Purifying organophosphorus compounds contaminated with chlorine

Patent metadata

Field	Value
Publication number	US-9676805-B2
Application number	US-201515109745-A
Country	US
Kind code	B2
Filing date	Jan 16, 2015
Priority date	Jan 31, 2014
Publication date	Jun 13, 2017
Grant date	Jun 13, 2017

Abstract

The invention relates to a process for the purification of a contaminated organophosphorus product which comprises at least one organophosphorus compound and, as contaminant, at least one chlorine compound. It is based on the object of indicating a purification method in which the chlorine content of an organophosphorus product which comprises at least one organophosphorus compound and at least one chlorine compound as contaminant, can be reduced from originally 1000 to 100 000 ppm to a total chlorine content between 10 ppm and 10 000 ppm. This is achieved by a process with the steps:
a) provision of the contaminated organophosphorus product; b) complete dissolution of the contaminated organophosphorus product in a solvent to give a contaminated solution; c) separation of the contaminated solution by means of a filter and/or by means of a membrane separation unit to give a purified solution; d) removal of the solvent from the purified solution to give a purified organophosphorus product.

First claim

The invention claimed is:

1. A process for the purification of a contaminated organophosphorus product which comprises at least one organophosphorus compound and, as contaminant, at least one chlorine compound, having the following steps:
a) providing the contaminated organophosphorus product;
b) completing dissolution of the contaminated organophosphorus product in a solvent to give a contaminated solution;
c) separating the contaminated solution by means of a filter and/or by means of a membrane separation unit to give a purified solution;
d) removing the solvent from the purified solution to give a purified organophosphorus product.

2. The process according to claim 1 , in which the steps
a) providing the contaminated organophosphorus product; and
b) completing dissolution of the contaminated organophosphorus product in a solvent to give a contaminated solution;
take place in one operation by providing the contaminated organophosphorus product completely dissolved in the contaminated solution.

3. The process according to claim 1 , wherein the total chlorine content of the purified solution is less than that of the total chlorine content of the contaminated solution.

4. The process according to claim 3 , wherein the total chlorine content of the contaminated organophosphorus product is between 1000 ppm and 100,000 ppm, and that the total chlorine content of the purified organophosphorus product is between 10 ppm and 10,000 ppm where the unit ppm refers to the weight.

5. The process according to claim 1 , wherein the contaminated organophosphorus product comprises at least one chlorine compound selected from the following group:
organic chlorides comprising at least one carbon atom;
inorganic chlorides without carbon atom;
where particularly preferably at least one of the following chlorine compounds is present:
phosphorus trichloride, chlorophosphites, dichlorophosphites, hydrochlorides of amines, hydrochlorides of alkali metals, chlorides of alkaline earth metals, chlorine-containing acids obtainable from the hydrolysis of phosphorus trichloride.

6. The process according to claim 1 , wherein the solvent used is a substance selected from the following group, or that a mixture of several substances from this group is used as solvent:
aromatic hydrocarbons such as in particular toluene, xylene, o-xylene, cresol;
ethers, such as in particular tetrahydrofuran (THF), petroleum ether, diethyl ether, methyl tert-butyl ether (MTBE);
nitriles such as in particular acetonitrile (ACN);
ethyl acetate;
acetone;
alcohols such as in particular methanol, ethanol, isopropanol, butanol.

7. The process according to claim 6 , wherein the contaminated solution forms a single organic phase, in particular, that alongside the organic phase, no aqueous phase is formed.

8. The process according to claim 1 , wherein the complete dissolution of the contaminated organophosphorus product in the solvent takes place at a temperature above 20° C. and below the boiling temperature of the selected solvent.

9. The process according to claim 1 , wherein the separation of the contaminated solution takes place by means of a filter, and that the purified solution is produced on the filter as filtrate with, if necessary, the separation of the contaminated solution being carried out in the presence of at least one filtration auxiliary, which has been added beforehand to the contaminated solution or the solvent.

10. The process according to claim 1 , wherein the separation of the contaminated solution takes place by means of a membrane separation unit, and that the purified solution is produced as retentate of the membrane separation unit.

11. The Process according to claim 10 , wherein the membrane separation unit has at least one membrane whose separation-active material is selected from the following membrane materials:
silicone-based polymers
polyethersulfone
polyimide.

12. The process according to claim 10 , wherein the separation of the contaminated solution takes place by means of the membrane separation unit at a temperature which deviates from the temperature during complete dissolution of the contaminated organophosphorus product in the solvent, in particular that the separation of the contaminated solution takes place by means of the membrane separation unit at a temperature of from 10° C. to 80° C.

13. The process according to claim 1 , wherein the organophosphorus product comprises at least one organophosphorus compound selected from the following group:
phosphines;
diphosphines;
phosphonites;
phosphinites;
preferably phosphoramidites;
preferably monophosphites;
particularly preferably bisphosphites, in particular one or more bisphosphites of the structural formulae (I) to (IV):

14. The process for producing a catalyst system comprising a metal and at least one organophosphorus compound as ligand, wherein during the production of the catalyst system a purified organophosphorus product is used which has been obtained according to claim 13 .

15. The process for the hydroformylation or for the hydrocyanation or for the hydrogenation of unsaturated compounds in the presence of a homogeneous catalyst system which has a metal and at least one organophosphorus compound as ligand, wherein the catalyst system has been produced according to claim 14 .

Assignees

• Evonik Degussa Gmbh

Inventors

• Dyballa Katrin Marie
• Franke Robert
• Fridag Dirk
• Priske Markus

Classifications

• C07C5/02

  by hydrogenation (simultaneous hydrogenation and dehydrogenation C07C5/52) · CPC title

• B01J2231/321

  Hydroformylation, metalformylation, carbonylation or hydroaminomethylation · CPC title

• C07C253/00

  Preparation of carboxylic acid nitriles (of cyanogen or compounds thereof C01C3/00) · CPC title

• C07F9/65746 Primary

  the molecule containing more than one cyclic phosphorus atom · CPC title

• B01J2231/645

  of C=C or C-C triple bonds · CPC title