Organic compounds -- part of the class 532-570 series – Organic compounds – Oxygen containing
Reexamination Certificate
1999-11-15
2001-03-20
Richter, Johann (Department: 1621)
Organic compounds -- part of the class 532-570 series
Organic compounds
Oxygen containing
C568S864000, C568S875000, C568S885000
Reexamination Certificate
active
06204417
ABSTRACT:
The present invention relates to a process for preparing aliphatic alcohols by hydrogenating aliphatic carboxylic acids or anhydrides or esters thereof or lactones in the presence of a catalyst.
Various processes for hydrogenating aliphatic carboxylic acids to give aliphatic alcohols are known.
The hydrogenation of hexanoic acid and decanoic acid to give the corresponding alcohols in the presence of a catalyst comprising Re
2
O
7
and OsO
4
on a carbon support is described in K. Yoshino et al., “Hydrogenation of carboxylic acids by rhenium-osmium bimetallic catalyst”, JAOCS 67 (1990), 21-24.
DE-A-27 15 667 describes a process for preparing 1,4-butanediol by hydrogenating maleic anhydride, maleic acid or fumaric acid using Pd and Re on a specific silicoacetate as catalyst. The reaction temperature is from 205 to 230° C.
EP-B-0 417 867 describes catalysts for hydrogenating carboxylic acids and anhydrides thereof to give alcohols or esters. The catalysts used include, for example, Pd, Pd/Re, Ag/Pd, Ag/Pd/Re on carbon. The conversions of acetic acid into ethanol and of maleic anhydride into gamma-butyrolactone are described. The reaction is carried out at from 194 to 251° C.
U.S. Pat. No. 4,214,106 describes a process for preparing ethylene glycol starting from glycolic acid. The reaction is carried out over Pd/Re, Pd/Ag, Ru/Rh, Pd/Au, Re/Ag, Pt/Rh or Pd/Re/Ag catalysts at from 145 to 241° C.
The known catalysts have insufficient activities or selectivities in some applications.
Furthermore, the use of carboxylic acids, in particular in the form of aqueous solutions, entails the risk of corrosion of the materials of construction of the equipment contacting the carboxylic acids, for example reaction vessels. For this reason, either very thick steels or noble and thus costly materials have to be used for the equipment. Accordingly, there is a need for a process in which the problem of corrosion is significantly reduced.
It is an object of the present invention to provide a process for preparing aliphatic alcohols by hydrogenating aliphatic carboxylic acids or anhydrides or esters thereof or lactones in the presence of a catalyst comprising Pt and Re, in the form of the metal or an oxide in each case, without the disadvantages of existing processes.
We have found that this object is achieved by using a catalyst comprising Pt and Re, in the form of the metal or an oxide in each case, and at least one further element from groups 5 to 12 and 14 and the lanthanides of the Periodic Table of the Elements in the form of the metal or an oxide.
The present invention further provides such a catalyst and its use for hydrogenating aliphatic carboxylic acids or anhydrides and esters thereof or lactones.
The inventors have found that, using the catalyst of the invention, the abovementioned reaction may be carried out at low temperatures, preferably of at most 200° C., which leads to a very strong reduction in the problem of corrosion in the equipment.
The catalyst of the invention comprises or, in particular, consists of Pt, Re and at least one further element from groups 5 to 12 and 14 and the lanthanides of the Periodic Table of the Elements (IVth main group, Ist, IInd, Vth, VIth, VIIth, VIIIth transition group of the Periodic Table of the Elements), in the form of the metal or an oxide in each case, optionally on a support.
The present invention further provides a catalyst obtainable by reducing an aqueous suspension and/or solution of oxides, oxide hydrates, carbonates, nitrates, carboxylates, chelates, sulfates, phosphates and/or halides of Pt, Re and at least one further element from groups 5 to 12 and 14 and the lanthanides of the Periodic Table of the Elements.
