WO1996005162A1 - Procede de preparation d'acides monocarboxyliques aliphatiques inferieurs - Google Patents

Procede de preparation d'acides monocarboxyliques aliphatiques inferieurs Download PDF

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Publication number
WO1996005162A1
WO1996005162A1 PCT/EP1995/003138 EP9503138W WO9605162A1 WO 1996005162 A1 WO1996005162 A1 WO 1996005162A1 EP 9503138 W EP9503138 W EP 9503138W WO 9605162 A1 WO9605162 A1 WO 9605162A1
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WO
WIPO (PCT)
Prior art keywords
process according
catalysts
activators
metals
hydrocarbons
Prior art date
Application number
PCT/EP1995/003138
Other languages
German (de)
English (en)
Inventor
Hans-Joachim Freund
Jörg WAMBACH
Oliver Seiferth
Bernd Dillmann
Original Assignee
Hoechst Aktiengesellschaft
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 DE4428567A external-priority patent/DE4428567A1/de
Priority claimed from DE1995120256 external-priority patent/DE19520256A1/de
Application filed by Hoechst Aktiengesellschaft filed Critical Hoechst Aktiengesellschaft
Priority to AU33431/95A priority Critical patent/AU3343195A/en
Publication of WO1996005162A1 publication Critical patent/WO1996005162A1/fr

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Classifications

    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C51/00—Preparation of carboxylic acids or their salts, halides or anhydrides
    • C07C51/15—Preparation of carboxylic acids or their salts, halides or anhydrides by reaction of organic compounds with carbon dioxide, e.g. Kolbe-Schmitt synthesis

