988) pages 81-84.
  • the catalysts may contain small amounts of other metals such as aluminium, gallium and iron (as described in European Patent Application 0226258).
  • United States Patent 4854976 relates to the use of these types of catalysts for the epoxidation of defines with H 2 O 2 and in this patent x may be in the range from about 0.0001 to about 0.04.
  • United Kingdom Patents 2083816 and 2116974 relate to the use of similar catalysts for the introduction of hydroxyl groups into aromatic substrates by oxidation with H 2 O 2 . These patents are incorporated herein by reference for their descriptions of the Infra-red and x ray diffraction analyses of the catalysts, as stated the band intensity at approximately 950 c ⁇ r 1 increases as the quantity of titanium present increases.
  • the invention therefore provides the use for the oxidation of saturated organic groups of a titanium containing silicalite catalyst having an infra red absorption band around 950 cm- 1 .
  • the catalyst is of the general formula:
  • These catalysts may be typically prepared by:
  • reaction mixture comprising:
  • the catalyst may be agglomerated to form crystal clusters which are also active and readily recovered after the oxidation reaction.
  • the invention further provides a process for the oxidation of saturated organic groups by the treatment of the compound containing the saturated organic group with an oxidising agent in the presence of a titanium containing silicalite catalyst having an infra red absorption band around 950 cm 1 .
  • the catalyst is of the general formula:
  • the oxidising agent is hydrogen peroxide or an organic peroxide and the compound containing the saturated organic group is liquid or in the dense phase at the conditions used for the reaction. It is also preferred that the reaction is carried out in the presence of a solvent.
  • the catalyst used in this invention is preferably prepared from a reaction mixture consisting of sources of silicon oxide, titanium oxide and possibly an alkaline oxide, a nitrogen containing organic base, possibly an organic solvent, and water, the composition in terms of the molar reagent ratios being as heretofore defined.
  • the silicon oxide source can be tetraalkylorthosilicate, preferably ' tetraethylorthosilicate, or simply a silicate in colloidal form, or again a silicate of an alkaline metal, preferably Na or K.
  • the titanium oxide source is a hydrolysable titanium compound preferably chosen from TiOC-U, TiOCl 2 and Ti(alkoxy) 4 , preferably Ti(OC 4 H 9 ) 4 or Ti(OC 2 H 5 ) .
  • the organic base is a tetraalkylammonium hydroxide, and in particular tetrapropylammonium hydroxide.
  • the organic solvent is preferably an alcohol, in particular isopropanol.
  • the mixture of these reactants is subjected to hydrothermal treatment in an autoclave at a temperature of between 130 and 200°C under its own developed pressure, for a time of 1-30 preferably 6 to 30 days until the crystals of the catalyst precursor are formed. These are separated from the mother solution, carefully washed with water and dried. When in the anhydrous state they have the following composition:
  • the precursor crystals are then heated for between 1 and 72 hours in air at 550°C to eliminate the nitrogenated organic base.
  • the final catalyst has the following composition:
  • the catalyst may also contain alkali metal cations M + where M is sodium or potassium and in this situation it is preferred that the molar ratio of M + :Si0 2 is in the range 0.001 to 0.5.
  • the saturated groups which may be oxidised by the process of this invention include long or short, branched or linear alkanes containing 3 or more, preferably 3 to 18, more preferably 3 to 12 carbon atoms, cyclic alkanes and mono- and poly- alkyl aromatics in which at least one of the alkyl groups contain at least two preferably at least three, more preferably 3 to 18, more preferably 3 to 12 carbon atoms and mono- and poly- alkyl cyclic alkanes.
  • the saturated groups may be oxidised with high selectivity to alcohols and ketones under relatively mild conditions.
  • One particularly useful application is in the oxidation of linear and branched paraffins to secondary alcohols and ketones.
  • the process is especially useful in the lower carbon number range to enable use of low-cost propane and butane feedstock in the manufacture of isopropanol alcohol, acetone, secondary butyl alcohol and methyl ethyl ketone.
  • the aliphatic substituent may be part of a totally aliphatic compound, an aryl compound (alkylaromatic) or an alkylnaphthene compound.
  • said compound may contain other functional groups which have electron-repulsive properties and which, accordingly, are not reactive. The reactivity sequence for the aliphatic compounds slows down from tertiary to secondary and to primary compounds.
  • the oxidising agents used in the reaction may be organic peroxides, ozone or hydrogen peroxide, aqueous hydrogen peroxide being preferred.
  • the aqueous • solution contains from 10-100, preferably 10 to 70 wt% hydrogen peroxide for example diluted hydrogen peroxide (40% by weight in water). It is also preferred that a polar solvent be present for example acetone or methanol, this will increase the solubility of the organic compound in the H 2 O 2 aqueous phase when aqueous hydrogen peroxide is used.
  • the process uses mild temperature and pressure conditions and the conversion and yield are high and by-product formation is small.
  • the conversion of hydrogen peroxide is high.
  • the optimum reaction temperature is between 50 and 150°C, preferably about 100°C.
  • the pressure should be such that all materials are in the liquid or dense phase.
  • the reaction can be carried out at room temperature but higher reaction rates may be involved at higher temperatures, for example under reflux conditions.
  • higher pressure either due to the autogeneous pressure created by the heated reactants or by use of a pressurised reactor still higher temperatures can be reached.
  • Use of higher pressures in the range of 1 to 100 bars (10 5 to 10 7 Pa) can increase the conversion and selectivity of the reaction.
  • the oxidation reaction can be carried out under batch conditions or in a fixed bed, and the use of the heterogeneous catalyst enables a continuous reaction in a monophase or biphase system.
  • the catalyst is stable under the reaction conditions, and can be totally recovered and reused.
  • the process of the present invention is preferably carried out in the presence of a solvent.
  • Choice of solvent is important since it should dissolve the organic phase and the aqueous phase which is generally present due to the use of aqueous hydrogen peroxide as the oxidising agent.
  • Polar compounds are preferred and examples of preferred solvents are alcohols, ketones, ethers, glycols and acids, with a number of carbon atoms which is not too high, preferably less than or equal to 6.
  • Methanol or tertiary butanol is the most preferred of the alcohols, acetone the most preferred of the ketones, and acetic or propionic acid the most preferred acid.
  • the amount of solvent is important and can influence the reaction product and conversion, the choice of solvent and the amount depending on the material to be oxidised.
  • catalyst A The thus obtained catalyst will be referred to as catalyst A.
  • a catalyst used in the prior art is prepared as described in US 4,410,501 (Example 1). This catalyst was also dried and calcined at 550°C in air for 20 hours.
  • catalyst B This comparative catalyst will be referred to as catalyst B.
  • catalysts A and B Chemical analysis was performed on catalysts A and B. It was found that catalyst A contains 1.6 m% Ti while catalyst B contains 6.5 m% Ti. The infra red spectra of the two catalysts is shown in Figure 1. Both catalysts contain an infrared absorption band at ⁇ 950 cm- 1 , but the intensity of the band is higher in catalyst A than in the comparative catalyst B.