The at least one further element is preferably selected from groups 6, 10 and 11 of the Periodic Table of the Elements. It is used in the form of the metal or an oxide. Particular preference is given to the elements Sn, V, Cr, Mo, W, Mn, Fe, Ru, Os, Co, Ni, Pd, Cu, Ag, Au, Zn, La and Ce. Especially preferred are Mo, Ag, Au and/or Pd in the form of the metal or an oxide. In one embodiment of the invention, the catalyst includes only one further element in the form of the metal or an oxide.
The catalyst may be employed as unsupported or supported catalyst. For use as supported catalyst, all suitable support materials may be employed, for example active carbons, SiO
2
, Al
2
O
3
, TiO
2
, ZrO
2
, clays such as montmorillonites, zeolites or mixtures thereof. The catalyst can be prepared in various ways. The catalyst is obtainable, for example, by reducing an aqueous suspension and/or solution of oxides, oxide hydrates, carbonates, nitrates, carboxylates, chelates, in particular with 1,3-diketo compounds, sulfates, phosphates and/or halides of Pt, Re and at least one further element from the groups 5 to 12 and 14 and the lanthanides of the Periodic Table of the Elements. The catalysts can be prepared by initially charging all of the components and reducing the initial charge, preferably with hydrogen. However, the reduction can also be carried out sequentially. In this case, the activation or reduction of the catalyst or catalyst precursors is preferably carried out at from 200 to 500° C., particularly preferably at from 210 to 400° C., in particular at from 220 to 300° C. Following the reduction, the catalysts are often not present, or are present only to a minor extent, in the form of intermetallic compounds.
For example, PtO
2
, an Re compound such as Re
2
O
7
and at least one additional compound of the third component are introduced into water and reduced with hydrogen. The catalyst obtained in this way can be directly employed for the hydrogenation. Supported catalysts can be prepared, for example, in such a way that platinum oxide or platinum oxide hydrate are already present on the support, it being possible to prepare the Pt/support mixture by impregnation or coprecipitation of platinum oxide precursor or platinum oxide hydrate precursor and support material and subsequent calcination. The Re compounds and the further component can also be added by impregnation or precipitation. It is possible, for example, for the platinum oxide or platinum oxide hydrate to have been reduced on the support previously.
The ratio by weight of Pt to Re or of Pt to the at least one further element is preferably 100-0.01, particularly preferably 50-0.05, in particular 10-0.1.
Pt is preferably employed in oxide or oxide hydrate form before reduction or activation. The Pt component is preferably present in the form of PtO
2
. Re sources that can be used are customary Re compounds; Re
2
O
7
is preferably used.
The catalysts may be prepared in the form of powders or shaped bodies such as extrudates, tablets, pellets, or as a fixed bed.
In principle, all aliphatic carboxylic acids or anhydrides or esters thereof or lactones can be hydrogenated in the process of the invention to give aliphatic alcohols.
The aliphatic carboxylic acid preferably contains at least 3 carbon atoms, particularly preferably at least 4 carbon atoms. The number of carbon atoms refers to the individual acid and includes the carboxyl groups. Derivatives of the carboxylic acid have correspondingly more carbon atoms.
In one embodiment, the carboxylic acid does not contain any OH groups adjacent to the carboxyl groups or any hydroxyl groups at all.
The number of carboxyl groups in the carboxylic acid is not critical. Mono-, di-, tri- or tetracarboxylic acids are usually employed, particularly preferably mono- or dicarboxylic acids.
The number of carbon atoms in the carboxylic acid is also uncritical. The carboxylic acid contains preferably from 3 to 30, in particular from 4 to 20, especially from 4 to 10, carbon atoms. The aliphatic moiety may be linear or branched. It may contain one or more double and/or triple bonds in its skeleton.
Customary anhydrides or esters can be employed in the process of the invention instead of the free carboxylic acid.
Examples of suitable carboxylic acids are monocarboxylic acids such as propionic acid, butyric acid, pentanoic acid, hexanoic acid, pen
Fischer Rolf
Pinkos Rolf
Wulff-Doring Joachim
BASF - Aktiengesellschaft
Davis Brian J.
Keil & Weinkauf
Richter Johann
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