Definitions

  • the invention relates to a process for the preparation of aliphatic monocarboxylic acids having 2 to 5 carbon atoms in the molecule by catalytic conversion of carbon dioxide and saturated or unsaturated hydrocarbons which contain up to 4 carbon atoms in the molecule.
  • Lower aliphatic monocarboxylic acids are among the most important basic organic chemicals and are used extensively in the chemical industry. The majority of these compounds are used to manufacture plastics based on vinyl esters and semi-synthetic fibers, which are derived from cellulose. Substantial amounts are also used as solvents immediately or after esterification with alcohols. Esters of the acids continue to be used as fragrance and aroma substances. Propionic acid is also a proven preservative for
  • the oxidizing agent is air, to which oxygen can be added, possibly also pure oxygen. Another way of working to obtain lower aliphatic monocarboxylic acids is the oxidation of paraffins.
  • the oxidizing agent is air or oxygen-enriched air.
  • the reaction leads to mixtures of normal and branched monocarboxylic acids. The reaction takes place at temperatures of 150 to 200 ° C and pressures between 3 and 8 MPa. The individually applicable pressures and temperatures are determined in particular by the type of paraffin used.
  • the reaction can be carried out with or without catalysts.
  • the industrially used production processes for lower, aliphatic monocarboxylic acids also include carbonylation, i.e. the reaction of olefins or alcohols with carbon monoxide.
  • the reaction proceeds in the presence of acidic catalysts, such as sulfuric acid, phosphoric acid or boron trifluoride. Mixtures of various carboxylic acids in which the branched compounds dominate result from isomerization, build-up and breakdown reactions.
  • the carbonylation of methanol is used especially for the production of acetic acid.
  • the reaction takes place in the presence of catalysts based on cobalt and iodine at pressures of 60 to 80 MPa and temperatures between 200 and 300 ° C. A variant of this method works with
  • Iodine / rhodium catalysts and requires pressures of only 2 to 4 MPa and temperatures up to about 200 ° C.
  • the object was therefore to provide a process which is as selective as possible and which, starting from inexpensive raw materials, leads to aliphatic monocarboxylic acids.
  • the invention consists in a process for the preparation of aliphatic monocarboxylic acids having 2 to 5 carbon atoms in the molecule. It is characterized in that carbon dioxide and saturated or unsaturated Hydrocarbons with 1 to 4 carbon atoms in the molecule at temperatures from 100 to 600 ° C and pressures from 0.1 to 20 MPa in the presence of catalysts which contain one or more metals from groups VIA, VIIA or VIIIA des
  • Carbon dioxide has rarely been described as the starting material for the production of carboxylic acids.
  • the implementation of Grignard compound with carbon dioxide is known, but only used as a laboratory method.
  • the reaction of carbon dioxide with hydrogen in the presence of catalysts has recently been investigated especially for the production of acetic acid.
  • the reaction of carbon dioxide with methane under the influence of silent electrical discharges results in a mixture of different oxygen-containing organic compounds, including acetic acid.
  • such a reaction path is not suitable for technical use.
  • the new process enables low-molecular, aliphatic monocarboxylic acids to be obtained under conditions that are common in the technical implementation of chemical syntheses.
  • the raw materials are available in large quantities, carbon dioxide as a by-product of technical processes, lower, saturated or unsaturated hydrocarbons, e.g. in the form of natural gas or as a by-product of oil processing in refineries.
  • Carbon dioxide is used in the commercial form with a content of at least 99.7%, preferably at least 99.9% CO 2 . It essentially contains the constituents of the air, namely nitrogen, oxygen and argon. A prior cleaning is therefore not necessary.
  • Reactants of the carbon dioxide are saturated or unsaturated hydrocarbons with 1 to 4 carbon atoms in the molecule. Examples are methane, ethane, propane and butane, furthermore ethylene, propene and butene, butane and butene also in the form of the structural isomers.
  • the hydrocarbons are used as uniform compounds or as a mixture, for example isomeric or saturated and unsaturated compounds of the same number of carbon atoms as raffinate II, in a purity of at least 99.5%, based on the hydrocarbon or hydrocarbon mixture. If appropriate, catalyst poisons, in particular sulfur compounds, must be removed beforehand by known processes.
  • the starting materials can be reacted in a molar ratio of 1: 1, but the excess of one of the reaction components does not interfere. Molar ratios of 1: 1.1 to 1: 1.5 are preferred.
  • catalytically active metals are used as catalysts in elemental form or as compounds. Chromium, rhenium, iron, nickel, rhodium, ruthenium and palladium are preferred among the metals mentioned, and chromium, nickel and rhodium are particularly suitable.
  • the catalytically active metals or metal compounds are used alone or as a mixture consisting of two or more metals or metal compounds.
  • the catalysts also contain carriers.
  • Aluminum oxide such as ⁇ - or ⁇ -Al 2 O 3
  • hydroxides of aluminum such as boehmite, silicon dioxide and hydrates of silicon dioxide in their various forms, such as precipitated silica or diatomaceous earth, are suitable.
  • Aluminum silicates and zirconium dioxide are preferred as a carrier.
  • the performance of the catalysts is improved in many cases by adding activators.
  • Alkali, alkaline earth and lanthanum compounds in particular the hydroxides and oxides of lithium, sodium, potassium, magnesium and calcium and lanthanum oxide, are successfully used.
  • the composition of the catalysts can be varied over a wide range with regard to the type and proportion of the components.
  • Catalysts which contain, based on the catalyst mass, 3 to 20% by weight of active metals and 80 to 95% by weight of carriers have proven successful.
  • the proportion of activators, based on the catalyst mass, is likewise 1 to 10% by weight.
  • the catalysts preferably contain 5 to 12% by weight of active metals, 85 to 90% by weight of carrier material and 2 to 3% by weight of activators.
  • the heterogeneous catalysts used according to the invention are produced by the processes known for this class of substances, in particular by precipitating the components or by impregnating carriers.
  • Precipitation catalysts are obtained by separating the components, which may also include precursors of the support material, from their solutions with suitable precipitation reagents, such as alkaline compounds, for example the alkali metal carbonates or the hydroxides of the alkali and alkaline earth metals.
  • suitable precipitation reagents such as alkaline compounds, for example the alkali metal carbonates or the hydroxides of the alkali and alkaline earth metals.
  • the carrier substance instead of precipitating the carrier substance together with the other catalyst components, it can also be suspended as an insoluble solid in the solution of the metal compounds and the dissolved components can be precipitated in their presence.
  • the catalyst precursor is separated from the solvent or suspension medium, dries, shaped and activated.
  • Impregnation processes are particularly suitable for the production of catalysts for the new process which, compared to the proportion of the support material, contain only minor amounts of the active metals.
  • the usual procedure is to soak the carrier material with a solution of the active metal or metals.
  • the treatment of the carrier can be carried out in one stage or in several stages. If the metal salt solutions act on the support in several stages, solutions of different concentrations and / or solutions of different compositions can be used in the individual stages, that is to say, for example, for the preparation of catalysts which contain several active metals and which apply components to the support one after the other. Additional reaction steps can be provided between the individual impregnation stages, for example the active metals can be individually fixed on the support.
  • the catalyst Before the reactants are converted, the catalyst must be converted into the active form. For this purpose, it is treated at temperatures from 200 ° C. to 600 ° C. with hydrogen or with a gas mixture containing hydrogen and also inert substances.
  • the catalytic conversion of hydrocarbons and carbon dioxide is carried out in reactors of conventional design in the temperature range of 100 to 600 0 C, preferably at temperatures between 150 to 300 0 C.
  • the pressures are between 0.1 and 20 MPa, the pressure range of 0 is preferred , 1 to 5 MPa.