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  • Chemical & Material Sciences (AREA)
  • Organic Chemistry (AREA)
  • Engineering & Computer Science (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Life Sciences & Earth Sciences (AREA)
  • Health & Medical Sciences (AREA)
  • General Health & Medical Sciences (AREA)
  • Food Science & Technology (AREA)
  • Microbiology (AREA)
  • Biochemistry (AREA)
  • Bioinformatics & Cheminformatics (AREA)
  • General Engineering & Computer Science (AREA)
  • Mycology (AREA)
  • Genetics & Genomics (AREA)
  • Wood Science & Technology (AREA)
  • Zoology (AREA)
  • Materials Engineering (AREA)
  • Catalysts (AREA)
  • Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)

Abstract

Des chaînes d'hydrocarbures saturés sont oxydées de préférence dans des solutions, au moyen d'un catalyseur aux silicalites de titane ayant une bande d'absorption des infrarouges située autour de 950 cm-1, les chaînes pouvant être des alcanes ou des groupes alkyles de composés cycliques alkyles.
PCT/EP1993/000186 1992-01-29 1993-01-27 Oxydation amelioree de chaines d'hydrocarbures satures WO1993015035A1 (fr)

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
GB929201872A GB9201872D0 (en) 1992-01-29 1992-01-29 Improved oxidation of saturated hydrocarbon chains
GB9201872.0 1992-01-29

Publications (1)

Publication Number Publication Date
WO1993015035A1 true WO1993015035A1 (fr) 1993-08-05

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Family Applications (1)

Application Number Title Priority Date Filing Date
PCT/EP1993/000186 WO1993015035A1 (fr) 1992-01-29 1993-01-27 Oxydation amelioree de chaines d'hydrocarbures satures

Country Status (3)

Country Link
AU (1) AU3494393A (fr)
GB (1) GB9201872D0 (fr)
WO (1) WO1993015035A1 (fr)

Cited By (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO1998051811A1 (fr) * 1997-05-16 1998-11-19 E.I. Du Pont De Nemours And Company Procede d'oxydation selective de composes organiques
AT408546B (de) * 1999-04-13 2001-12-27 Dsm Fine Chem Austria Gmbh Singlet sauerstoff oxidation von organischen substraten
WO2008059182A1 (fr) * 2006-11-16 2008-05-22 Arkema France Procede de fabrication de cetones

Citations (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO1990005126A1 (fr) * 1988-11-08 1990-05-17 Exxon Chemical Patents Inc. Oxydation de chaines d'hydrocarbures satures
EP0412596A1 (fr) * 1989-08-09 1991-02-13 ENIRICERCHE S.p.A. Procédé pour l'oxydation de composés paraffiniques

Patent Citations (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO1990005126A1 (fr) * 1988-11-08 1990-05-17 Exxon Chemical Patents Inc. Oxydation de chaines d'hydrocarbures satures
EP0412596A1 (fr) * 1989-08-09 1991-02-13 ENIRICERCHE S.p.A. Procédé pour l'oxydation de composés paraffiniques

Non-Patent Citations (1)

* Cited by examiner, † Cited by third party
Title
JOURNAL OF CATALYSIS vol. 130, no. 1, July 1991, pages 1 - 8 THANGARAJ ET EL. 'CATALYTIC PROPERTIES OF CRYSTALINE TITANIUM SILICALITES' cited in the application *

Cited By (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO1998051811A1 (fr) * 1997-05-16 1998-11-19 E.I. Du Pont De Nemours And Company Procede d'oxydation selective de composes organiques
AT408546B (de) * 1999-04-13 2001-12-27 Dsm Fine Chem Austria Gmbh Singlet sauerstoff oxidation von organischen substraten
WO2008059182A1 (fr) * 2006-11-16 2008-05-22 Arkema France Procede de fabrication de cetones
FR2908765A1 (fr) * 2006-11-16 2008-05-23 Arkema France Procede de fabrication de cetones.

Also Published As

Publication number Publication date
GB9201872D0 (en) 1992-03-18
AU3494393A (en) 1993-09-01

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