Preparation of rhodium(III)-2-ethylhexanoate

Patent metadata

Field	Value
Publication number	US-11225498-B2
Application number	US-201916690833-A
Country	US
Kind code	B2
Filing date	Nov 21, 2019
Priority date	Jul 2, 2015
Publication date	Jan 18, 2022
Grant date	Jan 18, 2022

Abstract

The present invention provides a method for preparing rhodium (III) 2-ethylhexanoate solutions which supplies the reaction product with higher space yield, as well as lower sodium and chloride ion content. An aqueous solution of an alkali salt of 2-ethylhexanoate is thereby initially converted with a rhodium (III) precursor. The rhodium (III) precursor is selected from rhodium (III) chloride solution, rhodium (III) chloride hydrate, and rhodium (III) nitrate. The mixture is heated for several hours. After cooling to room temperature, the rhodium (III) 2-ethylhexanoate formed is extracted from the aqueous solution with an alcohol that is immiscible in water or a carboxylic acid that is immiscible in water, and optionally washed with aqueous mineral acid. The rhodium (III) 2-ethylhexanoate solution obtainable in this way may be used directly as catalyst in hydroformylation reactions.

First claim

The invention claimed is:

1. Rhodium (III) 2-ethylhexanoate, obtained by a method comprising the steps
a) preparing an aqueous solution of an alkali salt of 2-ethylhexanoate by adding 2-ethylhexanoic acid to an aqueous alkali hydroxide solution at room temperature in a first reaction vessel, wherein the molar ratio of 2-ethylhexanoic acid to alkali hydroxide is 1.0:1.0 to 1.1:1.0 (mol/mol);
b) providing a rhodium (III) precursor selected from rhodium (III) chloride hydrate, rhodium (III) chloride aqueous solution, and rhodium (III) nitrate aqueous solution, as well as mixtures thereof, in a second reaction vessel;
c) mixing the aqueous solution of the alkali salt of 2-ethylhexanoate and the aqueous solution of the rhodium (III) precursor at an internal temperature of the reaction vessel of 20-30° C. to obtain a mixture;
d) heating of the mixture from step c)
to an internal temperature of the reaction vessel of 80-90° C., if the Rh(III) precursor is Rh(III) chloride aqueous solution or Rh(III) chloride hydrate, or
to an internal temperature of 80-100° C. if the Rh(III) precursor is Rh(III) nitrate aqueous solution,
to obtain a suspension;
e) cooling of the suspension from step d) while stirring
to an internal temperature of 40-50° C., if the Rh(III) precursor is Rh(III) chloride aqueous solution or Rh(III) chloride hydrate, or
to an internal temperature of 55-65° C., if the Rh(III) precursor is Rh(III) nitrate aqueous solution,
f) adding an alcohol that is immiscible with water, a carboxylic acid that is immiscible with water, or a mixture thereof, while stirring,
g) stirring for 30 minutes to 3 hours,
h) cooling to room temperature and leaving the resulting emulsion to settle,
i) draining off the bottom, aqueous phase, and

washing the top, product-containing organic phase with aqueous mineral acid, if the Rh(III) precursor in the step contains rhodium (III) chloride hydrate and/or rhodium (III) chloride aqueous solution, wherein the rhodium (III) 2-ethylhexanoate is free of rhodium (II) ethylhexanoate, which means that the UV/VIS spectroscopic measurement of a solution with a rhodium content of 1.9-2.1 wt % in 2 mm QS cuvettes at 597 nm exhibits an absorption band of an intensity less than of equal to 0.350.

2. The rhodium (III) 2-ethylhexanoate according to claim 1 , wherein the mixing of the aqueous solution of the alkali salt of 2-ethylhexanoate and the aqueous solution of the rhodium (III) precursors in accordance with step c) takes place discontinuously, wherein the solution of the rhodium (III) precursor is introduced first, and then the aqueous solution of the alkali salt of sodium 2-ethylhexanoate is added.

3. The rhodium (III) 2-ethylhexanoate according to claim 1 , wherein the alkali hydroxide in step a) is NaOH.

4. The rhodium (III) 2-ethylhexanoate according to claim 1 , wherein, in step f), the alcohol or the carboxylic acid is selected from 2-ethylhexanol, 2-ethylhexanoic acid, and texanol.

5. The rhodium (III) 2-ethylhexanoate according to claim 1 , wherein the aqueous mineral acid is sulfuric acid, nitric acid, or phosphoric acid.

6. A catalyst which comprises the rhodium (III) 2-ethylhexanoate according to claim 1 .

7. A method for a hydroformylation reaction comprising the steps of
providing rhodium (III) 2-ethylhexanoate according to claim 1 or a solution thereof; and
catalyzing the hydroformylation reaction with the the rhodium (III) 2-ethylhexanoate or its solution.

Assignees

• Umicore Ag & Co Kg

Inventors

• Doppiu Angelino
• Emrich Birgit
• Karch Ralf
• Rivas-Nass Andreas
• Woerner Eileen

Classifications

• C07C51/412 Primary

  by conversion of the acids, their salts, esters or anhydrides with the same carboxylic acid part · CPC title

• C07C53/128

  the carboxylic group being bound to a carbon atom bound to at least two other carbon atoms, e.g. neo-acids · CPC title

• B01J31/04

  containing carboxylic acids or their salts {(B01J31/0277 - B01J31/0298 take precedence; multi-metal carboxylate complexes like Pd (II) acetate, i.e. Pd3 (OAc) 6 or Cr(II)acetate, i.e. Cr2(OAc)4 B01J31/2226)} · CPC title

• C07F15/008 Primary

  without a metal-carbon linkage · CPC title

• C07C45/50 Primary

  by oxo-reactions · CPC title