Landscapes

  • Chemical & Material Sciences (AREA)
  • Organic Chemistry (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Engineering & Computer Science (AREA)
  • Oil, Petroleum & Natural Gas (AREA)
  • Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)

Abstract

Pour obtenir des acides monocarboxyliques aliphatiques ayant entre 2 et 5 atomes de carbone dans la molécule, on fait réagir des hydrocarbures saturés ou insaturés ayant entre 1 et 4 atomes de carbone dans la molécule avec de l'oxyde de carbone à des températures comprises entre 100 et 600 °C et à des pressions comprises entre 0,1 et 20 Mpa, en présence de catalyseurs qui contiennent un métal ou plusieurs métaux appartenant au groupe VIA, VIIA et VIIIA de la classification périodique des éléments.
PCT/EP1995/003138 1994-08-12 1995-08-08 Procede de preparation d'acides monocarboxyliques aliphatiques inferieurs WO1996005162A1 (fr)

Priority Applications (1)

Application Number Priority Date Filing Date Title
AU33431/95A AU3343195A (en) 1994-08-12 1995-08-08 Method of manufacturing lower aliphatic monocarboxylic acids

Applications Claiming Priority (4)

Application Number Priority Date Filing Date Title
DEP4428567.1 1994-08-12
DE4428567A DE4428567A1 (de) 1994-08-12 1994-08-12 Verfahren zur Herstellung von niederen, aliphatischen Monocarbonsäuren
DE19520256.2 1995-06-02
DE1995120256 DE19520256A1 (de) 1995-06-02 1995-06-02 Verfahren zur Herstellung von niederen, aliphatischen Monocarbonsäuren

Publications (1)

Publication Number Publication Date
WO1996005162A1 true WO1996005162A1 (fr) 1996-02-22

Family

ID=25939147

Family Applications (1)

Application Number Title Priority Date Filing Date
PCT/EP1995/003138 WO1996005162A1 (fr) 1994-08-12 1995-08-08 Procede de preparation d'acides monocarboxyliques aliphatiques inferieurs

Country Status (2)

Country Link
AU (1) AU3343195A (fr)
WO (1) WO1996005162A1 (fr)

Citations (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
FR768584A (fr) * 1933-03-23 1934-08-08 Procédé de fabrication des acides aliphatiques
US4016185A (en) * 1975-12-11 1977-04-05 Chevron Research Company Production of carboxylic acids from paraffins and carbon dioxide

Patent Citations (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
FR768584A (fr) * 1933-03-23 1934-08-08 Procédé de fabrication des acides aliphatiques
US4016185A (en) * 1975-12-11 1977-04-05 Chevron Research Company Production of carboxylic acids from paraffins and carbon dioxide

Non-Patent Citations (2)

* Cited by examiner, † Cited by third party
Title
CHEMICAL ABSTRACTS, vol. 90, no. 13, 26 March 1979, Columbus, Ohio, US; abstract no. 103345d, LAPIDUS,A. ET AL.: "CATALYTIC SYNTHESIS OF PROPIONIC ACID BY THE CARBOXYLATION OF ETHYLENE BY CARBON DIOXIDE." page 540; column 1; *
LAPIDUS,A. ET AL., IZV.AKAD.NAUK SSSR,SER.KHIM., no. 12, 1978, MOSCOW, pages 2814 - 2816 *

Also Published As

Publication number Publication date
AU3343195A (en) 1996-03-07

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